Bio-Assay Investigations
National Aniline Division
A]lied Chemical and Dye Corporation
Buffalos New York
Prepared by
Croswell Henderson, Aquatic Biologist
Sanitary Engineering Center, USPHS
Cincinnati, Ohio
and
H. A. Anderson, Public Health Engineer
IJC Field Unit, USPHS
Buffaloj, New York
Introduction
Purpose
In January 1956, field studies were initiated on a cooperative basis
to determine the possible effects of the wastes -from major Buffalo River
industries on the eastern end of Lake Erie and the Niagara River® Buffalo
River industries cooperating in this project were the National Aniline
Division-Allied Chemical and Dye Corporation, Donner-Hanna Coke Corporation,
and the Socony Mbbil Oil Company»
This report covers an investigation of the toxicity to fish of intake
waters and major effluents from the National Aniline Division-Allled Chamical
and Dye Corporation, Chemical and dye wastes contain some chemical compounds
-------
which are known to be toxic to aquatic life in low concentrations. Some of
these chemicals when mixed with or under the influence of other non-toxic
components of the effluent or receiving water may exert an entirely different
toxicity from that of the pure compounds., Bio-assays were made to evaluate
directly the toxicity of these chemically complex wastes.
Personnel Participating
National Aniline jJivxaion
jDi% m. Jdess, Coordinator of Pollution Research
C. J. Carney* Chemist
J. A, Gouckj Chemist
Public Health Service
Hayse H. Blacky Industrial Wastes Consultant
Groswell Henderson^ Aquatic Biologist
Dr. C. M. Tarzwell, Chief, Aquatic Biology Unit
H. A„ Anderson* Public Health Engineer
M. ¥„ Ruszaj, Chemist
Organization of Study
National Aniline Division personnel collected 2h hour composite .samples
of their intake water and effluents and determined the volume of effluents
discharged® The Public Health Service conducted bio-assays in laboratory
space provided by National Aniline and made phenol and cyanide determinations
in the IJC Unit laboratory# Phenol and cyanide determinations were also made
on some effluent samples by the National Aniline Pollution Research Laboratory®
-------
General Information
Production Operations
Hational Aniline Division is one of the largest producers of dyes, dye
intermediates, and synthetic organic chemicals, including surface active agents,
textile assistants, plastic intermediates, and pharmaceuticals in the United
States. Batch type operations are used in the production of many of the numerous
products of the Buffalo plant, fhe products "being manufactured at any one time
vary greatly according to market demand and stock on hand.
Water Supply
Buffalo city water is used for drinking, sanitary purposes, and as process
water, fhe major portion of the plant water supply is used for process cooling
and is obtained from the Buffalo Elver thro'ugh a shore intake located about 100
feet upstream from the Sational Aniline Plant "A" Sewer outfall and downstream
from plant "BSC", and "l" sewers. During periods of low river flow, there is some
recycling of the plant effluents.
Process Wastes
Wastes are discharged into the Buffalo liver through three separate outfalls
designated as plants "A", "BiSD", and MSM sewers. All of these sewer outfalls are
on the Sorth hank of the Buffalo Biver, Plant "A" outfall is located kOQ feet
downstream from South Park Bridge, plant HB&C" outfall immediately south of the
bridge, and plant 111" outfall about 1000 feet upstream from the bridge,
Sach of the above sewers receives wastes from numerous and varied production
processes# fhe wastes in each may be ejected to vary si^aificantly at times due
to changes in quantity or type of products being manufactured®
Waste Control Measures
1. Jot the past 20 years the company has supported and continues to support
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a program of research, on the effects of and methods for treating its wastes and
its fall scale application to reducing existing pollution and minimizing or avoid-
ing pollution by new processes.
2. For this purpose an especially equipped laboratory lias been provided and
manned with specially trained personnel for the entire period.
3. During recent years a pilot plant has "been provided and operated for in-
vestigating the chemical and biochemical treatment of objectionable wastes which
might result from expansions of production in the future.
