> 6743
Summary Report of Research Conducted on the Lower Fox River
by Staff of the Environmental Research Laboratory-Dul uth,
and by Personnel on Cooperative Agreements.
- 7
J/Tit: '
Kenneth E. Biesinger
U.S. Environmental Protection Agency
Environmental Research Laboratory-Duluth
6201 Congdon Boulevard
Duluth, MN 55804
-------
Introduction
The Lower Fox River, located in northeastern Wisconsin, is a
major tributary to Green Bay in Lake Michigan. It is ~ 64 km long
p
from Lake Winnebago to Green Bay, drains an area of 40,000 km , and
is one of the most heavily industrialized rivers in the country.
There are 15 pulp and/or paper mills, 8 municipal waste water
treatment plants and one electrical generating station (Toxic
Substances Task Force, 1983) on the river. The Fox River has had a
long history of organic pollution dating from soon after the turn of
the century when the pulp and paper industry started; this resulted
in the construction of dams for power, locks, and navigational
channels. The disposal of industrial and municipal wastes resulted
in increased biological demand (BOD) and fish die-offs as early as
1924 (Patterson 1980). Conditions began to improve as industries
installed secondary treatment in the early 1970's, prompted in part
by the Federal Water Pollution Control Act Amendment of 1972. A
continued effort by industries and various local and government
control agencies has resulted in great improvement in water quality.
However, problems remain particularly with xenobiotic compounds of
which 105 organic compounds have been identified f r ejm biota, water,
sediment and effluent discharges (Wiscons in*Department of Natural
Resources 1978). Many of these organic compounds are known or
suspected carcinogens and are of direct concern to man; however,
their effect on the aquatic biota is largely unknown.
-------
Results
An annotated bibliography of 75 papers compiled by Lozano (1985)
was used to identify potentially hazardous toxicants on the Lower Fox
River (see Appendix A). This was intended to be used to apply
existing fate and transport models as well as to develop new models
to assist regulatory decision makers in planning mitigation
strategies. However, studies concurrently being conducted did not
show general patterns of toxicity and so the modeling was not
developed.
Lozano (1985) summarized some of the literature and stated that
dissolved oxygen levels responded well to clean-up measures although
summer oxygen levels in some sections of the river drop below 2 mg/1
and occasionally to < 1 mg/1. The benthic fauna has not yet
recovered in many sections of the river and is characterized by fauna
which tolerate high organic sediment levels and low dissolved oxygen.
Chemical compounds which might have an effect, as reported by
Sullivan and Delfino (1982), include: chloroform, trichloroethane,
abietic acid, isopimaric acid, linoleic acid, linolenic acid, Bis
(2-ethyIhexyl-phthalate), and arsenic, cadmium, chromium, copper,
cyanide, lead, nickel, mercury and zinc. Effluent concentrations of
PCBs in effluents of 0.1-56 jug/1 were reported; the average water
concentration in 1982 was 0.097, although levels of 0.85 Mg/1 were
detected near pulp and paper mills. Sediment levels are usually
between 0.05-61 ng/\ dry weight as reported from the literature by
Lozano (1985).
Effluent, Instream and Sediment Toxicity
To test for possible toxicity of efluents, water quality instream
and sediments, a series of bioassays was made in 1983 and again in
-------
1985. Industrial and municipal effluents discharging into the Lower
Fox River were tested in 1983 (Anon, 1983) for toxicity using seven
day ceriodaphnid (Ceriodaphnia dubia), and seven day fathead minnow
(Pimephales promelas) tests. Effluent samples were collected
continuously over a twenty-four hour period, whereas dilution water
was collected each day as a grab sample immediately upstream of the
discharge. Solutions for both species were changed daily. A map
showing the location of the discharges is given in Appendix B-l and a
summary of the test results is given in Appendix B-2. Toxic dilution
water from just above the effluents was frequently found. In 12 of
the 18 effluent tests the dilution water was either toxic, or
suspected of being toxic, to one of the test organisms. However,
both species did not show marked toxicity on the same sample. Many
of the effluents mitigated the toxicity of the ambient water. In
general, effluents which were successfully tested showed low
toxicity; ambient toxicity could not be attributed to any one
eff1uent.
The water from ten instream (ambient) stations (see Appendix B-l)
was tested with ceriodaphnids and fathead minnows in March and April
1983 (Anon 1983). There were no adverse effects except at one
station on 4/29/83. Some stimulation of growth and reproduction
occurred at all stations on 3/24/83. Water and sediment grab samples
were collected from the Lower Fox River in January, March and April,
1985 from instream areas not located near effluents (see Appendix
B-3). Laboratory bioassays were conducted on river water, elutriate
water from the sediment, and in water with sediment added to evaluate
their potential toxicity (Lien et al. 1986). Daphnid (Daphnia magna)
acute tests, fathead minnow seven day survival and growth tests, and
5
-------
ceriodaphnid survival and reproduction tests were conducted on river
water from the various stations. There were no significant adverse
effects on survival of these organisms during the test periods.
However, growth of fathead minnows was significantly less at Station
D collected in January. Water collected in March significantly
reduced ceriodaphnid reproduction at most stations when compared to
reference stations although the reduction was not considered
biologically important (e.g., a reduction of young from about 28 to
about 22 in seven days). The general water chemistry results for
those tests are given in Appendix B-4.
Acute (2-day) and chronic (10-day) daphnid bioassays were run on
elutriate water. Daphnids in two of three replicates at station K in
April died in the chronic test, but since the third replicate had
100% survival and good young production, something other than a
toxicant effect was suspected. Waters from Station G in March and K
in April produced significantly fewer young than the reference
stat i on.
Ten day daphnid and Hva1e1 la bioassays were conducted in Fox
River water over sediments (solid phase test) from the same
stations. Survival and reproduction of daphnids was often less for
the reference stations than for the other stations. Water in the
solid phase test was not toxic to daphnids nor to Hva1e11 a azteca.
Sediment samples were collected as grab samples using an Ekman
dredge. The hard rocky bottoms at Stations H and M prevented
sampling at these locations. The depth of the river where samples
were obtained varied from 0.9 to 7.6 m (see Lien et al. 1986).
Concentrations of polychlorinated dibenzo-p-dioxins,
polychlorinated dibenzofurans and tetrachlorobiphenyls in these
6
-------
sediments are given in Table 1. Locations of the sampling stations
are given in Appendix B-3. Stations D and J tended to have the
highest concentration of tetrachlorobiphenyls. The methods of
measuring these compounds and the quality control are given in a
report by Gross (1986) .
Walleye Ova and Larval Survival and Growth
Contaminant effects on walleye reproduction were investigated by
collecting walleye from two areas known to have high concentrations
of organic pollutants and one area considered to be relatively clean.
Walleye brood stocks were collected from below the DePere Dam on the
Fox River and Sturgeon Bay on Green Bay, Wisconsin; a control stock
was collected from the Chippewa Flowage in Wisconsin. Walleye eggs
were stripped and fertilized and shipped to the Environmental
Research Laboratory-Duluth for incubation in Lake Superior water
(Hokanson and Lien, 1986). Ova fertility was determined and the
number of normal, deformed and dead yolk-sac larvae were counted at
the time of hatch. Larval walleye were fed and reared under optimum
conditions for three weeks; measurements included survival, total
length and dry weights at specific time intervals (first feeding,
resorption of the oil globule, commencement of the juvenile phase),
and at the termination of the study.
Larval survival at the post-larval I phase of development
(Appendix B-5) was significantly higher from the Chippewa Flowage
stock (90.8%), than from the Fox River (73.3%) and Sturgeon Bay
(58.9%) stocks. Walleye survival was highest in the pro-larval and
juvenile phases of development and lowest for the post-larval I
phase. The latter period of development is one of the most critical
stages when contaminant-induced mortality is expected to be the
7
-------
highest. Additional evidence of a contaminant problem was evident
from the relationship between biological effects and the size of the
females. Post-larval I developmental phase survival was negatively
correlated with adult female weight.
Overall larval survival was lowest from the Sturgeon Bay stock
and highest in the control stock from the Chippewa Flowage, although
there was no significant difference.
Embryo survival to hatch varied from 32.9% for the Lower Fox
River to 72.6% for Sturgeon Bay to 85.7% for the Chippewa Flowage
stock. The Lower Fox River stock had significantly lower embryo
survival than the other two stocks which reportedly was due primarily
to differences in the fertility of the ova. Fertility of ova was
46.5%, 79.1% and 88.6% for stocks from the Lower Fox River, Sturgeon
Bay and Chippewa Flowage respectively.
The walleye adults and ova used for the study in 1985 were
analyzed for dioxins, furans and biphenyls. Concentrations in whole
fish and ova are given in Table 2. (See report by Gross,. 1986, for
analytical methods and quality control.) Concentrations of dioxins
were generally higher from Sturgeon Bay walleye, whereas,
concentrations of furans were higher from Fox Ri ver via. I'l eye.
' /
Hokanson and Lien (1986) are currently analyzing the data and looking
i f
(
for correlations between chemical body burdens and biological
effects. Also given in Table 2 are concentrations of certain
pesticides and PCBs found in fish collected in 1983 from the Lower
Fox River (see report by Duke, 1984).
Auer and Auer (1986) studied the impact of river water quality on
walleye egg development not influenced by fungal infestation,
predation or siltation. They collected and fertilized eggs from the
-------
Fox River and placed them in river water in dialysis tubes which were
rotated in a large tank receiving a continuous flow of Fox River
water. Incubation was conducted in a mobile laboratory at the edge
of the Fox River on the grounds of the DePere, Wisconsin, waste water
treatment plant. Egg survival to hatch on day 7 ranged from 34 to
82% with a mean of 60%. All hatched larvae attained lengths of 8.5
to 10 mm after 5 days, although feeding was not observed. Chemical
conditions of the river water during egg incubation period are given
in Appendix B-6.
Water samples throughout the water column were collected on 21
April and 9 May, 1983 to characterize spatial heterogeneity (Auer and
Auer 1983). Samples were collected at 5-10 cm intervals beginning at
5 cm above the bottom. Chemical measurements showed little variation
with depth in dissolved oxygen, pH or dissolved sulfides. Dissolved
oxygen was near saturation, pH was from 8.1-9.2 and hydrogen sulfide
was < 0.001 jUg/L.
Sediment water chemistry at the sediment water interface during
the summer months of 1985 revealed dissolved oxygen ranging from 0.16
mg Oo/'" at sites with highly organic sediments to 7.2 mg 00/L
with sandy sediments; pH ranged from 7.22-8.45 (Auer and Auer 1986).
Ammonia and nitrite nitrogen, and hydrogen sulfide ranged from
0.073-2.372 mg N/L, 0.015-0.067 mg N/L and 0.0018-0.2899 mg/L,
respectively. Sediment chemical oxygen demand (COD) near DePere
ranged from 6-463 mg O^/g DW (see Appendix B-7).
Regions of the Lower Fox River sediment COD are classified in
Appendix B-8, B-9 and B-10, over ranges of 0-50, 51-100, 101-170 and
> 170 mg 02/9 DW (Auer and Auer, 1983). In general, only suitable
walleye spawning and egg development was observed over sediments
9
-------
having a chemical oxygen demand less than 50 mg Og/g DW where
dissolved oxygen, ammonia, nitrogen, and hydrogen sulfide
concentrations were suitable. Balcer et al. (1986) reported that
areas with less than 50 mg Og/g DW have sand and gravel substrates
and are suitable for walleye ova incubation, whereas levels greater
than 100 mg Oo/g DW are correlated with organic muck and soft clay
which is not suitable for incubation of walleye eggs.
Balcer et al. (1986) collected adult walleye from the Fox River,
stripped and fertilized their eggs. They incubated the eggs i n-si t u
in the Fox River using incubation trays, tissue culture plates,
incubation tubes, dialysis bags and on artificial reefs. Walleye ova
survival for eight days (until just before hatching) was 20%, 35% and
25%, respectively, for the incubation trays, tissue culture plates
and incubation tubes. These investigators found no significant
difference between ova incubated in mid-water and those incubated on
the bottom in areas of low COD; this indicated that at suitable
spawning sites physical and chemical conditions were adequate for
walleye ova incubation throughout the water column.
In 1986, ova were collected from walleye from the Lower Fox River
(Brooke, 1986); the fertilized ova were placed in tissue culture
plates and ova incubation trays and incubated on the river bottom at
ten sites located between the DePere Dam and the Fort Howard Paper
Company to evaluate the impact of substrate quality and ova survival
(Appendix B-ll). A subset of the incubators was lifted periodically
for grooming and examination of ova development. The 10 incubation
sites differed with respect to current velocity and substrate type,
ranging from areas with rapid currents and cobble substrates (sites 8
and 9) to backwater areas with reduced flow and fine organic
10
-------
substrates (sites 7, 10 and 12). All sites had similar values for pH
(8.1-8.8), conductivity (230-330 umho/cm ), total alkalinity
(140-160 mg/L CaC03) and EDTA hardness (160-195 mg/L CaCOg).
Oxygen remained near saturation at the bottom at all sites throughout
the incubation period. Although nitrite and sulfide were only at the
detection limit, high ammonia concentrations (_> 0.3 ppm) were
consistently found at site 4, below the DePere Treatment Plant. Ova
survival at the incubation sites was variable. Although no
statistical analyses have been made, examination of the survival data
from non-groomed tissue culture plate incubators (Appendix B-12)
suggested that survival of walleye ova in the Lower Fox River was
maximal near the DePere Dam (sites 8, 9 and 11) and below the Hwy 172
bridge (site 2). Ova survival was reduced at sites 4, 5 and 6
(between the Brown County Fairground and the DePere Treatment Plant)
and was extremely poor at sites with fine organic substrates (sites 7
and 10). Data from ova pumping, drift netting and ova collection
hoops indicated that walleye in the Lower Fox River used the cobble
areas below the DePere Dam (sites 8 and 9) as primary spawning
grounds and that survival of naturally spawned ova is good at
ovi pos i t i on sites.
Balcer et al. (1986) collected eighteen species of fish in the
Lower Fox River in April of 1985 (Appendix B-13). Walleye and yellow
perch were the most abundant species and spawned in the river.
Thirty-eight of the 643 adult walleye examined had lymphocystis-1ike
growths and tumors. The growths were more common to males than to
females and were most prevalent on the fins and opercula.
11
-------
Work Underway or Planned
Walleye adults and ova from the Fox River have been analyzed for
dieldrin; p,p DDE; p,p DDD; p,p DDT; cis-chlordane; cis-nanochlor;
trans-nanochlor; Araclor 1248; and Araclor 1254. Analyses of
polychlorinated dibenzo-p-dioxins (PCDDs); polychlorinated
dibenzofurans (PCDFs); and tetrachlorobiphenyls (TCBs) in walleye,
walleye ova and sediment have recently been completed. Preliminary
results are included in this report. An investigation is currently
underway to determine whether or not observed biological effects can
be correlated with chemical residues.
Work proposed, but not completed, includes the following: (1) use
of in-situ biomonitor ing tools to identify problems limiting survival
and the distribution of sensitive benthic macro-invertebrates; (2)
in-situ synoptic surveys of benthic macroinverte-brates along a
pollutant gradient to identify species and classify each into
functional ecological guilds reflecting environmental
requirements; (3) investigation of a possible correlation between
organic contaminant levels in ova and adult walleye and biological
effects on larval walleye; and (4) measure organic contaminants in
edible fish which threaten human health.
Studies should include development of a toxic residue model to
ascertain the origin of and to predict the fate and effects of
toxicants which bioaccumulate in the food chain from the Fox River
and Green Bay. The focus should be on the bioconcentration/
bioaccumulation of toxicants suspected or known to adversely affect
or threaten birds and humans consuming fish.
12
-------
Studies could also possibly include modeling the biological (BOD)
and chemical (COD) oxygen demand of the sediment, including the
origin of the materials contributing to the demand as well as the
time required to achieve suitable spawning substrate if certain
sources were reduced or eliminated.