This program is integrated into the entire organization.
5» Hew Processes, equipment installations and replacements are not operated
until approved for wastes control by the Pollution Re search Unit,
6. Two units for neutralization of waste acids with lime have been constructed
and are operated when necessary to maintain a pH of at least 6 in the Buffalo Biver.
7# Some wastes are segregated and discharged to the Buffalo Sewage System, with
written approval by the Buffalo Sewer Authority, for which fees are paid.
8. Wastes containing arsenic are placed in containers and disposed of by burial
100 miles at sea.
9« Certain wastes, including sulfides and thiosulfates, are destroyed "by chem-
ical treatment in especially designed equipment.
10. Some oily wastes are separated and used as fuel.
11. Some oils, tars, and various other kinds of combustible wastes are separ-
ated and burned in an especially designed incinerator.
12. Eon-combustible solids and sludges, including metallic compounds, are sep-
arated and deposited in dumps or sludge ponds for eventual sale or disposal in a
manner to avoid pollution.
13* Aluminum chloride wastes are sent to the Buffalo Sewage Treatment Plant
where they are used to advantage as a sludge conditioner.
Ik. Other wastes are recovered, refined and used in plant production processes#
Survey Methods
Flow Measurements
Waste flow in the sewers was determined by national Aniline personnel. How
in the Plant HE" Sewer was determined by a water level recorder which measured the
height of the liquid in a sewer. This device had previously been calibrated by
Pitot tube measurements.
-------
Flows in plants "A'® and "B&C" Sewers were estimated from the volume of intake
water. City intake water was measured "by positive displacement meters and river
water intake was measured lay orifice meters*
Following are the measured daily flows during a one week period. The average
Tallies were used in. all Mo-assay computations?
1000 gal./day
Date Plant *»A« Plants «B&0» Pleat WIM
1-19 11,3*9 7,231 1,753
1-20 11,265 7,3^1 1,680
1-21 11,225 6,113 1.770
1-2^ 11,151 6,529 2,090
1-25 11 .,386 6S896 1«918
Average agd 11.30 6.82 1.8^
ofs 17.* 10.5 2.8
Twenty-four hour composite effluent samples were collected "by means ©f auto-
matic samplers> Samples of Plant "A* Sewer were collected at the outfall. Plant
"B&O" samples were collected through a riser located 15 feet upstream from the
sewer outfall. Plant nSH samples were collected from "ib® influent to the wast®
treatment pilot plant. This influent is pumped from a point in'the sewer approxi-
mately 1000® above the sewer mouth»
Chemical Methods
All chemical determinations were made according to procedures is "Standard
Methods for the Immiaation of Water, Sewage8 and Industrial Wastes", 10th edition,,
published by the American Public Health Association..
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- 6 -
Bio-assay Methods
Bio-assays were made, essentially, by the method recommended by the
toxicity subcommittee of the Federation of Sewage and Industrial Pastes
Associations (Sewage and Industrial Wastes, Vol. 23, No. 11, 1360j Nov» 195l)»
This method consists of preparing various concentrations of effluent in a
selected dilution water, adding the test fish and observing their reactions
over a definite time period. A logarithmic series of numbers is generally
most convenient for preparing different test concentrations.
As the effluents were of unknown toxicity, exploratory or small scale
tests were made to determine the approximate toxic range., Test solutions
were prepared over a wide range of concentration (e.g. 100 s 1, and 0=1 percent
effluent) • Two fish were added to 2 liters of each concentration in 6-l/2 inch
diameter, 1-galIon wide mouth glass bottles. Observations for relatively short
time periods indicated test concentrations necessary for the full scale experiments,
In the full scale tests, 10 fish were generally used for each test
concentration. Five fish were added to 10 liter duplicate samples in 10 inch
diameter, 5-gallon widemouth glass bottles. The intermediate concentrations
s
tested were dependent upon information obtained from the exploratory tests.