13
-------
Summary and Conclusions
Effluents entering the Lower Fox River, which were tested in
1983, were often non-toxic to fathead minnows and ceriodaphids
although many tests were not successful because of the toxicity of
the water upstream from the effluents. It was concluded that, with
some reservations, some effluent additions may reduce ambient
toxicity. Laboratory studies on instream (ambient) Fox River water
using fathead minnows, daphnids, and ceriodaphnids in 1985 did not
show lethal effects although there were some subtle chronic effects
on fathead minnow growth and ceriodaphnid reproduction. Results of
these tests indicated sources of toxicity periodically but not
consistently. In evaluating these laboratory tests the inherent
limitations of the test results should be considered. Temporary
changes in the water quality are not apparent from grab samples taken
at a particular time. In addition, prolonged storage of samples,
aeration (which would remove volatile compounds) and changes in
temperature all change the physical and chemical characteristics of
the water. It is apparent that i n situ bioassays and instream
identification and enumeration of the biota would more accurately
evaluate the present condition of the Fox River, which has not yet
recovered from years of degradation. The benthic fauna inhabiting
the soft substrates of the lower Fox River were comprised mainly of
chironomids and oligochaetes (Markert, 1981), although some
caddisflies had become more common by 1980. It is evident that a
survey of the bottom fauna is again needed.
Instream water quality measurements for pH, alkalinity,
conductivity, hardness, chloride, nitrite and nitrate nitrogen,
phosphorus, sulfate, sulfides, and ammonia have shown that these
parameters were suitable for aquatic life. However, in the lower Fox
14
-------
' River sediment concentrations of ammonia-nitrogen, hydrogen sulfide
and dissolved oxygen were not suitable for fish egg development.
Areas with high sediment chemical oxygen demands had sulfide
concentrations of ~ 0.3 mg/L, ammonia-nitrogen concentrations from
2-5 mgN/L and oxygen concentrations of < 3 mg/L (Auer and Auer,
1986). Acute and chronic toxicity standards were exceeded in over
50% of the samples analyzed. These areas were chemically unsuitable
for fish egg development and for many macroinvertebrates. In
addition these sediments contained many chemicals which bioaccumulate
in aquatic animals. Additional analysis of toxic materials in the
sediment, as well as a scheme to deal with this problem, is needed.
Recent studies summarized in this report showed that eggs from
walleye were viable when incubated in Lake Superior water, Fox River
water, on artificial substrates on Fox River sediment, and naturally
on Fox River sediment with a COD of < 50 mg Oo/g DW. Approximately
35% of the sediment of the lower Fox River has COD concentrations
suitable for walleye spawning. In 1985 the walleye successfully
reproduced naturally in the lower Fox River. However, there was
evidence that contaminants were affecting reproduction. The negative
relationship between larval survival and female weight suggested a
contaminant problem as larger fish were known to have larger amounts
of toxicants which bioaccumulate. The biological effects were
evident in fish from the lower Fox River and also from Sturgeon Bay
in Lake Michigan. Mortality of walleye was highest in postlarval 1
phase of development when the yolk sac was absorbed. As the yolk sac
is the primary storage site for chlorinated hydrocarbons this is the
time when these compounds would be transferred to the larval fish.
In addition to contaminants present in fish, unsuitable temperatures
because of unsuitable weather and fluctuations from seiche activity
15
-------
may also contribute to year-class failures of walleye. In 1985 and
1986 there was successful walleye reproduction in the Lower Fox River
as water temperatures rose and other conditions were suitable.
Toxicants alone therefore are not responsible for walleye
reproductive failures, but further decrease environmental
resistance. Restoration of suitable sediment and lowering of organic
contaminants in the fish brood stock would provide for a better
hatch, especially in years when incubation conditions are marginal.
Additional research needed on the Fox River includes more
extensive sediment analysis for other chemicals, in si tu
biomonitor ing and surveys, investigating a possible correlation
between concentrations of organic contaminants in Fox River and Green
Bay fish and effects on larval fish survival, development of a toxic
residue model focusing on bioaccumulation of toxics known or
suspected of causing adverse effects to aquatic life, birds and man
and a model for the biological and chemical oxygen demand to predict
adverse effects and to predict the consequences of removing or
eliminating certain sources.
16
-------
Literature Cited
Anon. 1985. The toxicity of some industrial effluents and their
effects upon Fox River water quality. Unpublished report, U.S.
EPA, Environmental Research Laboratory-Duluth, MN.
Auer, N.A., and M.T. Auer. 1983. An investigation of walleye egg
hatching success in the Lower Fox River, Wisconsin. Draft,
submitted to U.S. EPA. Grant No. CR-810076020, Progress Report,
Duluth, MN. 33 pp.
Auer, N.A., and M.T. Auer. 1986. An i n-s i tu and laboratory
evaluation of barriers to walleye egg and larva survival in the
Lower Fox River (Wisconsin). Manuscript submitted to Transac-
tions of the American Fisheries Society.
Balcer, M.D., D.J. McCauley, G.J. Niemi, and L.T. Brooke. 1986.
Ecological assessment of factors affecting walleye ova survival
in the Lower Fox River. Progress Report to U.S. EPA,
ERL-Duluth, Cooperative Agreement No. CR-811723-02-0. 78 pp.
Brook, L., M. Balcer, and D. McCauley. 1986. Ecological assessment
of factors affecting walleye ova survival in the Lower Fox River
(personal communication).
Duke, D.J. 1984. Analysis of walleye fish and ova for pesticides
and PCBs. Internal Report.
Gross, M.L. 1986. Analysis of polychlorinated dibenzo-p-dioxins
(PCDD's), polychlorinated dibenzofurans (PCDF's) and
tetrachlorobiphenyls (TCB's) in fish, fish ova and sediment
samples from the Fox River, U.S.A. Internal report from
Cooperative Agreement CR-812004010.
Hokanson, K.E.F., and G.J. Lien. 1986. Effects of organic
contaminants in ova upon growth and survival of larval walleye
from the Lower Fox River and Sturgeon Bay areas of Green Bay,
Wisconsin. Unpublished report, U.S. EPA, Environmental Research
Laboratory-Duluth, MN.
Lozano, S. 1985. Risk analysis for toxic substances in the Lower
Fox River. Unpublished report, U.S. EPA, Environmental Research
Laboratory-Duluth, MN.
Lien, G.J., K.E. Biesinger, L.E. Anderson, E.N. Leonard, and M.A.
Gibbons. 1985. A toxicity evaluation of Lower Fox River water
and sediments. EPA-600/3-86-008. 28 pp.
Markert, B.E. 1981. Water quality improvements in the Lower Fox
River, Wisconsin, 1970-1980: an historical perspective.
Institute of Paper Chemistry, Technical Paper Series 105. 9 pp.
Patterson, D. 1980. Water quality modeling of the Lower Fox River
for wasteload allocation development. Wisconsin Department of
Natural Resources, Bureau Water Qual. 90 pp.
17
-------
Sullivan, J.R., and J.J. Delfino. 1982. A select inventory of
chemicals used in Wisconsin's Lower Fox River basin. Univ.
Wise. Sea Grant Inst., WIS-SG-82-238. 176 pp.
Toxic Substances Task Force. 1983. Final report of the Toxic
Substances Task Force on the Lower Fox River system. Coop.
Agencies: Wise. Dept. Nat. Res., U.S. Geological Survey, U.S.
Fish & Wildl. Serv., U.S. EPA-Region V, Univ. Wise. 70 pp.
Wisconsin Department of Natural Resources. 1978. Investigation of
chlorinated and nonchlorinated compounds in the Lower Fox River
watershed. EPA-905/3-78-004. U.S. Environmental Protection
Agency, Chicago, IL. 229 pp.
18
-------
111
in
CNI *»
a o
o r-~
a a
a
a
o
a
a
a
a
et
O
a
a
ID
in
a
rO
r-J
a
>- 0)
o o
a
O1
a a
to oo
O r^
a a
a
in
- CXI
N .
01 -o
a a a
a a «
vn
m
CNl
O
a
o
CD
LD CD
C LT>
O (O CO
o_ j= tn
O Q.
co a
m
CXt
UD
a
-o
a.
a
in
a.
o
a.
o
<_>
O
4) O
E
.- m
-*. oo
O CTl
> Q.
E
u o
O) O)
E -=
c 0)
O ^1
O. I
o o
*~ V) X
c o -o
o u-
CJ 0
-------
a>
a
o -»-
Z 01
6
0)
S
4) S
>
o
I
in
a
to
I
a
ro
in
a
a
a
in
ro
CNJ
o
o
Csl
oo
to
a
a
tO ^
in
> o
a
iv. i
i in
CM
O
to
at
to
ro
r>^ CNI in
ro _
i O
in i
a>
S
cu
a.
> a
-------
0)
en
W 1>
-o
X CJ
._ c
w
ce en
c
X O
ID
a
a
a
CO
I
a
a
S o
o
, E
-O 3
a c
a>
* c
o
e
o .
« o
L. >
a o
-------
APPENDIX A
ANNOTATED BIBLIOGRAPHY
-------
AHNOFF, M., B. JOSEFSSON, 6. LUNDE, and G. ANDERSSON
1979
MONITORING OF TOTAL AMOUNT OF LIPOPHILIC ORGANO CHLORINE COMPOUNDS
IN A SWEDISH RIVER
WATER RES. 13:1233-1237
A sensitive method for the determination of organic bound chlorine in river
water has been used in a monitoring program. The amount of organic bound
chlorine, extracted by cyclohexane and determined by neutron activation analysis,
was chosen as a parameter for detection and tracing of pollutants with annoying
or harmful properties. During one year, 216 samples, each collected continuously
during 48 h. were taken at seven stations, located at 7-23 km distance along
the Gota River, Sweden. The detection limit of the method was below 0.05 ug
Cll~l. Major sources of pollution were localized to certain sections of the
river.
W.F. AHRNSBRAK AND R.A. RAGOTZKIE
1970
MIXING PROCESSES IN GREEN BAY
PROG. 13TH CONF. GREAT LAKES RES. 880-890. INTERNAL ASSOC. GREAT LAKES RES.
A one-dimensional diffusion model based on the principle of conservation
of mass is applied to Green Bay. Observed diffusivities are compared with
those predicted on the basis of seiche activity and that mechanism is shown
to be primarily responsible for the observed concentration field. Diffusivities
in the vicinity of Long Tail Point are on the order of 0.25 x 10" cm^/sec
with an abrupt jump to 1 x 10° cm^/sec a few km beyond and gradually increasing
to 2 to 3 x 10^ cm^/sec in the central part of the Bay. Electrical conductivity
and light transmissivity are used to observe the distribution of Fox River
water in the Bay. Highest concentration gradients (40% km) were found in the
vicinity of Long Tail Point and along the eastern shore of the southern end
of the Bay. No appreciable transferse gradients were found in the mid and
northern portion of the Bay. (Key words: Diffusion; pollution; seiche;
Green Bay.)
ANDERSON, R.V.
1977
CONCENTRATION OF CADMIUM, COPPER, LEAD, AND ZINC IN
SIX SPECIES OF FRESHWATER CLAMS
BULL. ENVIRON. CONTAM. TOXICOL. 18(4):492-496
In summary the metal concentrations in the bodies of the freshwater
clams studied generally reflected that found in the environment, with the
exception of Zn. The shell had comparatively lower concentrations of all
metals which reflects its inactive role in filtering and feeding. While
concentrations of the studied metals are not the sane between saltwater and
freshwater clams the relationships between the metals, body parts, and
environment were similar.
A-l
-------
ARMSTRONG, D.E.
1983
PRELIMINARY DRAFT OF PROJECT REPORT. PROJECT 807836010
MEMORANDUM TO MIKE MULLIN, PROJECT OFFICER, GROSSE ILE, MI: 36 P
The purpose of this memo is to provide a preliminary report of information
to be contained in the final report on the project, "PCBs In Lake Michigan
Tributaries, Waters, and Sediments". The final report will be presented in
four sections: I. PCBs in Lake Michigan Tributaries, II. PCBs in Fish
Samples from the Ashtabula and Fox Rivers. Part of the data from sections II
and III has been transmitted previously. This memo focuses on the data on PCBs
in Lake Michigan tributaries and lake water samples. Additional results from
parts III and IV will be summarized in separate memos.
AUER, N.A. and M.T. AUER
1983
AN INVESTIGATION OF WALLEYE EGG HATCHING SUCCESS IN THE
LOWER FOX RIVER, WISCONSIN
DRAFT, SUBMITTED TO E.P.A. GRANT R810076010,
PROGRESS REPORT, DULUTH, MN: 33 P.
The walleye (Stizostedion vitreum) is endemic to Green Bay and the Fox
River (Becker, 1983) and has been a part of the commercial and sport-fishing
catch for many years. In 1885, the annual combined catch of pike and pickerel
(walleye and northern pike) from lower Green Bay was 365,000 pounds (Smith and
Snell, 1891). The walleye, however, has never been an abundant or highly
sought-after component of the fishery in either the Fox River or lower Green
Bay. Past commercial fishing operations in Green Bay have focused on lake
trout (Salvelinus namaycush), whitefish (Cpregonus clupeaformis), lake herring
(Coregonus artedii), smelt (Osmerus mordax), and alewife (Alosa pseudoharengus).
The most abundant catches of walleye have been associated with sport-fishing
activities in northern Green Bay and Big- and Little Bay-De-Noc in the 1940s
(Bertrand et aj_., 1976).
The Lower Fox River and southern Green Bay have, however, received sone
commercial fishing pressure. As late as 1973-74, walleye comprised 2.8-3.7%
(by number) of the commercial catch at a site just downstream of the DePere Dam
(Kernen, 1974). Analysis of data from commercial catch reports and Wisconsin
Department of Natural Resources (WDNR) surveys, shows that walleye accounted
for 3-15% of the catch in the Lower Fox River (fyke nets) and <1% of the
catch in southern Green Bay (drop nets). While direct comparison is difficult
due to differences in time and season of sampling and gear selectivity (fyke
vs. drop nets), these data show that walleye are a relatively small component
of the overall catch. The complete species composition breakdown for fyke
net surveys in the Fox River for 1973-79 is presented.
A-2
-------
BALL, J., F. PRIZNAR, and P. PETERMAN (COMPILERS)
1978
INVESTIGATION OF CHLORINATED AND NONCHLORINATED COMPOUNDS IN
THE LOWER FOX RIVER WATERSHED
U.S. NTIS PB-292 818; GREAT LAKES NATL. PROGRAM,
U.S. ENVIRON. PROT. AGENCY, CHICAGO, IL: 235 P.
This report concerns the existence, source and fate of chlorinated and
non-chlorinated organic compounds in the Lower Fox River of Wisconsin. Raw
and treated wastewaters, surface water, seston, snowmelt, sediment, fish and
clams were sampled. A total of 105 compounds were identified and an additional
20 compounds were characterized by GC/MS. Twenty identified compounds are on
the U.S. EPA Consent Decree Priority Pollutant List. The study shows PCBs
and some other chloro-organics in effluents are reduced by efficient suspended
solids removal. It is possible, but not proven, that some chloro-organics are
formed by process or effluent chlorination. Clams were found to rapidly bio-
accumulate PCBs. Fish fillet samples contained PCB concentrations up to 90 mg/kg.
Sediments throughout most of the river were found to be contaminated with PCBs.
An extensive bibliography is included.
BERGH, A.K. and R.S. PEOPLES
1977
DISTRIBUTION OF POLYCHLORINATED BIPHENYLS IN A
MUNICIPAL WASTEWATER TREATMENT PLANT AND ENVIRONS
SCI. TOTAL ENVIRON. 8:197-204
Distribution of polychlorinated biphenyls (PCB) in sewage wastes at a
municipal sewage treatment plant was studied, showing that the great bulk of
PCBs entering such a treatment plant become adsorbed onto the grit chamber
solids and the sludge that is passed from the anaerobic digesters. When
appreciable quantities of PCBs are present in sewage, as was the case in this
study, significant quantities can nevertheless pass with the effluents dis-
charged from the treatment plant. The PCB concentrations in the treatment
plant waters undergoing secondary and tertiary treatment tend to be consistent
with the limited solubility properties of the PCBs. However, appreciably
higher concentrations can be found in the sediments of waters receiving treat-
ment plant discharges and bioaccumulation in fish is demonstrated readily.
Also described are quantitative data on PCBs in soils fertilized with PCB-
contaminated sludge.
A-3
-------
BROWNLEE, B. and W.M.J. STRACHAN
1976
PERSISTENT ORGANIC COMPOUNDS FROM A PULP MILL IN A
. NEAR-SHORE FRESHWATER ENVIRONMENT
IN: L.H. KEITH (ED.), IDENTIFICATION & ANALYSIS OF
ORGANIC POLLUTANTS IN WATER
ANN ARBOR SCI. PUBL. INC., ANN ARBOR, MI: 661-670
Our objective was to determine if any organic compounds present in the
mill effluent could be detected at significant distances (up to 5 km) from
the effluent outfall and therefore might be considered to be persistent.