For example, if fish were killed in concentrations above 10 percent and not
affected in concentrations of 1 percent, intermediates were set up within this
range (e.g., 10, 5°6, 3*2, 1.8, and loO percent concentration of effluent).
The dilution water used was raw Lake Erie water obtained at the
Buffalo, N» I., water plant. This water was hauled into the laboratory,
allowed to come to room temperature, and aerated vigorously for at least one
hour to bring it to equilibrium with atmospheric, gases. Characteristics of this
water at time of use were as followss Dissolved oxygen ?<.6«8»2 ppm| pH 8#0~8,2j
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Total alkalinity (CaCO^) 9I4-IOO ppm? Total acidity (CaCO^) 0-1 ppmj Versenate
hardness (CaCO^) 120-135 ppm.
The test fish used were fathead minnows (Pimephales proroelas) of a
fairly uniform siae, ranging in length from 2 to 2-1/2 inches and in
weight from 1 to 1-1/2 grams. These fish were obtained in uniform lots
from the Newtown, Ohio, Fish Hatchery and acclimated to laboratory conditions.,
This species is of intermediate tolerance to chemicals comparable to bass,
sunfish, perch, and other warm water species, and sill tolerate fairly low
oxygen conditions (l-2 ppm).
Another species, the emerald shiner (Notropis atherinoides) obtained
locally from a Buffalo bait dealer was used in some experiments in. order to
obtain a comparison of the toxicity to fatheads and this locally abundant species.
The bio-assays were made at ordinary laboratory temperatures which were
within the range from 22 to 2$e C. and would compare favorably with 'maximum
summer water temperatures in this area.
The tests were designed so that no oxygenation or aeration was generally
needed. Absorption of atmospheric oxygen by the exposed water surface was
normally adequate for fish requirements during the test period. However, in
some of the bio-assays, high oxygen demand effluents caused oxygen depletion.
When necessary, oxygen was maintained by bubbling pure oxygen through the test
solution by means of a suitable arrangement of valves and small tubing• The
rate (60-180 bubbles per minute) was adjusted to maintain adequate oxygen for
fish survival with minimum agitation to prevent the loss of volatile materials.
Physical and chemical determinations (temperature, dissolved oxygen, pH,
alkalinity, and hardness) were made on each concentration both initially, after
-------
fish mortality, or at the completion cf the test.. This was done primarily to
maintain control of oxygen conditions and to differentiate between fish,
mortality due to oxygen deficiency or acidity and other toxic properties»
Fish reactions ware observed over a 96 hour period. From the mortality
in the different; concentrations, 2h$ I48, and 96 hour TL (Median Tolerance Limit)
HI
values were obtained ¦> The Median Tolerance Limit is the concentration of
effluent in dilution water that kills just $0 percent of the test fish. These
values were obtained by straight line graphical interpolation from percent
survival of fish and log concentrations bracketing the 50 percent point.
Effluent samples were normally brought into the laboratory in the morning
immediately following collection and exploratory tests set up. Observations by
late afternoon indicated the toxic range and full scale tests were then set up.
As some of the effluents were highly acid and at pH values which would be
rapidly fatal to fish, similar bio-assays were set up with portions of sample
that had been neutralized with lime to pH ?.
Bio-assays were also made on mixtures of and "Ew effluents,
mixed in proportion to the volumes released into the Buffalo River.
Results
Physical and Chemical Characteristics
A general description and some of the chemical characteristics of the
plants "ABS "BSC", and "E" effluents and the river intake waters are shown in
Table 1.
All of these effluents were highly colored, with the intensity or shade
varying so ire what in the different composite samples. The nAM effluent was
generally from green to blue, the "B&Cn effluent from orange to red, and the "En
effluent from pink to dirty-orange. A mixture of these effluents gave a dark
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- 9 -
brown color, similar to, but of higher intensity than* that of Buffalo
River intake water.
Odors were variable in intensity but sons samples of "A" and
effluents smelled of very strong solvents (chlorobenzene, etc.). Little
or no odor was noticeable in the "B&C" effluent. All effluents were
relatively clear, containing only a small amount of suspended matter, oil,
or other extraneous material* Some samples, especially the WE" effluent,
formed precipitates "when added to the dilution water.
Dissolved oxygen values were high in most "A« and "E" effluent
samples and low values were reflected only when river intake values were
also low. Evidently organic materials in these effluents are very slowly
oxidizable« "B&C" samples, however, were either very low in or free of
dissolved oxygen.
With the exception of two samples of "A", all effluents were highly
acid with pH values ranging from 2 to 1) and acidity values from 100 to 1200 ppm»
The HEH effluent was normally the most acid, followed by "BSC" and then "A"*
When neutralized with lime to oil 7, medium to heavy precipitates formed in the
and but little or none in the "A" effluents. A color change from
blue to green was apparent in "A" samples when neutralized.
Phenols were highest in HB&CW effluent samples ranging upward to about
2 ppm with other effluents containing generally less than 0.5 ppisu Cyanides
were at very low values in all effluents«
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Source
TABLE 1 - PHYSICAL AND CHEMICAL DATA
RATIONAL ANILINE EFFLUENTS
Date Description
1956 Color,odor,etc.
Dissolved
• Oxygen
ppm pH
Alkalinity Acidity Hardness Phenols
(CaCOo) (0a003)
-------
Source
Same efflu- 2-15
eats as
above. Neu-
tralized.
with lime 2-23
Plant "BAG" 1-18
Effluent
2*t~Hr .Com-
posite
TABLE 1 (Cont'd) - PHYSICAL AND CHMICAL DATA
NATIONAL ANILINE EFFLUENTS
Date Description
1956 Color8 odor, etc.
Changed color from
blue to green.
No precipitate.
Slight precipitate.
Dark reddish-orange.
Faint solvent .
Slight turbidity.
Dissolved
Oxygen
PPm
8.0
1-19 Dark red.
Faint solvent.
Slight turbidity.
2-l4 Dark reddish-orange.
No odor.
No turbidity.
2-21 Dark orange-red „
No odor.
No turbidity.
3-13 Dark orange-red.
Faint burnt rubber.
No turbidity.
3-21 Dark orange-red.
No odor.
Slight turbidity.
8.4
0.0
2.0
2.0
0.0
0.0
7.2
7.4
2.6
2.4
2.9
3.2
2.9
2.5
Alkalinity Acidity Hardness Phenols
(CaCO^) (CaCO^) (CaCO^) ppb
ppm ppm ppm 4AA Qibbs
54
58
0
16
20
380
660
350
810
600
305
330
7*»0
200
280
1026 1180
1983 1836
2091 2039
*480 1014 1071
300
Cyanide
PP*
<5
<5
<5
12
1
1—•
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TABLE 1 (Cont'd) - PHYSICAL AMD CHEMICAL DATA
NATIONAL ANILINE EFFLUENTS
Dissolved Alkalinity Acidity Pardness Phenols
Source
Date
1956
Description
Color8 odor,etc.
Oxygen
ppm
pH
(CaC03)
ppm
(C aCO-j )
ppm
(CaCQo)
ppm
ppb
4AA Gibbs
9 yanide
PPb
6-20
Dark orange-red.
Sweetish solvent .
No turbidity.
0.0
2.6
0
420
520
210
<5
Same eff-
luent as
above#
Neutralized
with lime.
1-19
2-14
Fairly heavy brown
precipitate.
Dark "brown precip-
itate .
-
7.0
7.0
-
-
-
-
-
2-21
Small amount of brown -
precipitate.
7.0
-
-
-
_
-
>13
Heavy dark "brown
precipitate.
-
6.7
2+4
18
1050
-
-
Plant "E«
Effluent
2^-Hr.Com-
posite
1-24
Light orange.