Procedurally this involved first, identifying as many constituents as possible
in the mill effluent and second, determining if any of these compounds could
be detected in water, seston or sediment samples taken according to a pre-
determined pattern of sampling sites. Conversely, those compounds which were
not detectable outside the immediate mill area could be considered to be
relatively nonpersistent.
Effluent plume movement was a major consideration as we were concerned
primarily with compounds detectable outside the area influenced by the plume.
Local reports were that predominant plume movement is in a southeasterly
direction extending as far as Five Mile Point. This predominance was taken
into account when the sampling pattern was chosen.
Fish tainting has been a problem for the commercial fishery in this
area. Another study conducted at the same time as ours was directed toward
the identification of suspect compounds in fish taken from the mill area.
We hoped to be able to correlate our results with this study.
BROWNLEE, 8. and W.M.J. STRACHAN
1977
DISTRIBUTION OF SOME ORGANIC COMPOUNDS IN THE/RECEIVING WATERS
OF A KRAFT PULP AND PAPER MILL
J. FISH. RES. BOARD CAN.'34:830-837
Water, seston, sediment, and macrophyte samples were collected from Nipigon
Bay, Lake Superior at distances up to 6.8 km from the effluent discharge of
a kraft pulp and paper mill at Red Rock, Ontario. Fifteen compounds have been
identified in mill effluent and six of these were found in samples from the Bay.
Mi 11-related compounds were found most often in water and sediment samples,
less often in seston samples, and in none of the macrophytes samples. Dehydro-
abietic acid, present in mill effluent in excess of 1 mg/1, was found in most
water and sediment samples and a few seston samples. This compound is a good
indicator of the areal influence of the effluent. Palmitic acid and dioctyl
phthalate were also widely distributed. Acetovanillone and sandaracopimaric
acid were found in one water sample 1.0 km from the discharge. 7-oxodehy-
drobietic acid was found in five water samples at distances of up to 4.7 km from
the discharge. This is apparently the first time that this compound has been
reported in a mill effluent or in environmental samples.
A-.4
-------
BROWNLEE, B., M.E. FOX, W.M.J. STRACHAN, and S.R. JOSHI
1977
DISTRIBUTION OF DEHYDROABIETIC ACID IN SEDIMENTS
ADJAG&NT TO A KRAFT PULP AND PAPER MILL
J. FISH. RES. BOARD CAN. 344:838-843
Sediments adjacent to a kraft pulp and paper mill on western Nipigon
Bay, Lake Superior, were examined for resin acids. Dehydroabietic acid was
the predominant resin acid with surficial concentrations of less than 5-100 ug/g,
The areal distribution indicated the mill to be the primary source of this
compound. Depth profiles of the acid and core dating by 210Pb methods enabled
the calculation of a mean sediment accumulation rate of 0.11 cm^yr"1 and a
half-life for the disappearance of dehydroabietic acid in the sediments of
approximately 21 yr. A half-life of 0.12 yr was estimated for this compound in
the water column. It appears, therefore, that the primary removal mechanism
of dehydroabietic acid is degradation in the water column.
BUELOW, C.R.
1982
ORGANICS IN THE LOWER FOX RIVER SYSTEM: SELECTED NEUTRAL COMPOUNDS
MS. THESIS, UNIVERSITY OF WISCONSIN, MADISON, WISCONSIN
This study investigated the origin(s) of retene and related diterpene
hydrocarbons in the Lower Fox River sediments. The following hypotheses were
considered:
1. Retene and related compounds are generated from resin acid
precursors during biotreatment of pulp and paper mill effluents.
2. Resin acids as precursors to retene are discharged to the river and
are biodegraded in the sediments to intermediate hydrocarbons and
retene.
3. Retene and related compounds are discharged to the river in pulp
mill effluents as wood extractives, or in paper mill effluents as
components of rosin size.
A second objective was to relate the distribution of retene in the
sediments to the locations of discharges from pulp and paper mills or municipal
wastewater treatment plants.
Objectives A and B required the adaptation and evaluation of analytical
methods for the extraction and analysis of these compounds.
A minor objective was to describe the present distribution of poly-
chlorinated biphenyls in the Lower Fox River sediments.
A-5
-------
CAIRNS, M.A., A.V. NEBEKER, J.H. GAKSTATTER, and D.F. KRAWCZYK
1983
TOXICITY OF TWO WISCONSIN FRESHWATER SEDIMENTS TO INVERTEBRATES
USING LIQUID (ELUTRIATE) AND SOLID PHASE BIOASSAYS
PRELIMINARY DRAFT, U.S. E.P.A., CORVALLIS,
ENVIRON. RES. LAB, CORVALLIS, OR: 28 P.
Contaminated freshwater sediments from the Lower Fox River/Green Bay and
the Phillips Lakes Chain, Wisconsin, were bioassayed for acute toxicity using
Hyalella azteca, Gammarus lacustris, and Daphnia magna. D^ magna were exposed
for 48 hours and the two amphipods were exposed for 10 days to sediment and
water in a 1:4 ratio in solid phase bioassays. D. magna were also exposed for
48 hours in liquid phase (elutriate) bioassays. The two most contaminated
Green Bay/Fox River sediment samples caused highly significant (
-------
DELFINO, J.J. and D.B. EASTY
1979
INTERLABORATORY STUDY OF THE DETERMINATION OF
POLYCHLORINATED BIPHENYLS IN A PAPER MILL EFFLUENT
ANAL. CHEM. 51(13):2235-2239
Six laboratories collaboratively studied a method for determining poly-
chlorinated biphenyls (PCBs) in paper mill effluent. In preliminary studies,
the recovery and relative standard deviation (RSD) for the PCB Aroclor 1242
added to and extracted from distilled water were 95.6% and 14.7%, respectively.
Because the RSD of data from direct injection of Aroclor 1242 solutions into
the gas chromatograph was of similar magnitude, 15.6%, gas chromatographic
analysis appeared to provide the principal source of variation in the overall
determination. Participating laboratories achieved an average 93.7% recovery of
Aroclor 1242 added to a paper mill effluent; their data had a RSD of 16.0%.
The results indicate that the method is satisfactory for use with paper mill
effluents having PCB concentrations above 2 ug/L and it compares favorably
with findings from studies in other environmental matrices. Greater variation
might be expected from effluents containing significant interferences.
DELLIN6ER, R.W.
1980
DEVELOPMENT DOCUMENT FOR PROPOSED EFFLUENT LIMITATIONS
GUIDELINES AND STANDARDS FOR THE PULP, PAPER AND
PAPERBOARD AND THE BUILDERS' PAPER AND ...
OFFICE WATER WASTE MANAGE., EPA 440/1-80/025-B,
U.S. EPA, WASHINGTON, DC.; U.S. NTIS PB81-201535: 634 P.
This document presents the findings of a study of the Pulp, Paper, and
Paperboard and the Builders' Paper and Board Mills Point Source Categories
for the purpose of developing effluent limitations guidelines for existing
and new point sources and to establish pretreatment standards for existing
and new dischargers to publicly owned treatment works to implement Sections
301, 304, 306, 307, 308, and 501 of the Clean Water Act (the Federal Water
Pollution Control Act Amendments of 1972, 33 USC 1251 et seq., as amended by
the Clean Water Act of 1977, P.L. 95-217 (the "Act";).
The information presented in this document supports regulations proposed
in December 1980. Information is presented to support best available technology
economically achievable (BAT) best convertional pollutant control technology
(BCT), new source performance standards (NSPS), pretreatment standards for new
and existing sources (PSNS and PSES) for the Pulp, Paper, and Paperboard and
the Builders' Paper and Board Mills Point Source Categories. The report pre-
sents and discusses data gathering efforts, subcategorization, water use,
pollutant parameters, control and treatment technologies, development of
regulatory options, cost and non-water quality considerations, and the metho-
dology for development of effluent limitations.
A-7
-------
.DOSKEY, P.V. and A.W. ANDREN
1981
MODELING THE FLUX OF ATMOSPHERIC POLYCHLORINATED
BIPHENYLS ACROSS THE AIR/WASTE INTERFACE
ENVIRON. SCI. TECHNOL. 15(6):705-711
Problems involved in measuring and modeling polychlorinated biphenyl
(PCB) fluxes across the air/water interface are addressed. Speciation of air-
borne PCBs, operationally defined by partitioning through a glass-fiber filter,
indicate that greater than 90% exist in the vapor phase. Indirect calculations
based on semi empirical expressions predict that particlebound Aroclors are
primarily associated with submicrometer-size aerosols. Mono- and dichlorobi-
phenyl vapor is collected poorly by available collection methodologies.
Quantification of environmental samples is further complicated by weathering
of individual Aroclor components. A model of the PCB flux across the air/water
interface, employing Lake Michigan as an example, is presented which includes
the processes of vapor and particle deposition, volatilization, and bubble
ejection. The importance of vapor deposition and volatilization is dependent
upon the magnitude of the Henry's law constant derived from laboratory and
environmental data are used to elucidate the flux of atmospheric PCBs to
Lake Michigan.
A-8
-------
ELLIS, R.H.
1967
EFFECTS OF KRAFT PULP MILL EFFLUENT ON THE PRODUCTION AND
FOOD RELATIONS OF JUVENILE CHINOOK SALMON IN LABORATORY STREAMS
TECHNICAL BULL. NO. 210, NATIONAL COUNCIL FOR STREAM IMPROVEMENT, INC: 55 P.
The effects of kraft pulp mill effluent (KME) on the growth, production, and
food consumption of juvenile Chinook salmon, Oncorhynchus tschawytscha (Walbaum),
and on the abundance of their food organisms were studied in simplified communities
in six laboratory streams. The investigation was conducted between June 1966
and June 1967 at the Pacific Cooperative Water Pollution and Fisheries Research
Laboratory, Oregon State University.
The waste, which was collected weekly from settling lagoons of a kraft
pulp mill producing paper from unbleached pulp, was introduced into the laboratory
streams at a constant flow rate. The toxicity of each batch of waste was
characterized by acute toxicity bioassays for which 96-hour median tolerance
limit (TLm) values were established. The concentration of acutely toxic sub-
stances added to each stream was expressed as a decimal fraction of the TLm values.
Salmon growth rate and production were reduced in laboratory streams that
received KME at a concentration of 15 ml/liter (1:67 dilution) and a toxicity
ranging from 0.14 to 0.36 TLm. Little or no reduction was found to occur in
streams that received waste at a concentration of 5 ml/liter (1:200 dilution)
and a toxicity ranging from 0.05 to 0.08 TLm. The reductions in growth rate
and production in the 15 ml/liter streams were greater at high stocking densities
than at low stocking densities. With the exception of the highest stocking
levels, food consumption was usually as high in the 15 ml/liter streams as in
the control or 5 ml/liter streams. Estimates of food abundance in the laboratory
streams did not indicate any reduction attributable to the waste.
The reductions in growth rate and production at concentrations of 15
ml/liter were attributed to a direct toxic effect of the waste. Information
on the food abundance, food consumption, and activity of'the salmon at the
highest stocking densities indicated that the waste w-3s affecting either the
desire or the ability of the salmon to feed. Tte interaction between salmon
stocking density and KME toxicity indicates the need for understanding the
influence of other environmental factors in studies of the effect of kraft
pulp mill effluents on fishery resources.
A-9
-------
EPSTEIN, E., M. BRYANS, D. MEZEI, AND D. PATTERSON
1974
LOWER GREEN BAY: 'AN EVALUATION OF EXISTING AND HISTORICAL CONDITIONS
U.S NTIS PB-236 414; EPA CONTRACT NO. 68-01-1572,
REGION V, U.S. ENVIRON. PROT. AGENCY: 281 P.
A survey is made of current and historical information relating to the
quality of the waters of Green Bay, Lake Michigan. The steady decline in
water quality over the last four decades is documented. A historical shift
in fish production from high quality native species to low quality exotic
species has occurred. Increasing areas of the Bay exhibit low oxygen levels.
In winter, under the ice, low oxygen levels now extend into the Bay as far as
40 kilometers. Nutrient loads have caused the areas where eutrophic conditions
exist to increase. These and other factors have led to a dislocation of
recreational use.
Documentation of the expected reduction in pollutant loads due to present
control strategies is also provided. Field studies performed in this program
indicate slight improvements in Bay water quality over recent years. A water
quality model, suitable for winter conditions, is also being developed which
will allow predictions of improvement in Bay water quality due to present and
future pollution control strategies. The final report will be available in
January, 1975.
FOX, M.E.
1976
FATE OF SELECTED ORGANIC COMPOUNDS IN THE DISCHARGE OF
KRAFT PAPER MILLS INTO LAKE SUPERIOR
IN: L.J. KEITH (ED.), IDENTIFICATION & ANALYSIS OF ORGANIC POLLUTANTS IN WATER
ANN ARBOR SCI. PUBL. INC., ANN ARBOR, MI: 641-659
In 1973, studies on pulp mill wastewater discharges on Lake Superior were
initiated by the International Joint Commission, Upper Lakes Reference Group.
This group had the task of reporting to the International Joint Commission (IJC)
on the impact of point source effluent discharges on the basically high-quality
receiving waters of the Upper Great Lakes (Huron and Superior). Apart from
domestic sewage, pulp and paper mill effluents constitute the major polluting
discharges into the Upper Great Lakes. Pulp and paper mill effluents have been
implicated in oxygen depletion, toxicity and production of taste and odor
problems in the receiving water and its aquatic communities.
The studies initiated were wide-ranging in scope and included many projects
in the chemical, physical and biological fields. This chapter will report on
the findings of one of those projects. Its object was to determine the fate
and effective zone of persistence of dissolved organic compounds in the effluent
plume.
A-10
-------
FOX, M.E.
1977
PERSISTENCE OF DISSOLVED ORGANIC COMPOUNDS IN
KRAFT PULP AND PAPER MILL EFFLUENT PLUMES
J. FISH. RES. BOARD CAN. 34:798-804
The persistence of dissolved organic compounds in the effluent plumes of
a pulp and paper mill on the north shore of Lake Superior was studied in 1974.
Approximately 90 organic compounds were observed of which 36 (including all
the major ones) were identified.
The dispersion of five of these compounds was examined quantitatively.
Dehydroabietic acid was the only major organic compound observed to exhibit
measurable persistence >2000 m from the effluent discharge. At 2000 m from
the discharge, levels of 30 ug/1 dehydroabietic acid were detected within the
plume and 15 ug/1 outside the effluent plume. The disappearance of dehydro-
abietic acid parallels that of the conservative ion Na+, indicating dilution
by the receiving water as the only significant short-term removal mechanism.
FOX, M.E., D.M. WHITTLE, and K.L.E. KAISER
1977
DEHYDROABIETIC ACID ACCUMULATION BY RAINBOW TROUT
(SALMO GAIRDNERI) EXPOSED TO KRAFT MILL EFFLUENT
J. GREAT LAKES RES. 3(1-2) :155-158
Rainbow trout (Salmo gairdneri) were examined for the presence of dehydro-
abietic acid after exposure to kraft mill effluent. Levels of 2 to 10 ug/g
dehydroabietic acid on a whole fish wet weight basis were found in fish exposed
to 3 to 18% effluent for 48 to 144 hours. Less than 1 ug/g dehydroabietic acid
was found in control fish which had been acclimated in Nipigon Bay water for
two weeks and no residue was detected in an unexposed fish. It is concluded
that fish exposed to kraft mill effluent accumulate dehydroabietic acid to a
level which is likely to result in sublethal toxic effects.
A-ll
-------
FUJIYA, M.
1961
EFFECTS OF KRAFT PULP MILL WASTES ON FISH
J. WATER POLLUT. CONTROL FED. 33(9):968-977
In recent years, the many pulp mills built in Japan have been the source
of serious liquid waste problems. As a result, extensive and intensive studies
have been carried out to determine the effects of these wastes on fish, shell-
fish, seaweed, and other aquatic organisms from various points of view.
Among the studies carried out have been ecological researches on the lethal
dose, avoidance reaction, and others. Physiological studies by the paper elec-
trophoretic method of serum separation had already been performed on fish.
On the other hand, the effects on the activity of seaweeds for phosphorus
assimilation and the calcium absorption by shellfish had been studied, and dis-
cussed physiologically. Although satisfactory results were obtained from these,
a histo-pathological approach also would be necessary for investigating the
effects on fish. Therefore, a cyto-chemical experiment was inaugurated to
study the histo-pathological effect on fish exposed in the water influenced by
the waste. It was deemed important to determine the toxicity of the waste to
fish.