Strong solvent
(chlorobenzene).
No turbidity.
1.9
0
770
240
864 896
<5
2-15
Light pink.
Faint solv ent(swee t)
No turbidity.
9.4
•
3.0
0
280
150
774 739
<5
2-17
Light dirty-orange .
Faint solvent(sweet)
Slight turbidity .
7.0
•
2.7
0
*480
125
166
<5
2-21
Light tan.
Faint solvent(sweet)
Slight turbidity.
10.0
e
2.5
0
1020
135
461 422
<5
-------
Source
TABLE 1 (Cont'd) - PHYSICAL AND CHEMICAL DATA
NATIONAL ANILINE EFFLUENTS
Date Description
1956 Color, odor, etc.
Dissolved
Oxygen
ppm
pH
Alkalinity Acidity Hardness Phenols
(CaCO^) (CaCO^) (CaC0~) pp"b .Cyanide
ppm ppm ppm ^AA Gibbs ppb
3-13 Dirty "bluish-gray.
Strong solvent
(butyl aldehyde) .
Slight turbidity.
3-20 Pink.
Solvent (sweet).
No turbidity.
3-21 Pink.
Strong solvent(sweet)
No turbidity .
6-20 Light dirty-orange .
Solvent «
No turbidity.
Same efflu- 1-2^ Light colored pre-
8.8
2.6
960
135 182 179
20
10.1k
0,0
ents as
above. Neu-
tralized
with lime
cipitate .
2-17 Fairly heavy light
colored precipitate.
2-21 Heavy light colored
flocculent precipi-
tate a
3-13 Dark brown flocculent
precipitate-settles
to clear solution.
6.8
7.6
2.3
2.5
2.6
7.0
7.^
7.3
7.^
30
90
90
1200
680
2^5
180
185
210
650
1150
1130
168 181
182
<5
9
<5
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TABLE 1 (Cont'd) - PHYSICAL AND CHEMICAL DATA
NATIONAL ANILINE EFFLUENTS
.Dissolved. .Alkalinity Acidity Hardness .Phenols
¦Date Description Oxygen (CaCO^) (CaC0«) (CaCO,,) ppb .Cyanide
.Source 195^ Color,odor,etc. ppm pH ppm ppm ppm MAA Gdbbs ppb
Mixed "A% A -3-1^ Dark purplish- ^.0 2.6 0 320 230
"B&Cand BSC-3-13 brown.
"E" efflu- E -3-13 Sweetish solvent.
ents. In Slight turbidity.
proportion
to volume A,BfiG# Dark "brown color. 2.6 0 Jj-00 280 - - -
released, and E~ Solvent odor.
3-21 Slight precipitate.
A -6-21 Dark red-orange. - 5»5 . 2^ 100 325 - - -
B&C-6-20 Sweetish solvent.
E -6-20 Slight tur"bidity.
River In- 1-18 Brown. 8.0 6.7 72 30 2l6 651 980 <5
take water Faint oil & sewage.
8-Hr.Com- Slight turbidity,
posite
2-1^ Light grayish-tan. 11.0 7-3 80 6 135 92 79 <5
Faint sewage.
Slight turbidity.
2-16 Light grayish-tan. 7«6 7*6 6k k 110 52 29 <5
Faint sewage#
Slight turbidity.
2-21 Light grayish-tan. 9.0 7-5 66 6 125 70 73 <5
Gasoline & sewage.
Slight turbidity.
H
f=~
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Date
Source 195 6
TABLE 1 (Cont'd) - PHYSICAL AND CHEMICAL DATA
NATIONAL ANILINE EFFLUENTS
Description
Color,odor,etc.
-Dissolved
Oxygen
ppm
pH
•Alkalinity Acidity Hardness Phenols
(CaCO^) (CaCO-s) (CaCO-) pp"b Cyanide
ppm ppm ppm ^AA Gi"b"bs pp"b
3-13 Light grayish-tan. 10.0 7.5 72
Faint gasoline.
Slight turbidity.
>21 Grayish-tan. 10.8 7.2 86
Faint gasoline.
Slight turbidity.
6-21 Dark "brown. 0,k 6.8 72
Faint solvent.
Slight turbidity.
12
30
115 11 10
155
250
H-1
vn
t
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- 16 -
Toxicity to Fish
A summary of bio-assay results showing the direct toxicity of the
effluents to fish is shown in Table 2. The information on which these results
are based, including concentrations tested, time for fish mortal ity, percent
of mortality, and bio-assay control data are shown in the Appendix.
Median tolerance limit (TLm) values were obtained for 2k, U8j and 96
hour periods. The 96 hour TL^ was used to compute the dilution ratio, which
is the ratio of a unit volume of effluent to dilution water which produces a
50 percent mortality of the test fish. This ratio times the effluent flow
gives the dilution volume or the total flow or volume of receiving water
required to reduce the toxicity of the effluent to where a"50 percent
mortality of the test fish is produced. The following fbrmula may be used
for directly computing this dilution volume;
100 - TL
m
x Effluent Flow - Dilution Volume
TL
IT!
The dilution volumes represent conditions which would cause direct
injury to fish upon short time exposure and are a direct comparative measure
of toxicity. Liberal application factors must be applied to these results for
complete protection of aquatic life.
All samples of "A", "B&C", and "Ew effluents were toxic to fish. "A"
and "E" were about equally toxic and "B&C" considerably less. The toxicity was
variable with 96 hour TLm values ranging from lj.2 to 1$ percent for the "A"
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- 17 -
effluent, 13 »5 to 28 percent for the and U*0 to 2lt percent for the n£"
effluent. Intake water samples were relatively non-toxic, a significant
mortality of fish occuring only in the June (low flow) intake sample.
The difference in 2lj. and 1+8 hour 1L values for the "A" effluent was signifi-
nt
cantly greater than for the others, which may reflect some chronic or accumu-
lative toxicity.
Neutralization with lime did not significantly reduce the toxicity of
the "A" or "E" effluents but considerably reduced that of the "B&C" effluent.
In some of the samples, the addition of dilution water to the raw effluent
raised pH values to "safe" levels and yet a rapid mortality of fish occurred.
Neutralization would not he expected to reduce toxicity very much in these
situations.
Some difficulty was encountered in maintaining adequate oxygen in the
high concentrations of neutralized "B&C" effluents Whether fish loss was
due to oxygen depletion or toxicity could not he clearly distinguished.
This difficulty was also encountered in a few samples of the "A" effluent. In
most samples of "A" and "E", oxygen was adequate for fish survival without
maintaining it artificially>
The effluents were more toxic to shiners (Notropis atherinoides), a
locally important forage species, than to fathead minnows.
Mixing the "A", "BSC", and "E" effluents did not significantly alter
the toxicity in two of three samples. In the others the toxicity was reduced
by one-half.
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- 18 -
TABU! 2 - SUMMARY OF SIOASSAY DATA
UATIOHAL ANILINE IffLUEHfS
Source
Sffluent
Date " Flow
1956 cfs
fLm (Median, folerance Limit)
(Per cent Concentration)
24 hr, ^i8 hr. $6 hr
Plant "A"
1-26
17,4
10
4.2
4.2
Effluent
24-hr,
2-15
ii
20
16
15
Composite
Neutralized
42
24
21
2-16
ii
20
13.5
13.5
2-23
n
24
11
11
Neutralized
24
-
-
3-14
ii
10
7.5
7.5
3-21
M
16
7
6,2
Shiners
7
4.5
4.5
6-21
tt
7.5
6.2
6.2
Average
17.4
9.1
Dilution.
Dilution Volume
Ratio of s
1122.8 396
1*5.7 98
1*6.4 112
U8.1 l4l
1:12,3 214
1815.1 264
1:15.1 257^
212
(l) Intake toxicity subtracted.