JAMES E. GROOSE
1982
ORGANICS IN THE LOWER FOX RIVER SYSTEM: SELECTED ACIDIC COMPOUNDS
MS. THESIS, UNIVERSITY OF WISCONSIN, MADISON, WISCONSIN
The overall goal of this thesis was to determine the extent of con-
tamination in the Lower Fox River and lower Green Bay due to certain acidic
organic compounds.
This goal was approached by considering five specific objectives:
1. To perform a literature review of selected acidic organic
compounds related to pulp and paper mill activities;
2. To optimize the methodology for extraction, derivatization and
analysis of selected acidic organic compounds;
3. To quantify the concentrations of selected compounds in wastewaters
discharged to, and present in, river water and sediments of the Lower
Fox River system;
4. To determine sources and sinks for selected organic compounds;
and
5. To generate a "limited mass balance" for selected acidic organic
compounds through a municipal wastewater treatment plant and an
integrated pulp and paper mill.
A-12
-------
MICKEY, J.J., J.A. KEITH, and F.B. COON
1966
AN EXPLORATION OF PESTICIDES IN A LAKE MICHIGAN ECOSYSTEM
J. APPL. ECOL. 3 (SUPPL):141-153
The primary purpose of this study has been to determine what pesticide
residues, if any, are present at different trophic levels in a Lake Michigan
ecosystem with particular reference to the Green Bay area. Our main findings
of this exploratory study are summarized in the present report. A secondary
purpose, contingent upon the finding of DDT contamination, involved an attempt
to understand the biological significance, if any, of pesticide residues
encountered in various layers of the Lake Michigan animal pyramid. The
research strategy behind this project was a direct development of the concept
of ecological concentration of a pesticide in an aquatic ecosystem. The
second strategic element was the concept of pesticide transport by soil
particles.
W.D. JOHNSON, F.D. FULLER and L.E. SCARCE
1967
PESTICIDES IN THE GREEN BAY AREA
PROCEEDINGS, TENTH CONFERENCE ON GREAT LAKES RESEARCH, 1967
Pesticides in man's environment are being studied with increasing
intensity and interest because of the rapid increase in their usage in
agriculture. As national concern has increased, several of the Federal Water
Pollution Control Administration laboratories were equipped to analyze samples
from the aqueous biosphere. As part of this Federal effort, the Great Lakes-
Illinois River Basins Project initiated pilot studies to investigate the
effects of pesticides on the aqueous environment of Green Bay. The areas
studied were Door County, located at the northerly end of Green Bay Peninsula,
and tributaries on the western, southern and northern shores of Green Bay.
This paper describes analytical methods used, type of samples analyzed,
and concentration of the various common chlorinated pesticides detected. The
significance and effects of these compounds at the observed levels are
discussed, relative to their toxic effects on the aquatic environment and
man.
A-13
-------
KEITH, L. H.
1975
ANALYSIS OF ORGANIC COMPOUNDS IN TWO KRAFT MILL WASTEWATERS
ENVIRON. MONITOR. SER. EPA-600/4-75-005,
U.S. EPA, CORVALLIS, OR: US. NTIS PB247 698: 99 P.
Wastewaters from two kraft paper mills in Georgia were sampled at various
points in the waste treatment systems. Gas chromatography of the organic
extracts and identification of many of the specific chemical components by gas
chromatography-mass spectrometry provided a "chemical profile" of the effluents.
The mills, in different geographical locations, have very similar raw waste-
water compositions but different effluents are qualitatively similar in compo-
sition although the quantities of the various components differ. After two years
the raw and treated effluents of both mills were re-sampled. Analyses showed
that although concentrations of the organics varied, the same compounds are still
present.
KERNEN, L.T.
FISHERY INVESTIGATIONS ON THE LOWER FOX RIVER AND
SOUTH GREEN BAY IN 1973-1974
WISCONSIN DEPT. NATURAL RESOURC., MEMO
Fish populations in the Fox River and South Green Bay were investigated
through the use of three types of gear, with emphasis on the two and one-half
mile section of the Fox River downstream from the DePere Dam. Data was collected
by monitoring commercial net lifts, electro-fishing, and shoreline seining. In
the Fox River, 45 fish species were recorded with bullhead spp., carp, white bass,
and white sucker accounting for approximately 80% by number of 23,202 fish
examined over the two-year period. A total of 32 speci'es of fish were identified
from Green Bay, with yellow perch, alewife, bulkhead spp., burbot, and white
sucker comprising 90% by number in 1973 and 98% in 1974 of a 182,852 fish
sample.
A-14
-------
KINAE, N., T. HASHIZUME, T. MAKITA, I. TOMITA, I. KIMURA, and H. KANAMORI
1981 A
STUDIES ON THE TOXICITY OF PULP AND PAPER MILL EFFLUENTS -
I. MUTAGENICITY OF THE SEDIMENT SAMPLES DERIVED FROM KRAFT PAPER MILLS
WATER RES. 15:17-24
Sediment samples collected at three different coastal points (Shinguu,
Ooigawa and Tagonoura) were extracted with diethylether and then methanol. Each
extract was separated into five fractions by high-speed liquid chromatography
and they were submitted to mutagenic assay using B. subtil is and S. typhimurium
and to GC-MS analysis.
The ether fraction of sediment sample from Shinguu showed DNA damaging potency
on B. subtilis and exhibited mutagenic effect on S. typhimurium TA 98, TA 100
andTA 1537. 2,4,6-Trichlorophenol, 3,4,5,6-tetrachloroguaiacol, dehydroabietic acid,
pyrene and fluoranthene were mutagenic substances among 28 substances identified
and tested.
KINAE, N., T. HASHIZUME, T. MAKITA, I. TOMITA, I. KIMURA, and H. KANAMORI
1981 B
STUDIES ON THE TOXICITY OF PULP AND PAPER MILL EFFLUENTS- II.
MUTAGENICITY OF THE EXTRACTS OF THE LIVER FROM SPOTTED SEA TROUT
(NIBEA MITSUKURII)
WATER RES. 15:25-30
The liver samples of spotted sea trout (Nibea mitsukurii) caught in three
different coastal waters of Japan were extracted with diethylether and then
methanol. The extracts were submitted to mutagenic assay using Bacillus subtilis
and Ames strains of Salmonella typhimurium. The ether extract of the liver was
found to have DNA damaging potency on B. subtilis. The extract was applied to a
high-speed liquid chromatography to separate into five fractions and each was
tested for the mutagenic effects. The fraction of HLC-9 showed DNA damaging
and mutagenic potency on B. subtilis and S. typhimurium TA 98 respectively.
Gaschromatographic-mass spectrometric examination of each fraction revealed
18 organic compounds of which 12 substances were identical with those found
in the sediment samples. 9,10-Epoxystearic acid was mutagenically active among
them.
A-15
-------
LANDNER, L., K. LINDSTROM, M. KARLSSON, J. NORDIN, and L. SORENSEN
1977
BIOACCUMULATION IN FISH OF CHLORINATED PHENOLS FROM
KRAFT PULP MILL BLEACHERY EFFLUENTS
BULL. ENVIRON. CONTAM. TOXICOL. 18(6):663-673
The present work is an attempt to find out if the low-molecular chlori-
nated compounds, identified to be present in low concentration in the
effluents from Swedish kraft pulp bleacheries and some of which have been
shown to be acute-toxic to fish, furthermore show tendencies to accumulate
in fish. If such a bioaccumulation is demonstrated to occur, this would be
a strong rationale for further studies on possible long term or chronic
effects of this group of compounds.
LEACH, J.M. and L.T.K. CHUNG
1980
DEVELOPMENT OF A CHEMICAL TOXICITY ASSAY FOR PULP MILL EFFLUENTS
EPA-600/2-80-206, U.S. EPA, CINCINNATI, OH: 96 P.
A chemical analysis procedure was developed to measure, within 1.5 hours,
compounds responsible for the toxicity of pulp mill effluents to fish.
Analytical results for 113 samples of raw and biologically-treated bleached
and unbleached kraft, sulphite and groundwood effluents were converted via
toxic units into estimates of acute lethal toxicity. Agreement between 96-h
medial lethal concentrations calculated by this method, and values from
bioassays of the effluents using rainbow trout was within 30% for 73% of
the samples examined.
Biological treatment was highly effective in removing the known toxic
compounds at pulp mills on the Willamette River, OR. and the Androscoggin
River, N.H. and ME., based on estimates of toxicant loadings into and out of
the biobasins.
A-16
-------
LEACH, J.M. and A.N. THAKORE
1973
IDENTIFICATION OF THE CONSTITUENTS OF KRAFT PULPING EFFLUENT
THAT ARE TOXIC TO JUVENILE COHO SALMON (ONCORHYNCHUS KISUTCH)
J. FISH. RES. BOARD CAN. 30(4):479-484
The nonvolatile constituents that are acutely toxic to juvenile coho
salmon (Oncorhynchus kisutch) have been fully identified in a kraft pulping
effluent derived from Douglas fir and western hemlock. Toxicity and material
balances were maintained throughout a fractionation procedure leading to
isolation of the toxic factors.
Over 80% of the toxicity was caused by three resin acid soaps: sodium
isopimarate (55%), sodium abietate (22%), and sodium dehydroabietate (5%).
The remaining toxicity (18%) was contributed by sodium salts of the unsaturated
fatty acids: palmitoleic, oleic, linoleic, and linolenic.
LEACH, J.M. and A.N. THAKORE
1975
ISOLATION AND IDENTIFICATION OF CONSTITUENTS TOXIC TO JUVENILE
RAINBOW TROUT (SALMO GAIRDNERI) IN CAUSTIC EXTRACTION EFFLUENTS
FROM KRAFT PULPMILL...
J. FISH. RES. BOARD CAN. 32:1249-1257
Chemical constituents in effluent from the caustic extraction stage of
the bleach plant at a western Canada kraft pulpmill were fractionated to identify
factors responsible for their toxicity to juvenile rainbow trout (Salmo
gai rdneri). At all stages in the fractionation procedure bioassays were
carried out to monitor toxicities of the isolated materials. Five toxic
compounds, separated in a pure state from the effluent, were characterized
by chromatography, spectroscopy, and chemical synthesis. The compounds and
their 96-h median lethal concentrations (LC50) measured in static bioassays
were: 3,4,5-trichloroguaiacol (0.75 mg/liter), 3,4,5,6-tetrachloroguaiacol
(0.32 mg/liter), monochlorodehydroabietic acid (0.6 mg/liter), dichlorodehy-
droabietic acid (0.6 mg/liter), 9,10-epoxystearic acid (1.5 mg/liter).
The same compounds were shown to be present in caustic extraction effluents
collected from six other western kraft mills. For two samples, the concentra-
tion - toxicity graphs from bioassays of solutions containing only the pure
toxicants in the amounts found by analysis were similar to those of the actual
effluents produced by the mills. Concentrations of the toxic constituents in
samples from six different mills were equivalent to 2.3-24 TU (toxic units),
confirming that they are important factors in the toxicity of caustic extraction
effluents.
A-17
-------
LEACH, J.M. and A.N. THAKORE
1976
TOXIC CONSTITUENTS IN MECHANICAL PULPING EFFLUENTS
TAPPI 59 (2):129-132
Constituents toxic to fish were identified in mechanical pulping effluents
from mills operating on mixtures of spruce (75-85%), pine (15-25%), and fir (5%).
Chemical fractions separated from effluent sanples were monitored for toxicity to
juvenile rainbow trout throughout stages of a fractionation procedure based on
chromatographic techniques. Individual toxic compounds were identified by
comparison of their spectroscopic characteristics with those of chemically
synthesized materials. Acute toxicities of pure samples of the identified com-
pounds were measured in bioassays using rainbow trout. The predominant toxicants
were the resin acids, isopimaric, palustric, dehydroabietic, abietic, pimaric,
sandaracopimaric and neoabietic, which together accounted for 60-90% of overall
toxicity in the mechanical pulping effluents studied. Minor toxic factors included
alcohols related to the above acids, in particular pimarol and isopimarol,, and
an insect growth regulator, juvabione, and some of its derivatives. Other
potentially toxic compounds included diterpene aldehydes, unsaturated fatty acids,
and (epi)manool. Total resin acid concentrations in mechanical pulping effluents,
measured by gas chromatography, ranged from 12-62 mg/liter, whereas median
lethal concentrations (96-hr LC50) of these compounds for juvenile rainbow trout
were 0.4-1.1 mg/liter in static bioassays. Resin acids were also present in
effluent samples that were only partly detoxified by biological treatment.
A-18
-------
LEACH, J.M. and A.M. THAKORE
1977
COMPOUNDS TOXIC TO FISH IN PULP MILL WASTE STREAMS
PROG. WAT. TECH. 9:787-798
The major toxic factors in effluents from Canadian softwood kraft, sulphite
and mechanical pulping operations, and in wood debarking effluents, were seven
resin acids; dehydroabietic, abietic, isopimaric, palustric, pimaric, sandaraco-
pimaric, and neoabietic. Median lethal concentrations (96-h LC50) of the pure
compounds for juvenile coho salmon (Oncorhynchus kisutch) were 0.2 - 0.8 mg I"1
in bioassays with solution replacement every 4 - 8 h. Pulping and debarking
effluents frequently contained resin acids at levels equivalent to 100 toxic units,
The long-chain unsaturated fatty acids, oleic, linoleic, linolenic and palmitoleic
also contributed to the toxicity of these waste streams.
In mechanical pulping effluents, minor toxic factors included the diterpene
alcohols, pimarol and isopimarol, (96-h LC50, 0.3 mg I"1), and several naturally
occurring insect juvenile hormone mimics related to juvabione (96-h LC50, 0.8 -
2.0 mg I'1).
A completely different group of compounds was responsbile for the toxicity
of effluents from pulp bleaching plants. A major toxic factor in chlorination-
stage bleaching effluent was identified as chlorolignin. In caustic extraction
effluents, the predominant toxic contributors were trichloro- and tetrachloro-
guaiacol, monochloro-and dichloro- dehydroabietic acid, (96-h LC50, 0.3 -
0.75 mg I'1), and 9, 10-epoxy- and 9,10-dichloro- stearic acid (96-h LC50, 1.5
and 2.5 mg 1~1, respectively). Pitch dispersant additives were also implicated
as minor toxic factors in some caustic extraction effluents.
Contributions of the identified materials to effluent toxicity are described
in terms of the toxic units concept. The toxicants are discussed in relation to
their origin, to effluent discharge regulations, and to the choice of effluent
treatment techniques.
A-19
-------
LEACH, J.M., J.C. MUELLER, and C.C. WALDEN
1976
IDENTIFICATION AND REMOVAL OF TOXIC MATERIALS FROM KRAFT AND
GROUNDWOOD PULP MILL EFFLUENT
PROCESS BIOCHEM. 11 (1):7-10
Pulp and paper mills discharge large volumes of effluent that can be
detrimental to aquatic fauna in receiving waters. In many countries regula-
tions exist limiting the suspended solids content, biochemical oxygen demand
and in some cases the color of pulp mill effluents. Federal and Provincial
Government regulations in Canada are additionally concerned with the toxicity
to fish of pulp mill wastes. Efforts have been made to identify the nature
and sources of toxic materials in effluents from paper pulp manufacture and
to improve detoxification techniques. Recent progress in these areas relative
to kraft and goundwood mill effluents is summarized in this article.
LEUNG, P. - S.K. and N.J. SELL
1982
EFFECT OF THE PAPER INDUSTRY ON WATER QUALITY OF THE LOWER FOX RIVER
WATER RESOUR. BULL. 18(3): 495-502
The Lower Fox River, Wisconsin, hosts the densest concentration of
paper mills in the U.S., with 18 located along a 40-mile stretch between
Lake Winnebago and Green Bay, Lake Michigan. Some of these companies use
only primary, others also secondary, waste treatment techniques. Comparison
of the quantities of wastes discharged with the legal limits indicates that
all plants discharge only 40-50 percent or less of the allowable suspended
solids; most discharge <50 percent of the allowable BOD. This is equal or
better than the performance of paper companies elsewhere in the state.
Reductions in pollutant discharges have corresponded to improved water quality,
though too much BOD is still discharged to be adequately assimilated by the
Fox River. The relatively low current level of discharges means permit levels
would have to be drastically cut to make any significant impact on water quality.
Only a few companies might be seriously affected by such changes. Flow and
temperature related permits would likely be more effective, but more difficult
to comply with for the industry. Toxic substances are also a potential pro-
blem, particularly chlororganic compounds that can form in situ from the
chlorine frequently used for pulp bleaching.
A-20
-------
LINKO, R.R., P. RANTAMAKI, and K. URPO
1974
PCB RESIDUES IN PLANKTON AND SEDIMENT IN THE SOUTHWESTERN COAST OF FINLAND
BULL. ENVIRON. CONTAM. TOXICOL. 12(6):733-738
The purpose of this study was to determine residues of PCBs in the
plankton from the Turku Archipelago off the southwestern coast of Finland.
Preliminary experiments were also made to find PCBs absorbed into the sediment.
NATIONAL COUNCIL OF THE PAPER INDUSTRY FOR AIR AND STREAM IMPROVEMENT
1982
EFFECTS OF BIOLOGICALLY STABILIZED BLEACHED KRAFT MILL EFFLUENT
ON COLD WATER STREAM PRODUCTIVITY AS DETERMINED IN EXPERIMENTAL STREAMS- FIRST ...
TECH. REPT. NO. 368, NCASI, NEW YORK, NY: 66 P.
This technical bulletin presents the results of the first years' effluent
study in which two controlled streams received 0.5 ppm BOD addition of biologically
treated bleached results of increasing effluent concentrate additions. Separate
reports will be developed after several years of stream study to provide a
comprehensive discussion of cummulative knowledge developed relative to fish
production and other components of the food web (benthic and algal production).
NG, K.S., J.C. MUELLER, AND C.C. WALDEN
1974
PROCESS PARAMETERS OF FOAM DETOXIFICATION OF KRAFT EFFLUENT
PULP PAPER MAGAZINE CAN. 75(7) : 101-106
This study has been directed to assess the effective range of process
variables for detoxification and to investigate the possiblity of reducing
the treatment time from the 24-hr reuiqred previously. Optimum conditions
were used to develop a continuous system and the beneficial effects under
normal operating conditions were examined. Based on the findings, preliminary
cost estimates have been made for the foam separation process.
A-21
-------
MARY E. PARISO, JAMES R. ST. AMANT, AND THOMAS 8. SHEFFY
1984
MICROCONTAMINANTS IN WISCONSIN'S COASTAL ZONE
IN TOXIC CONTAMINANTS IN THE GREAT LAKES, ED.: J.O. NRIAGU AND M.S. SIMMONS,
JOHN WILEY AND SONS, NEW YORK
Microcontaminants were identified in Wisconsin's coastal zone almost
20 years ago. Fourteen studies conducted between 1965 and 1979 provide a
partial record of these microcontaminants. A subsequent three-year study
conducted by the Wisconsin Department of Natural Resources compiles a complete
and up-to-date inventory of microcontaminants in Wisconsin's coastal zone.
In 1979, problem drainage systems were identified using fish as a
biological indicator. The results of this survey showed that of the 16 toxic
substances monitored, only four represented problems for Wisconsin's coastal
zone: PCB, DDT, chlordane, and dieldrin. PCB was found to be the worst
contaminant statewide. Fish tested from Lake Superior and its tributary
streams showed that the quality of fish from this basin is high. Fish from
Lake Michigan and its tributary streams were found to contain varying levels
of PCB, chlordane, DDT, and dieldrin.
In 1980, intensive sampling of problem areas identified in the first
year survey defined more precisely the limits and potential sources of
contamination. Fish and sediment data indicated that a PCB problem persists
in specific areas of the following drainage systems: Sheboygan River, Milwaukee
River, Kinnickinnic River, Menomonee River, Pike River, Root River, and Fox
River. Mass spectrometry analysis of selected fish tissue samples identified
the presence of a variety of compounds that had not been monitored before.
In 1981, fish, sediment, and effluent monitoring continued for the
purpose of evaluating trends in contaminant levels and continuing the effort
to identify and eliminate point sources of toxic substances. PCB problem
areas were again found in the Fox, Milwaukee, Kinnickinnic and Pike Rivers.
A-22
-------
PATTERSON, D.
1980
WATER QUALITY MODELLING OF THE LOWER FOX RIVER FOR
WASTELOAD ALLOCATION DEVELOPMENT
WISCONSIN DEPT. NATURAL RESOUR., BUREAU WATER QUAL.: 90 P.
The Fox River from Lake Winnebago to the DePere Dam was modelled using a
finite difference water quality model. The QUAL model was adopted and exten-
sively modified by the Wisconsin DNR staff which used the QUAL II model as a
starting point for model development. The final model simulates dissolved
oxygen, two terms of BOD, total phosphorous, organic nitrogen, ammonia,
nitrate, chlorophyll-a and sediment oxygen demand. The model can be run in
both the steady state and dynamic mode.
The QUAL III nodel as developed was successfully calibrated for eleven
separate synoptic water quality surveys and verified with nine dynamic runs
that each covered a minimum of 27 days of simulation. The surveys covered
the years 1972 to 1979 and generally fell in the annual low flow high tempera-
ture period. Wasteload allocations (WLAs) have been developed for the several
dischargers on this river segment based on the models results.
A-23
-------
PETERMAN, P.H., J.J. DELFINO, D.J. DUBE, T.A. GIBSON, and F.J. PRIZNAR
1980
CHLORO-ORGANIC COMPOUNDS IN THE LOWER FOX RIVER, WISCONSIN
IN: B.K. AFGHAN AND D. MACKAY (EDS.), HYDROCARBONS AND HALOGENATED
HYDROCARBONS IN THE AQUATIC ENVIRONMENT, PLENUM PRESS, NEW YORK: 145-160
The Lower Fox River, Wisconsin is one of the most densely developed
industrial river basins in the world. During 1976-1977 about 250 samples
were analyzed by GC and GC/MS including biota, sediments, river water and waste-
waters from 15 pulp and/or paper mills and 12 sewage treatment plants. A
total of 105 compounds were identified in selected extracts by GC/MS with
another 20 compounds characterized but not conclusively identified. Twenty
of the 105 compounds are on the EPA Priority Pollutant List. Other compounds
identified in pulp and paper mill wastewaters, including chloroguaiacol s,
chlorophenols, resin acids and chloro-resin acids have been reported toxic to
fish by other investigators. Several compounds apparently not previously
reported in wastewaters are chloro-syringal dehyde, chl oroindole, trichlorodi-
methoxyphenol, and various 1-4 chlorinated isomers of bisphenol A. Concentra-
tions of the various compounds, when present in final effluents, ranged from
0.5 to ca. 100 ug/L. An exception was dehydroabietic acid, a toxic resin
acid not found on the EPA Priority Pollutant List. It was frequently found
in pulp and paper mill effluents in concentrations ranging from 100 to 8500
ug/L. PCBs were found in al 1 of the matrices sampled. Sixteen of the 35 fish
exceeded the FDA limit of 5 mg/kg, while 31 of the 35 exceeded the Canadian
limit of 2 mg/kg. Concentrations of PCBs and other chloro-organics were
related to point source discharges. There was a direct correlation of the
concentrations of these compounds in wastewater with suspended solids values.
A-25
-------
SAGER, P.E. AND J.H. WIERSMA
1972
NUTRIENT DISCHARGES TO GREEN BAY,
LAKE MICHIGAN FROM THE LOWER FOX RIVER
PROC. 15TH CONF. GREAT LAKES RES.:132-148
Seasonal variations in discharge of nutrients and organic matter from the
Fox River to Green Bay were related to the quality of Lake Winnebago discharges
and to processes of assimilation sedimentation and release in the river.
Lake Winnebago's effects on the river included increased levels of ammonia-
nitrogen in spring, total phosphate in summer and orthophosphate in fall.
Anoxic conditions in portions of the river indicate excessive organic
loading and are significant in ammonia-nitrogen releases. Phosphate assimila-
tion in the river is evident from decreases in loadings between Lake Winnebago
and Green Bay in summer and fall. Maximum loadings of phosphates and organics
during winter and spring reflect high flows, reduced assimil iation and releases
from the drainage system.
Annual average loadings of orthophosphate and total phosphate from municipal
treatment plants were 4400 and 6670 Ib/day, respectively. Discharges from
Lake Winnebago included annual average loadings of 2070 and 6620 Ib/day of
orthophosphate and total phosphate, respectively. Annual average loading of
ammonia-nitrogen from treatment plants was 4440 Ib/day and from Lake Winnebago
5200 Ib/day.
At the mouth of the river, annual average loadings to Green Bay in Ib/day
included 3080 for orthophosphate, 13,200 for total phosphate, 17,100 for nitrate-
nitrogen and 12,400 for ammonia-nitrogen.
A-26
-------
SERVIZI, J.A.
1974
TOXICITY TO AQUATIC ORGANISMS CAUSED BY CHLORINATION
PROC. BRITISH COLUMBIA WATER WASTE ASSOC.,
VANCOUVER, B.C., CANADA:172-182
Field and laboratory studies have demonstrated that chlorinated municipal
sewage is highly toxic to fish and in some cases disrupts natural migration and
species distribution. In each case, the principal source of toxicity was
chlorine applied during disinfection, which increased toxicity of primary and
secondary effluents by several fold. However, in the absence of chlorine,
primary effluents were toxic, while effluents from the secondary treatment
process were virtually nontoxic.
Chlorinated municipal sewage typically has a combined available chlorine
residual which may vary from 0.1 mg/1 to several times this value and the
optimum residual may be 3 to 4 mg/1 measured amperometrically. On the other
hand, information presented herein indicates that acute toxicity or sublethal
toxic conditions for fish are likely when chlorine residuals exceed 0.02 mg/1.
Therefore, the major step in obtaining a nonlethal treated municipal sewage
is limitation of chlorine residual to less than 0.02 mg/1 chlorine in the
effluent, measured amperometrically. In addition to limiting chlorine residual,
acute toxicity of municipal sewage can be reduced to virtually nil if it under-
goes secondary treatment. These objectives can be attained using known tech-
nology and principles and without jeopardizing public health or other water
uses.
A-27
-------
SERVIZI, J.A. and R.W. GORDON
1973
DETOXIFICATION OF KRAFT PULP MILL EFFLUENT BY AN AERATED LAGOON
PULP PAPER MAGAZINE CAN. 74(9):103-110
An 8-month study of the aerated lagoon at Kami oops Pulp and Paper Ltd.
revealed that black liquor spills were responsible for substandard detoxifica-
tion on some occasions. Effluents resulting from pulping green Douglas fir
or spruce chips were sometimes associated with substandard detoxification,
but not always. Evidence was found that residual toxic materials, whatever
their source, might be resistant to biological treatment.
SERVIZI, J.A., D.W. MARTENS, and R.W. GORDON
1978
ACUTE TOXICITY AT ANNACIS ISLAND PRIMARY SEWAGE TREATMENT PLANT
PROGRESS REPT. NO. 38, INTERNATIONAL PACIFIC SALMON
FISH. COMM., NEW WESTMINSTER, B.C., CANADA: 12 P.
Continuous flow and static bioassays of dechl orinated primary sewage
were conducted at Annacis Island sewage treatment plant using fingerling
sockeye salmon (Oncorhynchus nerka). Geometric mean survival time (CMST)
was determined using undiluted effluent, and survival during 96 hr exposure
to a range of dilutions was measured. Acute toxicity was greater during
continuous flow than during static bioassays. In addition, acute toxicity
was greater during dry weather than during wet weather flow conditions.
Mortalities were usually 100% during bioassays of 65% v/v dechlorinated
sewage but no mortalities occurred at 10% v/v.
Results were compared with acute toxicities measured at three other
primary sewage treatment plants in the Greater Vancouver Sewerage and
Drainage District, plus primary plants in San Francisco and Seattle.
Summation of toxic units attributed to anionic surfactants, un-ionized
ammonia, cyanide, nitrite and metals measured failed to account for all the
acute toxicity measured.
A-28
-------
SERVIZI, J.A., E.T. STONE, and R.W. GORDON
1966
TOXICITY AND TREATMENT OF KRAFT PULP BLEACH PLANT WASTE
PROG. REPT. NO. 13, INT. PACIFIC SALMON FISH.
COMM., NEW WESTMINSTER, B.C., CANADA: 34 P.
Some lethal and sub-lethal effects of neutralized kraft pulp bleach
waste (NBW) on sockeye and pink salmon in fresh water were investigated.
Sockeye and pink salmon alevins suffered reduced growth at concentrations
of NBW much lower than those found toxic to fingerling sockeye. Prolonged
exposure to dilute NBW resulted in deaths of adult migrant sockeyp, but
differences between adults and finger-lings in resistance to NBW was not
demonstrated conclusively. Viability of sperm and ova was not reduced in the
case of adult sockeye which survived exposure to NBW. Experiments with
biological treatment of the waste indicated that, although the initial toxic
and chemical strength of NBW varied widely, a reduction of BOD by about 60%
would render the waste almost non-toxic to fingerling sockeye. Possible
mechanisms by which lethal and sub-lethal toxic effects occur are discussed
and recommendations are made for further research.
SERVIZI, J.A., R.W. GORDON, and D.W. MARTENS
1968
TOXICITY OF TWO CHLORINATED CATECHOLS, POSSIBLE COMPONENTS OF
KRAFT PULP MILL BLEACH WASTE
PROGRESS REPT. NO. 17, INTERNATIONAL PACIFIC SALMON FISH. COMM.,
NEW WESTMINSTER, B.C., CANADA: 43 P.
Young pink salmon were less tolerant of tetrachlorocatechol than were
sockeye. Advanced sockeye alevins were more tolerant of tetrachl orocatechol
than were freshly hatched alevins, fry or smolts. Sublethal concentrations of
di- and tetrachl orocatechol caused an increase in respiration rate which, it
is believed, indicated disruption of cellular processes by uncoupling oxi dative
phosphoryl ation. Tetrachl orocatechol was apparently oxidized by biological
treatment with activated sludge and it was concluded that all chlorinated
catechols and phenols, except pentachl orophenol , would be oxidized by this
treatment, if present in bleach waste. Toxic strengths of chlorinated
catechols and phenols were between those of the non-chlorinated molecules
and a common insecticide. Application of the results was discussed in light
of the possible synergistic effects resulting from a mixture of chlorinated
organic compounds and other toxicants of industrial and domestic origin.
A-29
-------
SHEFFY, T.B. and J.R. ST. AMANT
1980
TOXIC SUBSTANCES SURVEY OF LAKE MICHIGAN, SUPERIOR
AND TRIBUTARY STREAMS: FIRST ANNUAL REPORT
WISCONSIN OEPT. NATURAL RESOURCES: 96 P.
In July, 1979, the Department of Natural Resources received a grant from
the Wisconsin Coastal Management program to conduct a systematic and compre-
hensive survey of 16 toxic substances in Wisconsin's coastal zone. The first
year of the ongoing project involved the collection and analysis of 283 fish
samples from 63 locations in the coastal zone, including 23 nearshore, 3
offshore and 37 tributary stream sampling stations along Lakes Michigan and
Superior. The major objectives of this survey, the sampling plan and the
findings are discussed.
SHUMWAY, D.L.
1968
THE EFFECTS OF UNBLEACHED KRAFT MILL EFFLUENTS ON SALMON.
II. FLAVOR OF JACK COHO SALMON
TECH. BULL. NO. 217, NCASI, NEW YORK, NY: 47-53
A preliminary study was conducted on the influence of exposure to untreated
and biologically treated unbleached kraft mill effluent on the flavor of coho
salmon flesh. Measurable cooked flavor impairment resulted from exposure
to untreated effluents for 72 to 96 hours at volume concentrations above 1.5
percent. No flavor impairment was noted when fish were exposed to 2.9 volume
percent, the highest concentration tested, of biologically treated effluent.
JAMES R. ST. AMANT, MARY E. PARISO, AND THOMAS B. SHEFFY
1984
POLYCHLORINATED BIPHENYLS IN SEVEN SPECIES OF LAKE MICHIGAN FISH, 1971-1981
IN TOXIC CONTAMINANTS IN THE GREAT LAKES. ED.: 0. NIRAGU AND S. SIMMONS,
JOHN WILEY AND SONS, INC. NEW YORK
In a recent study by the Wisconsin Department of Natural Resources,
seven species of fish from Lake Michigan and Green Bay were monitored for
PCBs from 1971 to 1981. An overall decrease in PCS concentration was observed
for all species except walleye. High levels of PCBs (maximum 22,40 ppm)
identified at the beginning of the study decreased steadily to the present
condition where all species monitored were below the U.S. Food and Drug
Administration tolerance level of 5.00 ppm. These trends demonstrate the
effectiveness of legislation which banned production, established strict
controls on use and disposal, and ultimately reduced the input of PCBs to
Lake Michigan.
A-30
-------
STERN, A.M. and C.R. WALKER
1978
HAZARD ASSESSMENT OF TOXIC SUBSTANCES: ENVIRONMENTAL FATE TESTING OF
ORGANIC CHEMICALS AND ECOLOGICAL EFFECTS TESTING
IN: J. CAIRNS, JR., K.L. DICKSON, AND A.W. MAKI (EOS.),
ESTIMATING THE HAZARD OF CHEMICAL SUBSTANCES TO AQUATIC LIFE,
ASTM SPECIAL TECH. PUBL. 657, ASTM, PHILADELPHIA, PA: 81-131
In order to evaluate the potential hazards associated with the commercial
use of chemical substances, an assessment of their ultimate environmental fate
must he made. Fate, in this sense, can be defined as the transport and disposi-
tion of a chemical after it is released into the environment from a point source
(manufacturing plant) or a disposal site (landfill, waste treatement plant, etc.).
Determination of chemical fate could have considerable impact on predicting the
potential adverse environmental effects of chemical pollutants, since it would
help identify: (a) the areas over which pollutants would be distributed;
(b) the types of reactions they would be subjected to during transport and after
deposition; (d) the sensitive biological targets that would be brought under
their influence; and (e) the sequence of biological tests and conditions relative
to the site of impact, concentration, period of exposure, and specificity
of biological impact. Therefore, tests designed to allow assessments to be made
of the environmental fate of chemical contaminants must address the generic
areas of chemical mobility and persistence, and toxicological and ecological
significance of the exposure of the organism, population, and community.
Several studies have reviewed and evaluated test methods for determining the
environmental fate of chemical contaminants. While these reports cover current
test methods, few attempts have been made to design test protocols or to
prioritize test for individual chemicals. Unfortunately, available documents on
environmental fate testing indicate that the design of experimental procedures
is often made on an ad hoc basis and is extremely variable. In contrast to the
documentation of toxicity testing, literature concerned with environmental fate
testing is virtually unknown. This lack of standardization is perhaps a result
of the almost infinite ways that chemicals may be released into and reside in
the environment. However, the hazard involved in using unstandardized tests is
that, despite the expenditure of a great deal of money and effort, little insight
is provided regarding the mobility of a chemical through the environment and its
subsequent fate as a result of degradation and alteration processes. This
is particularly true if the test is not well designed. Furthermore, the
interpretation of unstandardized tests frequently varies and thus, in turn,
makes it difficult to compare one chemical with another.
The following discussion is intended to furnish systematic guidelines for
the testing of chemical-environmental fate. It is an attempt to provide a basis
for constructing logical test protocols which are both cost effective and pro-
ductive in that they would expedite reasonable adjudications concerning the
safety of commercially useful chemicals. It must be emphasized that the
development of any methodology is dependent upon the state of the art at the time
it is devised. Therefore, the approach described here must be considered an
interim solution to the problem of assessing the environmental fate of chemical
pollutants and must be amenable to revision as new information and technologies
are made available.
A-31
-------
SULLIVAN, J.R. andJ.J. DELFINO
1982
A SELECT INVENTORY OF.CHEMICALS USED IN WISCONSIN'S LOWER FOX RIVER BASIN
UNIVERSITY OF WISCONSIN SEA GRANT INSTITUTE, MADISON, WI: 176 P
Increased awareness of the sources, distribution and fate of chemicals
in natural waters led to an assessment of the use or production of these
potentially hazardous materials in the Lower Fox River Basin in northeastern
Wisconsin. The inventory is one phase of a program for assessing which organic
compounds may be troublesome when they reach the aquatic environment. In
effect, the inventory is a companion approach to an analytical effort designed
to locate potentially toxic organic pollutants. Rather than doing countless
and expensive scans on gas chromatography/mass spectrometry systems to identify
organic compounds, certain chemicals can be traced down through an approach
outside the laboratory. Though useful itself, the inventory must be interwoven
with an analytical program so the findings may be applied to the aquatic
environment.
In essence, the inventory provides a means of ascertaining the types of
chemicals that may be expected to occur in the aquatic environment; then the
analytical program can focus on or intensify its efforts by looking for
specific compounds and their structurally altered products. When a chemical
is identified from the inventory as being used, produced or manufactured within
the basin, further effort can follow.
THOMANN, R.V.
1978
SIZE DEPENDENT MODEL OF HAZARDOUS SUBSTANCES IN AQUATIC FOOD CHAIN
ECOL. RES. SER., EPA-600/3-78-036, ENVIRON. RES. LAB.,
U.S. EPA, DULUTH, MN: 39 P.
In order to incorporate both bioaccumulation of toxic substances directly
from the water and subsequent transfer up the food chain, a mass balance
model is constructed that introduces organism size as an additional independent
variable. The model represents an ecological continuum through size dependency;
classical compartment analyses are therefore a special case of the continuous
model. Size dependence is viewed as a very approximate ordering of trophic
position.
The analysis of some PCS data in Lake Ontario is used as an illustration
of the theory. A completely mixed water volume is used. Organism size is
considered from 100 urn to 10^ urn. PCS data were available for 64 urn net hauls,
alewife, smelt, sculpin and coho salmon. Laboratory data from the literature
were used for preliminary estimates of the model coefficients together with
the field data. The analysis indicated that about 30% of the observed 6.5 ug
PCB/gm fish at the coho salmon size range is due to transfer from lower levels
in the food chain and about 70? from direct water intake. The model shows
rapid accumulation of PCS with organism size due principally to decreased
excretion rates and decreased biomass at higher trophic levels.
The analysis indicates that if a level of 5 ug PCB/gm at 10^ urn is sought,
total (dissolved and particulate) water concentration would have to be about
36 ng/1 or about 66% of the present 55 ng/1 .
A-32
-------
U.S. ENVIRONMENTAL PROTECTION AGENCY, REGION V
1977
GUIDELINE FOR THE POLLUTIONAL CLASSIFICATION OF GREAT LAKES HARBOR SEDIMENTS
U.S. EPA, REGION V, CHICAGO, IL: 7 P.
Guidelines for the evaluation of Great Lakes harbor sediments, based on
bulk sediment analysis, have been developed by Reigon V of the U.S. Environmental
Protection Agency. Thpse guidelines, developed under the pressure of the need
to make immediate decisions regarding the disposal of dredged material , have
not. been adequately related to the impact of the sediments on the lakes and are
considered interim guidelines until more scientifically sound guidelines are
developed.
The guidelines are based on the following facts and assumptions:
1. Sediments that have been severely altered by the activities of men
are most likely to have adverse environmental impacts.
2. The variability of the sampling and analytical techniques is such
that the assessment of any sample must be based on all factors and
not on any single parameter with the exception of mercury and poly-
chlorinated biphenyls (PCBs).
3. Due to the documented oioaccumul ation of mercury and PCBs, rigid
limitations are used which override all other considerations.
Sediments are classified as heavily polluted, moderately polluted, or
nonpollutedby evaluating each parameter measured against the scales shown
below. The overall classification of the sample is based on the most pre-
dominant classification of the individual parameters. Additional factors
such as elutriate test results, source of contamination, particle size
distribution, benthic macroinvertebrate populations, color, and odor are also
considered. These factors are interrelated in a complex manner and their
interpretation is necessarily somewhat subjective.
VAN HORN, W.M., J.B. ANDERSON, and M. KATZ
1949
THE EFFECT OF KRAFT PULP MILL WASTES ON SOME AQUATIC ORGANISMS
TRANS. AM. FISH. SOC. 79:55-63
A study has been made of the toxic substances which may be found in
kraft pulp-mill waste-waters. It has been determined that the sulphides,
mercaptans, resin acid soaps, and sodium hydroxide constitute the greatest
hazard. The minimum lethal concentration of these and other materials to
fresh-water minnows, Daphnia, and aquatic insect larvae has been established.
Methods have been devised for evaluating these materials in kraft-waste waters,
and data from the examination of the wastes of a typical northern kraft mill
are presented.
A-33
-------
VEITH, G.D.
1975
BASELINE CONCENTRATIONS OF POLYCHLORINATED BIPHENYLS AND
DDT IN LAKE MICHIGAN FISH, 1971
PESTIC. MONIT. J. 9(l):21-29
Responding to the recommendations of the Lake Michigan Interstate
Pesticide Committee, the author aimed to establish baseline data on poly-
chlorinated biphenys (PCBs) and DDT in Lake Michigan fish in 1971. Because
the past 2 years had witnessed unprecedented legislative action to protect
food resources and other aquatic species near the top of the food chain from
persistent hazardous chemicals, the author also attempted to gauge the
impact of cooperative legislative action on the quality of large lakes.
Thirteen species of fish taken from 14 regions of Lake Michigan in the fall
of 1971 were analyzed for PCBs and DDT analogs. Mean wet-weight concentrations
of PCBs similar to Aroclor 1254 ranged from 2.7 ppm in rainbow smelt to 15 ppm
in lake trout. Most trout and salmon longer than 12 inches contained PCBs at
concentrations greater than the tolerance level of 5 ppm established by the
Food and Drug Administration, U.S. Department of Health, Education, and Welfare.
Mean concentrations of total DDT ranged from less than 1 ppm in suckers to
approximately 16 ppm in large lake trout. The presence of the major chlorinated
hydrocarbons was confirmed by gas-liquid chromatography/mass spectrometry;
additional PCB confirmations were obtained through perch!orination. The most
abundant PCBs were tetra-, penta-, hexa-, and heptachlorobiphenyls which are
similar to commercially prepared Aroclor 1254; lesser chlorinated PCBs were
present in fish from nearshore waters.
WALDEN, C.C., T.E. HOWARD, and G.C. FROUD
1970
A QUANTITATIVE ASSAY OF THE MINIMUM CONCENTRATIONS OF KRAFT MILL
EFFLUENTS WHICH AFFECT FISH RESPIRATION
WATER RES. 4:61-68
Procedural variables, in the buccal cavity technique for measuring the
cough response of fish to kraft mill effluents, have been examined. The
quantitative procedure which was developed can measure the threshold concentra-
tion level at which effluents produce respiration abnormalities in fish. The
elapsed time requirement for this assay is the same as for an acute bioassay.
t
Minimum response concentrations, for neutralized pulping and bleaching
effluents from a typical modern kraft pulp mill, were 1.1 and 4.0 per cent
respectively.
The nature of aberrations observed in the respiration of fish exposed
separately to pulping and bleaching effluents was identical, indicating
that these effluents may contain similar toxic principles. Cough response
observations indicate that fish acclimate to sublethal concentrations of
kraft effluents, the time required for acclimation being related directly
to the effluent concentration.
A-34
-------
WARREN, C.E.
1972
PHASES I AND II: EFFECTS OF PULP AND PAPER MILL
EFFLUENTS ON GROWTH AND PRODUCTION OF FISH
RES. GRANTS #B-004-ORE AND B-013-ORE, OFFICE WATER RESOURC. RES.,
U.S. OEPT. INTERIOR: 115 P
This report ia an Oregon State University research project on the
effects of primary treated and of biologically stabilized kraft mill effluents
on the growth and production of salmon and trout. The research was planned
to be conducted in two phases.
Phase I was concerned with two kinds of laboratory studies of the effects of
kraft mill effluents on salmon. In some of these laboratory studies,
juvenile chinook salmon (Oncorhynchus tshawytscha) were held in continuous-
flow aquaria or in exercise channels at different concentrations of kraft
mill effluent and fed different ration levels, in order to determine the
concentrations that have little or no direct effect on the relationship
between the food consumption and growth rates of the fish.
Phase II of this research has been conducted in three large experimental
stream channels, much more nearly representative of natural streams. Each
stream channel is about 6 feet wide and 320 feet long, and each receives a
flow of 0.67 cfs of water pumped from the Willamette River. Different species
of salmon and trout were stocked in these stream channels, one of which
received primary treated effluent for about one year, then biologically
stabilized effluent for more than one year. Studies of the growth and pro-
duction of the sal mom" ds, their food habits, the kinds and availability of
insects and other fish food organism, and the composition and density of
the algal community component were conducted.
A-35
-------
WARREN, C.E., J.H. WALES, G.E. DAVIS, and P. DOUDOROFF
1964
TROUT PRODUCTION IN AN EXPERIMENTAL STREAM ENRICHED WITH SUCROSE
J. Wild!. Manage. 28(4):617-660
From 1960 through 1963, three experiments were performed on the production,
food habits, and food consumption of coastal cutthroat trout (Salmo clarki clarki)
in sucrose-enriched and in unenriched sections of Berry Creek, a small woodland
stream in the Willamette River Basin of Oregon. These experiments were part of
a general investigation of the trophic pathways through which energy from
light, organic debris, and dissolved organic matter enters into the production
of fish and other organisms.
The flow in a 1,500-foot portion of Berry Creek was controlled by means of a
diversion dam and a bypass canal. Four sections of this portion of the
stream, each consisting of a riffle and a pool, were separated by fine screens
which prevented the drifting of fish-food organisms from one section to the
next. The water in two sections was continuously enriched by introducing a
few milligrams of sucrose per liter, and most of the deciduous forest canopy
was removed from one of the enriched and one of the unenriched sections. Only
the enrichment with sucrose led to large and consistent increases in food
consumption and production of trout: food consumption was increased about
twofold and trout production usually much more than sevenfold. Trout production
increased so much more than food consumption because only a relatively small
portion of the comparatively large amount of food consumed in the enriched
sections was required for maintenance of the trout stocks. The maintenance
food produced and available in the unenriched sections was required for main-
tenance, with little left for promoting growth.
Food consumption values are believed to be more reliable measures of the
relative productivity of the different sections for trout than are production
values. Results of studies of food habits of the trout and available data on
biomasses of insects in the riffles indicate that increased food consumption
and production of trout in the enriched sections were made possible by greater
abundance of aquatic food organisms, especially of tendipedid (chironomid)
larvae, the consumption of terrestrial food being roughly equal in all sections.
Introduction of sucrose resulted in growth of the bacterium Sphaerotilus
natans, a slime organism frequently associated with organic pollution. This
bacterial growth provided food and habitat for tendipedid larvae, the most
important food organisms of trout in the enriched sections. Concepts of
trophic relations in aquatic ecosystems and the application of these concepts
to problems of water resource management are discussed in the light of the
findings.
A-36
-------
WARREN, C.E., W.K. SEIM, R.O. BLOSSER, A.L. CARON, and E.L. OWENS
1974
EFFECT OF KRAFT EFFLUENT ON THE GROWTH AND PRODUCTION OF SALMONID FISH
TAPPI 57(2): 127-132
Studies of the effects of kraft mill effluents - receiving only primary
treatment or biological stabilization as^well - on the growth of salmonid fish
in aquaria and on their growth and production and the availability of their food
organisms in laboratory stream communities and in large experimental stream
channels were conducted over a period of 6 years. Neither primary treated
nor secondary treated effluent had much, if any, effect on the growth of
salmonids in aquaria at BOO concentrations below about 0.5 mg/liter, but
these effluents usually did affect growth at higher concentrations. The
effluents did not deleteriously affect the growth and production of salmonids
in laboratory stream communities and experimental stream channels but did
change the composition of the benthic community of algae and insects at a
BOD concentration of 0.75 mg/liter.
WEBB, P.W. and J.R. BRETT
1972
THE EFFECTS OF SUBLETHAL CONCENTRATIONS OF WHOLE BLEACHED KRAFTMILL
EFFLUENT ON THE GROWTH AND FOOD CONVERSION EFFICIENCY OF UNDERYEARLING SOCKEYE .,
J. FISH. RES. BOARD CAN. 29(11):1555-1569
Changes in growth rate and gross conversion efficiency were measured for
underyearling sockeye salmon during and after exposure to full bleached kraft
mill effluent (BKME). Five groups of fish were exposed for 56 days to 0, 1.0,
2.5, 10, and 25% BKME (v/v). Fresh 24-hr composite effluent at pH 6.8 was used
daily after filtering. Growth was followed for a further 56 days after BKME
exposure. Temperature was held at 15 C and dissolved oxygen between 90 and 100%
air saturation. Growth rate and conversion efficiency were unaffected at 1.0
and 2.5% BKME. Reduced mean growth rate and conversion efficiency at 10% BKME
were not statistically significant from controls but were considered to be
biologically important in estimating threshold response levels. Significant
reductions were found at 25% BKME. No recovery in retarded growth was found
after exposure to RKME. Condition factor and percentage dry weight were not
affected. It was concluded from computed response curves that the EC50 of the
effluent was approximately 3.7% (v/v).
A-37
-------
WECKWERTH, H.W. and B.A. FENSKE
1982
AUTOMATIC WATER QUALITY MONITORING OF THE FOX AND WISCONSIN RIVERS 1972-1981
WATER QUALITY EVALUATION SEC., BUREAU WATER RESOUR. MANAG.,
WISCONSIN DEPT. NAT. RESOUR., MADISON, WI: 325 P.
The automatic water quality monitoring system for the Lower Fox River and the
Wisconsin River was installed in 1970-1971. The system consists of eleven
stations, five on the Fox River and six on the Wisconsin River. All stations
are located in existing buildings, either hydroelectric plants or papermills.
No special heating arrangements were necessary except in some cases power supplies
are covered or ventilated depending upon the season.
Two basic systems of flow are utilized. One system uses the head of the
water source to supply a continuous flow to the monitor. The monitor in this
installation is located below the source water level. The other system uses a
nonsubmersible pump to lift the water to the water monitor.
About half the stations have been relocated from the original installation.
All have been modified and refined to improve reliability and serviceability.
Special emphasis has been placed upon getting reliable water flow to the monitor
water chamber and achieving a reliable effluent system. This has involved
designing water filter and flushing systems to fit the station. In cases of
excessive debris, a filter system to assure adequate influent sample, yet
prevent debris from affecting the monitor apparatus, is necessary for reliable
performance.
Each station of the system is cleaned, checked and calibrated on an average
of ten days to two week intervals depending upon the season and flow conditions.
Necessary repairs and electronic servicing and testing is done as required
in addition to the routine maintenance.
After about ten years of operation, the performance is at about an 80 to 90
percent satisfactory unit response level. This includes all problem factors
that affect system operation. Some of these factors are powerline failures,
storms, computer downtime, teletype lines, plumbing apparatus, electronics,
flow problems, hydroelectric plants repair and human error.
A-30
-------
WISCONSIN DEPARTMENT OF NATURAL RESOURCES
1978
INVESTIGATION OF CHLORINATED AND NONCHLORINATED COMPOUNDS IN THE
LOWER FOX RIVER WATERSHED
EPA 905/3-78-004 U.S. EPA, CHICAGO, IL : 229 P.
This study was developed because of the increasing concern over potentially
toxic chlorinated and nonchlorinated organic compounds entering the environment.
The Lower Fox River was studied because of the large number of industrial and
municipal wastewater treatment systems discharging to this 64-kilometer stretch
of river. Effluents, surface water, seston, snowmelt, sediment, fish, and
clams were sampled.
A total of 105 compounds were identified by gas chromatography/mass
spectrometry. An additional 20 compounds were characterized but not conclusively
identified. Twenty identified compounds are on the U.S. EPA Consent Decree
Priority Pollutant List. The study indicates that PCBs and some other chloro-
organic compounds are associated with effluent suspended solids and that solids
removal reduces effluent contaminant concentrations.
Effluent concentration ranges in ug/L for compounds quantified by GC/MS were:
benzothiazole 10-30, hydroxybenzothiazole 10-30, methyl thiobenzothiazole
10-40, trichloroquaiacols 10-60, tetrachloroguaiacol 10-50, dichlorophenol
15-40, Trichlorophenol 5-100, Tetrachlorophenol 2-20, Pentachlorophenol 5-40,
dehydroabietic acid 100-8500, and PCBs 0.4-68.0. It is possible, but not
proven, that some compounds were formed by process or effluent chlorination.
Clams were found to rapidly bioaccumul ate PCBs. After a 27-28 day exposure,
PCS concentrations in clams ranged from 255 to 740 ug/kg. Fish fillet samples
contained PCB concentrations up to 90 mg/kg. Sediments throughout most of the
river were found to be contaminated with PCBs. Toxicity data are lacking on
many of the identified compounds and additional data are needed.
WISCONSIN DEPARTMENT OF NATURAL RESOURCES
1978
FOX RIVER WASTE LOAD ALLOCATION-MODEL DATA
WATER QUALITY EVALUATION SECTION, DIV. OF ENVIRON. STANDARDS,
WISCONSIN DEPT. NAT. RESOUR., MADISON, WI: 75 P.
Water Quality Surveys were conducted in the Lower Fox River and Green Bay
between the DePere Dam and Long Tail Point. A slow long term improving trend
can be seen in comparison to previous years, but the river and inner bay are
still heavily enriched, causing heavy algae blooms. Dissolved oxygen and
temperature stratification still occur occasionally. Sediment Oxygen Demand
is lower than in previous years.
A-39
-------
I
WI D.N.R., U.S.G.S., U.S. FISH WILDL. SERV., U.S. EPA REGION V, and
UNIV. WI WATER CHEM. DEPT.
1983
FINAL REPORT OF THE TOXIC SUBSTANCES TASK FORCE ON
THE LOWER FOX RIVER SYSTEM
WI DEPT. NAT. RESOUR., U.S. GEOL. SURV., U.S. FISH WILDL. SERV.,
U.S. EPA REGION V, and UNIV. WI WATER CHEM. DEPT.: 70 P.
More than 100 chemicals have been identified in the Lower Fox River System.
The chemicals have been placed into categories based on their known or potential
effects on man or fish and wildlife. Chemicals of primary concern (Category I)
are those which may cause chronic toxicity to humans or other animals through
consumption of fish and wildlife, and those which may cause acute/chronic
toxicity or taste and odor effects to fish and wildlife of the Lower Fox River
and Green Bay. Chemicals in category I include PCBs, PCDDs, PCDFs, resin and
chlorinated resin acids, chlorophenols and ammonia. This category is the main
focus of this report. Chemicals placed in Category II (found less frequently
than Category I chemicals and not believed to be a problem) and Category III
(present but effects uncertain) are not reviewed in detail.
PCBs
Polychlorinated biphenyls (PCBs) are documented as being present in the Fox River/
Green Bay ecosystem. Although PCBs are considered toxic pollutants and a large
toxicological data base exists, some uncertainties remain in the overall under-
standing of toxic effects. Of particular significance is the fact that micro-
contaminants in PCB mixtures, such as the polychlorinated-dibenzofurans, may
be responsible for some of the observed toxic effects. The dominant PCB mixture
identified in the Fox River, Aroclor 1242, comes from wastewater discharges
associated with secondary fiber paper mills which deink carbonless copy paper.
PCDDs
Polychlorinated dibenzo-p-dioxins (PCDDs), particularly 2,3,7,8-tetrachloro-
dibenzo-p-dioxin (TCDD), are extremely toxic compounds^ The degree of chloro-
nation and substitution pattern on the parent dioxin molecule determines its
toxicity. PCDDs occur as microcontaminants of ctil orinated phenols, such as
2,4,5-trichlorophenol and pentachlorophenol . '
PCDFs
Polychlorinated dibenzofurans (PCDFs) are not well-studied compounds. Certain
isomers are extremely toxic to certain species, rivalling certain dioxin
isomers in toxicity. The existence of PCDFs in the Fox River/Green Bay system
is suspected because they occur as contaminants of PCB mixtures and various
chlorinated phenolic compounds.
Resin and Chi orinated Resin Acids
Resin acids are naturally occurring compounds in the environment. They occur
in wood, especially pine species, and are released to the aquatic environment
through the pulping of wood. Resin acids are also a major component of rosin
size, a raw material used by the pulp and paper industry.
A-40
-------
Page 2
Final Report of the Toxic Substances Task Force on the Lower Fox River System
Chlorophenols
Most chlorophenols, especially pentachlorophenol , have an adequate toxicological
data base. It should be noted, however, that the presence of chlorinated dioxins
as micro contaminants in certain commercial chlorophenol mixtures accounts for
a substantial portion of chlorophenol toxicity.
Ammon i a
Ammonia is a naturally occurring compound found in all surface water as the decay
product of nitrogen-containing organic matter. Ammonia is also found in sewage
effluents and some industrial discharges.
A-41
-------
APPENDIX B
B-l Fox River Stations - Municipal and Industrial Waste Discharges to
the Lower Fox River (Anon, 1985).
B-2 Toxicity and Percent of Stream Flow of Effluent Discharges to the
Fox River (Anon, 1985).
B-3 Map of Study Area and Locations of Sampling Stations for Toxicity
Evaluation of Lower Fox River Water and Sediments (RKM TT river
kilometers) (Lien et al., 1985).
B-4 Physical and Chemical Data for Water Collected from the Lower Fox
River at Various Locations and Dates (Lien et al., 1985).
B-5 Decoded Pecentage Survival (i.e. grand average) of Young Walleye
of Different Developmental Phases for Three Stock Sources From
Wisconsin Waters (Hokanson and Lien, 1986).
8-6 Water Chemistry at River Intake During Hatching Experiments (Auer
and Auer, 1986).
B-7 Chemical Conditions at the Sediment-Water Interface (Auer and
Auer, 1986).
B-8, Chemical Oxygen Demand (Auer and Auer, 1983).
B-9, &
B-10
B-ll Walleye Egg Incubation Sites in 1986 (Brooke et al., 1986).
B-12 Survival of Walleye Ova Incubated in Non-groomed Tissue Culture
Triads During April 1986. (Average of all Replicates and all
Females, Uncorrected for Initial Ova Viability) (Brooke et al., 1986).
B-13 Abundance of Fish Species Caught by Fyke Nets in the Lower Fox
River, April, 1985 (Balcer et al. 1986). '
-------
Fox River Scations
Greeft Bay STP
Green Bay Packaging
Procter & Gamble
American Can
Fort Howard
GREEN BAY
GREEN BAY
10
DePero STP _
Nicolet Paper
OE PERF
Wrightttown STP«
N
KAUKAUNA
NEENAH
LAKE
WINNEBAGO
Heart of th« ValUy STP
Thilmany Paper
Appleton Paper
Midtec
Appleton STP
Menasha SO East & West
.Wisconsin Tissue
u i^rlr-George Whiting
imoerly-ClarR
4eenoh-Menasha STP
"Bergstrom Paper
'Kimberly-Clark
Badger Globe
Municipal and Industrial Waste Discharges to the lower Fox River.
(Anon, 1985)
B-l
-------
Toxicity and Percent of Stream Flow of Effluent Discharges to the Fox River,
(Anon, 1985)
Effluent ID or
River Station No.
FHM NOEL
% Concentration
Oaphm'd NOEL
% Concentration
% Stream Flow
at Sample Time
% Stream
at 7Q10
Bergstrom Paper
Kimberly Clark J
Kimberly Clark L
Kerwin Paper
Appleton Paper
Mid-Tech. Paper
Wisconsin Tissue
Nicolet Paper
Thilmany Paper
Green Bay STP
Neenah-Menasha STP
rort Howard Paper
James River Paper
Kerwin Paper (2)
3roctor Gamble
3reen Bay Packaging
Mid Tech (2)
-ppleton STP
'70.7
**
>100
**
**
**
**
**
**
17.7
>100
70.7
>100
>100
70.7
>100
>100
35.4
70.7
>100
35.4
**
70.7
**
**
>100
>100
<100*
**
**
**
<100*
70.7
>100
**
35.4
.121
.137
.052
.021
.088
.186
.140
.258
.680
.92
.22
.54
.23 j
.05
.11
.22
.26
.28
.624%
.704
.268
.202
.842
1.768
.411
.757
1.992
5.35
1.20
2.89
1.62
.31
.82
1.53
1.52
1.51
Not calculable at concentrations lower than 100% due to toxicity of dilution water.
" Not calculable
B-2
-------
10
A. Mouth.
C. RKM 2.6..
I.RKM39.9
J. RKM 4S.4
K. RKM 52.8
L. RKM 63.2
F. RKM 10.5
G. RKM II.I
B. RKM 1.0
E. RKM 7.6
H. RKM 28.3
.M. LakeW
Map of Study Area and Locations of Sampling Stations for Toxi-
city Evaluation of Lower Fox River Water and Sediments (RKM =
river kilometers). (Lien et al ., 1985)
B-3
-------
Physical and Chemical Data for Water Collected
From the Lover Fox River et Varioua location! and Datea
Sampling Stetioo1 (Lien 6t dl . , 1985)
!.. 30-31, 1985
pH
alkal mg/l
cond UI/CB
hardnee* mg/l
Cl mg/l
NO; mg/l
N03 mg/l
P04 mg/l
S04 mg/l
(fflft* mg/l (total)
NH3-R mg/l2
aulfidea mg/l
March 13-14, 1985
temp 'C3
pH
alkal mg/l
cond ye /cm
hardneaa mg/l
Cl mg/l
N02 mg/l
N03 mg/l
P04 mg/l
S04 mg/l
Iffl.* mg/l (total)
KHj-N mg/l2
sulfidea mg/l
April 30, 1985
temp *C'
pH
7.96
164.8
397
193.9
18
<0.2
0.9
<0.2
22.7
0.56
0.015
3
7.63
133.6
440
164.9
20
<0.05
4.0
<0.15
22.5
1.07
0.014
<1.0
18
8.38
alkal mg/l 153.7
cond u*/cm 419
hardneaa mg/l 188.1
Cl mg/l
N02 mg/l
N03 mg/l
P04 mg/l
S04 mg/l
Iffl4* mg/l (total)
NHj-N mg/l2
aulfidea mg/l
31.3
<0.05
1.1
<0.10
36.0
1.93
0.102
<1.0
JJ
7.97
163.8
361
188.0
10
<0.2
1.4
<0.2
19.7
£
8.00
163.4
309
187.6
14
<0.2
1.4
<0.2
19.7
0.24 0.26
C.007 0.008
3
7.80
146.4
380
175.5
16
<0.05
4.0
<0.15
19.0
3
7.87
145.7
348
178.0
16
<0.05
4.0
<0.15
19.0
0.40 0.44
0.008 0.010
<1.0
17
8.90
141.8
300
159.1
13.4
<0.05
l.l
<0.10
16.0
0.26
0.048
<1.0
<1.0
17
8.75
141.3
315
159.2
13.6
<0.05
1.1
<0.10
16.0
0.24
0.035
-------
Decoded percentage survival (i.e. grand average) of young
walleye of different developmental phases for three stock
sources from Wisconsin waters. (Hokanson and Lien, 1986)
Phase of
development
Prolarvae
Source
Lower Fox River Sturgeon Bay Chipoewa Flowage P a/
b/96.3
98.4
98.1
0.7168
Post larvae I
(P,) 73.3
Postlarvae II
(Pi) 84.3
Juvenile
(Pi) 96.4
Overall
survival c/ 53.8
58.9 90.8 0.0001
94.8 95.2 0.0830
97.0 90.6 0.2683
51.6 72.3 0.0440
Probability level of significance in survival of young walleyes among
sources as determined by ANOVA.
Underscore signifies no significant differences in mean response for the
indicated stock source (p < .05; Tukey's multiple range test).
Overall survival probability for a given stock is equal to P^ x ?2 x Pj x
where Pi is expressed as a decimal fraction for survival of offspring
from each female.
B-5
-------
Water chemistry at river intake during hatching experiments
(Auer and Auer,'1986)
Date
4/18
4/19
4/20
4/21
4/22
4/23
4/24
4/25
4/26
4/27
4/28
4/29
4/30
5/1
pH
8.76
8.94
8.70
8.97
8.83
8.88
8.82
8.88
8.87
8.54
8.91
8.90
8.92
8.94
DO
(mg02/L)
14.6
16.5
11.0
12.8
10.3
9.5
10.0
11.0
10.4
10.5
11.0
10.6
10.6
10.2
NH3-N
(ugN/L)
110
80
86
129
187
162
153
183
44
159
203
207
205
74
N02-N
(ugN/L)
8
9
9
9
7
4
5
11
11
7
12
10
10
9
H2S
(ug/L)
0.9
0.8
0.9
0.5
0.8
0.7
0.8
0.6
0.6
1.6
0.7
0.7
0.6
0.5
Mean 8.85 11.4 142 9 0.8
B-6
-------
Chemical conditions at the sediment-water Interface
(Auer and Auef, 1986)
24 June 1985 ^ Temperature = 22 °C
Station
1
2
3
4
5
6
7
8
9
10
PH
7.45
7.22
8.23
8.11
7.65
7.39
7.54
7.75
8.25
8.18
UU
(mg02/U
6.6
5.9
5.3
6.4
0.2
0.5
4.0
3.1
6.9
4.2
m3-N
(ugN/L)
105
289
143
99
817
1874
163
386
168
257
14 August 1985 -
Station
1
2
3
4
5
6
7
8
9
10
PH
7.31
7.59
7.86
7.73
7.47
7.49
7.32
7.36
8.43
8.45
DO
(mg02/L)
3.9
5.3
6.9
6.8
0.6
0.9
2.9
1.5
7.2
7.0
NH3-N
(ugN/L)
115
155
84
272
2339
2372
1778
5199
74
73
N02-N
(ugN/L)
48
64
54
55
68
15
21
37
61
46
Temperature .=
N02-N
(ugN/L)
~
Sed..COD
(mg02/9DW)
12
41
16
24
183
157
353
463
27
319
24 ±C
Sed. COD
(mg02/gDW)
26
13
6
39
224
140
375
224
~
.._
H2S
-------
Chemical Oxygen Demand (Auer and Auer, 1983)
GREEN BAY
GREEN BAY
METROPOLITAN SEWERAGE DISTRICT
GREEN BAY PACKAGING, INC.
PROCTER a GAMBLE
PAPER PRODUTS CO
JAMES RIVER -
DIXIE NORTHERN. INC.
FOX RIVER
(SECTION I)
\ in \ ii \ i
COD (mg02/gDW)
DO-50 m\0\-\7Q
03 51-100 9 171 +
B-8
-------
X
Chemical Oxygen Demand (Auer and Auer, 1983)
LOWER
FOX RIVER
(SECTION II)
COD (mg02/gDW)
QO-50 ^101-170
H 51-100 171 +
FORT HOWARD
PAPER CO.
0 J 2 .3 .4
B-9
-------
V ;
Chemical Oxygen Demand (Auer and Auer, 1-983)
DEPERE
WASTEWATER TREATMENT©
Dl AH^
LOWER
FOX RIVER
(SECTION III)
' \ in \
:OLET PAPER
co.
COO (mg02/gDW)
DO-50
O SHOO
B-10
-------
Walleye Egg Incubation Sites in 1986 (Brooke et al., 1986)
-------
Survival of walleye ova incubated in non-groomed tissue culture
triads during April 1986. (Average of all replicates and all
females, uncorrected for initial ova viability). (Brooke et al., 1986)
Site Number Percent Survival to Hatch
9 38.2
2 36.9
8 34.7
11 27.7
5 9.5
4 8.7
6 1.9
7 0.9
10 0
B-12
-------
Abundance of Fish Species Caught by Fyke Nets in
the Lower Fox River, April, 1985 (Balcer et al. 1936)
Walleye (Stizostedion vitreum vitreum) 792'
Yellow Perch (Perca -flavescens) 807
Carp (Cvprinus carpio) 122
White Bass (Horone chrysops) 113
White Sucker (Catostomus commersoni) 106
Black Bullhead (Ictalurus melas) 22
Quillback (Carpoides cyprinus) 18
Northern Pike (Esox lucius) 11
Brown Bullhead (Ictalurus nebulosus) 8
Freshwater Drum (Aplodinotus orunniens) 7
Sauger (Stizostedion canadense) 4
Channel Catfish (Ictalurus punctatus) 4
Rock Bass (Ambloplites rupestris) 3
Burbot (Lota lota) 3
Crappie (Pomoxis sp.) 2
Redhorse Sucker (Moxostoma sp.) 1
Longnose Sucker (Catostomus catostomus) 1
Trout Perch (Percopsis omiscomaycus) 1
* Walleye collected from 22 net lifts; other species enumerated
in 8 lifts.
B-13
-------
APPENDIX B
B-l Fox River Stations - Municipal and Industrial Waste Discharges to
the Lower Fox River (Anon, 1985).
B-2 Toxicity and Percent of Stream Flow of Effluent Discharges to the
Fox River (Anon, 1985).
8-3 Map of Study Area and Locations of Sampling Stations for Toxicity
Evaluation of Lower Fox River Water and Sediments (RKM IT river
kilometers) (Lien et al., 1985).
B-4 Physical and Chemical Data for Water Collected from the Lower Fox
River at Various Locations and Dates (Lien et al., 1985).
B-5 Decoded Pecentage Survival (i.e. grand average) of Young Walleye
of Different Developmental Phases for Three Stock Sources From
Wisconsin Waters (Hokanson and Lien, 1986).
f
8-6 Water Chemistry at River Intake During Hatching Experiments (Auer
and Auer, 1986).
B-7 Chemical Conditions at the Sediment-Water Interface (Auer and
Auer, 1986).
B-8, Chemical Oxygen Demand (Auer and Auer, 1983).
B-9, &
B-10
B-ll Walleye Egg Incubation Sites in 1986 (Brooke et al., 1986).
B-12 Survival of Walleye Ova Incubated in Non-groomed Tissue Culture
Triads During April 1986. (Average of all Replicates and all
Females, Uncorrected for Initial Ova Viability) (Brooke et al., 1986)
B-13 Abundance of Fish Species Caught by Fyke Nets in the Lower Fox
River, April, 1985 (Balcer et al. 1986).
-------
Fox River Station*
Green Boy STP
Green Boy Packaging
Proctor & GambU
American Can
Fort Howard
'GREEN BAY
GREEN BAY
DePere STP
NicoUt Paper
06 PERF
Riverside*
NEENAH1
Wrightstown STP
KAUKAUNA
CENASHA
LAKE
WINNEBAGO
Hoartof th« ValUy STP
Thitmany Paper
Appleton Paper
AppUron STP
Mtnasha SD East & West
Wisconsin Tissue
't> u i Z?lr-George Whiting
(iinberly-Clorlt
^eenoh.Menasha STP
ftergstrom Paper
'Kimberly-Clark .-
Badger Globe
Municipal and Industrial Waste Discharges to the Lower Fox River.
(Anon, 1985)
B-l
-------
Toxicity and Percent of Stream Flow of Effluent Discharges to the Fox River
(Anon, 1985)
Effluent ID or
River Station No.
FHM NOEL
% Concentration
Daphnid NOEL
% Concentration
% Stream Flow
at_ Sampl e _Time
% Stream
at 7Q10
Bergstrom Paper
Kimberly Clark J
Kimberly Clark L
Kerwin Paper
Appleton Paper
Mid-Tech. Paper
Wisconsin Tissue
Nicolet Paper
Thilmany Paper
Sreen Bay STP
Neenah-Menasha STP
rort Howard Paper
James River Paper
Kerwin Paper (2)
3roctor Gamble
3reen Bay Packaging
Vid Tech (2)
-ppleton STP
'70.7
**
>100
**
**
**
**
**
**
17.7
>100
70.7
>100
>100
70.7
>100
>100
35.4
70.7
>100
35.4
**
70.7
**
**
>100
>100
<100*
**
**
**
<100*
70.7
>100
**
35.4
.121
.137
.052
.021
.088
.186
.140
.258
.680
.92
.22
.54
.23
.05
.11
.22
.26
.28
.624%
.704
.268
.202
.842
1.768
.411
.757
1.992
5.35
1.20
2.89
1.62
.31
.82
1.53
1.52
1.51
* Not calculable at concentrations lower than 100% due to toxicity of dilution water.
** Not calculable
B-2
-------
I.RKM39.9
J. RKM 45.4
K. RKM 52.8
A. Mouth.
C. RKM 2.6..
0. RKM 4.8
F. RKM 10.5.
G. RKM II.I
L. RKM 63.2
B. RKM 1.0
E. RKM 7.6
H. RKM 28.3
.M. Lake W
Map of Study Area and Locations of Sampling Stations for Toxi-
city Evaluation of Lower Fox River Water and Sediments (RKM =
river kilometers). (Lien et al ., 1985)
B-3
-------
Physical and Chemical Data for Water Collected From the Lover Fox River ac Variou* Location! and Datea
station* (Lien et al., 1985)
J.n. 30-31, 1985
pH
alkal mg/l
cond pi/cm
hardaeaa mg/l
Cl mg/l
N02 mg/l
N03 mg/l
P04 mg/l
S04 mg/l
A
7.96
164.8
397
193.9
18
<0.2
0.9
<0.2
22.7
HH.* mg/l (total) 0.56
NHj-H mg/l2 0.015
7.97
163.8
361
188.0
10
<0.2
1.4
<0.2
19.7
C
8.00
.163.4
309
187.6
14
<0.2
1.4
<0.2
19.7
0.24 0.26
C.007 0.008
0
8.05
163.6
318
189.4
14
<0.2
1.4
<0.2
20.2
0.23
0.008
I I £
8.08
168.9
360
195.1
13
<0.2
1.5
<0.2
19.7
0.23
0.008
H
8.02
162.9
362
188.4
13
<0.2
1.4
<0.2
18.3
0.16
0.005
-
-
-
-
-
-
-
-
-
-
2
-
-
-
-
-
-
-
-
-
£ i
7.99
166.6
328
188.4
13
<0.2
1.3
<0.2
14.8
0.05
0.002
K
8.19
172.4
367
197.4
11
<0.2
1.3
<0.2
16.8
0.34
0.015
ulfide« mg/l <1.0 <1.0 <1.0 <1.0 - - <1.0 <1.0 - - <1.0 - <1.0
March 13>I4, 1985
temp *C3
pH
alkal mg/l
cond M*/cm
hardneaa mg/l
Cl mg/l
N02 mg/l
N03 mg/l
P04 mg/l
S04 mg/l
3
7.63
133.6
440
164.9
20
<0.05
4.0
<0.15
22.5
KH * mg/l (total) 1.07
NHj-N mg/l2 0.014
sulfidea mg/l
April 30, 1985
temp 'C'
pH
alkal mg/l
cond fa /cm
hardneaa mg/l
Cl mg/l
N02 mg/l
N03 mg/l
P04 mg/l
S04 mg/l
"V «*/l {'«'>
NHj-N mg/l2
ulfidea mg/l
<1.0
18
8.38
153.7
419
188.1
31.3
<0.05
1.1
<0.10
36.0
1.93
0.102
<1.0
3
7.80
146.4
380
175.5
16
<0.05
4.0
<0.15
19.0
0.40
0.008
<1.0
17
8.90
141.8
300
159.1
13.4
<0.05
1.1
<0.10
16.0
0.26
0.048
-------
Decoded percentage survival (i.e. grand average) of young
walleye of different developmental phases for three stock
sources from Wisconsin waters. (Hokanson and Lien, 1986)
Phase of
development
Prolarvae
Postlarvae I
(P2)
Postlarvae II
(P3>
Source
Lower Fox River Sturgeon Bay Chippewa Flowage P a/
b/96.3
73.3
84.3
98.4
58.9
94.8
98.1
0.7168
90.8 0.0001
95.2 0.0830
Juvenile
(Pi) 96.4
Overall
survival c/ 53.8
97.0 90.6 0.2683
51.6 72.3 0.0440
Probability level of significance in survival of young walleyes among
sources as determined by ANOVA.
Underscore signifies no significant differences in mean response for the
indicated stock source (p < .05; Tukey's multiple range test).
2_/ Overall survival probability for a given stock is equal to
x P x
where Pi is expressed as a decimal fraction for survival of offspring
from each female.
B-5
-------
Water chemistry at river intake during hatching experiments
(Auer and Auer,'1986)
Date
4/18
4/19
4/20
4/21
4/22
4/23
4/24
4/25
4/26
4/27
4/28
4/29
4/30
5/1
pH
8.76
8.94
8.70
8.97
8.83
8.88
8.82
8.88
8.87
8.54
8.91
8.90
8.92
8.94
DO
(mg02/L)
14.6
16.5
11.0
12.8
10.3
9.5
10.0
11.0
10.4
10.5
11.0
10.6
10.6
10.2
NH3-N
(ugN/L)
110
80
86
129
187
162
153
183
44
159
203
207
205
74
N02-N
(ugN/L)
8
9
9
9
7
4
5
11
11
7
12
10
10
9
H2S
(ug/L)
0.9
0.8
0.9
0.5
0.8
0.7
0.8
0.6
0.6
1.6
0.7
0.7
0.6
0.5
Mean 8.85 11.4 142 9 0.8
B-6
-------
Chemical conditions at the sediment-water interface
(Auer and Auer, 1986)
24 June 1985 - Temperature _» 22 °C
Station
1
2
3
4
5
6
7
8
9
10
PM
7.45
7.22
8.23
8.11
7.65
7.39
7.54
7.75
8.25
8.18
uu
(mg02/L)
6.6
5.9
5.3
6.4
0.2
0.5
4.0
3.1
6.9
4.2
""3-N
(ugN/L)
105
289
143
99
817
1874
163
386
168
257
14 August 1985 -
Station
1
2
3
4
5
6
7
8
9
10
PH
7.31
7.59
7.86
7.73
7.47
7.49
7.32
7.36
8.43
8.45
DO
(mg02/L)
3.9
5.3
6.9
6.8
0.6
0.9
2.9
1.5
7.2
7.0
NH3-N
(ugN/L)
115
155
84
272
2339
2372
1778
5199
74
73
N02-N
(ugN/L)
48
64
54
55
68
15
21
37
61
46
Temperature .=
N02-N
(ugN/L)
~
__
Sed. COD
(mg02/9DW)
12
41
16
24
183
157
353
463
27
319
24 1C
Sed. COD
(mg02/gDW)
26
13
6
39
224
140
375
224
__
H2S
(ug/L)
9.7
16.6
3.3
3.6
43.8
55.5
69.2
11.5
1.8
4.8
H2S
(ug/L)
17.5
7.7
5.1
8.2
189.9
95.0
289.9
237.0
1.7
1.7
B-7
-------
Chemical Oxygen Demand (Auer and Auer, 1983)
GREEN BAY
GREEN BAY
METROPOLITAN SEWERAGE DISTRICT
GREEN BAY PACKAGING INC.
'/ PROCTER a GAMBLE
PAPER PRODUTS CO I O\A/ ET D
JAMES RIVER- I UX RIVER
DIXIE NORTHERN INC
(SECTION I)
COD (mg02/gDW)
QO-50 m 101-170
03 51-100 O 17! +
B-8
-------
/
Chemical Oxygen Demand (Auer and Auer, 1983)
LOWER
FOX RIVER
(SECTION II)
in \ ii \ i
COD (mg02/gDW)
QO-50 1101-170
m 51-100 171 +
FORT HOWARD
PAPER CO.
0 J 2 .3 .4
B-9
-------
Chemical Oxygen Demand (Auer and Auer, 1-983)
OEPERE
WASTEWATER TREATMENT©
LOWER
FOX RIVER
(SECTION III)
\ in \ ii
COLET PAPER
CO.
COO '(mg02/gDW)
DO-SO ^ 101-170
a SHOO
B-10
-------
Walleye Egg Incubation Sites in 1986 (Brooke et al., 1986)
,OWER FOX RIVER
SOUNDINGS IN FEET
FEET
-------
Survival of walleye ova incubated in non-groomed tissue culture
triads during April 1986. (Average of all replicates and all
females, uncorrected for initial ova viability). (Brooke et al., 1986)
Site Number
9
2
8
11
5
4
6
7
10
Percent Survival to Hatch
38.2
36.9
34.7
27.7
9.5
8.7
1.9
0.9
0
B-12
-------
Abundance of Fish Species Caught by Fyke Nets in
the Lower Fox River, April, 1985 (Balcer et al. 1936)
Walleye <5tizostedion vitreum vitreum) 792*
Yellow Perch (Perca flavescens) 807
Carp (Cvprinus carpio) 122
White Bass (Horone chrysops) 113
White Sucker (Catostomus commersoni) 106
Black Bullhead (Ictalurus melas) 22
Guillback (Carpoides cyprinus) 18
Northern Pike (Esox lucius) 11
Brown Bullhead (Ictalurus nebulosus) B
Freshwater Drum (Aplodinotus qrunniens) 7
Sauger (Stizostedion canadense) 4
Channel Catfish (Ictalurus punctatus) 4
Rock Bass (Ambloplites rupestris) 3
Burbot (Lota lota) 3
Crappie (Pomoxis sp.) 2
Redhorse Sucker (Moxostoma sp.) 1
Longnose Sucker (Catostomus catostomus) 1
Trout Perch (Percopsis omiscomaycus) 1
* Walleye collected from 22 net lifts; other species enumerated
in 8 lifts.
B-13
------- |