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- 19 -
TAB IE 2 (Cont'd) - SUMMARY OF BIQASSAY DATA
lAflOIAL ANILIBX IlfLOTirTS
Source
Iffluent fla (Median tolerance Limit)
Bate flow (Per cent Concentration)
195^ efB 2^ hr» ^40 hr> 96 hr*
•Plant "MC« 1-18 10.5
Iffluent
2k hr. 1-19 *
Composite
Neutralized
2-lk "
Neutralized
2-21 «
Neutralized
3-13 "
Neutralized
3-21 «
Shiners
6-20 «
28
2**
75
21
65
22
>56
13.5
>56
13.5
8
2k
28
2k
19
k2
22
k7
13.5
39
13.5
6.2
2k
28
2k
18
16
13.5
35
13.5
6,2
2k
•Dilution
Dilution Volume
latlo cfs
182.6 2?
153.2 33
1*4.6
115.3
li6,k
lt$*k
113.2
i©
55
6?
67
id)
Average
10.5
19.6
k6
(1) Intake toxicity subtracted.
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- 20 -
TABLE 2 (Cont'd) - SUMMABY OF 1IOASSAY DATA
NATIONAL ANILINE BFFLUEHTS
Effluent TLrn (Median Tolerance Limit)
"Dilution
Bate
flow
(Per cent Concentration)
Dilution
¦Volume
Source
1956
cf B
24 hr.
^8 hr.
96 hr.
Batio
cfs
Plant "B«
Iffluent
24 hr.
Composite
1-24
Neutralized
2-15
2,8
II
6.2
7.5
24
4.2
7.5
24
4.0
5.6
24
1:24
1:3.2
67
9
2-1?
II
7.5
6.2
4.2
1:22.8
64
neutralized
8
7
4,2
2-21
M
7.5
7.5
7
1:13.3
37
Neutralized
22
16
16
3-13
«
7.5
7.5
7.5
1:12.3
35
Neutralized
>18
>18
>18
3-20
H
7.5
5.6
5.6
1:16.9
4?
3-21
II
¦4.5
4.2
4.2
1:22.8
64
Shiners
2.4
2.4
2.4
6-20
M
20
20
20
1|4
1Q(1)
Average
2.8
9.6
42
I
Mixed "A",
and
A ~3~l4
MO-3-13
a -3-13
30.7
9
9
9
1:10.1
310
Iffluent a
3-21-56
«
13.5
13.5
13.5
1:6.4
197
In propor-
tion to
volume
released
A -6-21
B&3-6-20
K —6—20
it
13.5
11
8.?
1:10.5
322
CD
1 Intake toxicity
subtracted*
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- 21 -
TABLE 2 (Cont'd) - SUMMARY Of BIOASSAY DATA
NATIONAL miim EFFLUENTS
Sate
6-21
Iffluent fIn (Median tolerance Limit)
Flow (Per cent Concentration)
dilution
30.?
(3)
75
70
70
1tQ»&3
Dilution
Volume
Source
1956
cfs
2^ hr»
k8 hr„
96 hr. Hatio
cfs
Jtiver
1-18
30.7
10058
surv.
9036
surv.
70$ surv.^
Intake
Water
2-14
N
10058
surv.
100$
surv.
10058 surv.
«*
8-hr.com-
posite
2-16
II
100$
surv.
100$
surv.
IO058 su,rv.
-
2-21
II
90$
surv.
90$
surv.
90$ surv.
-
3-13
M
100$
surv.
100$
surv.
9058 surv.
-
3-21
II
100$
surv.
100$
surv.
IOO58 surv.
-
Shiners
II
100$
surv.
10058
surv.
80$ surv.
12
(1) Intake toxicity subtracted,
(2) Per cent survival of fish in undiluted sainple.
(3) liver water used ty plant. Dilution volume was subtracted
from that for plant effluents to determine that contributed
"by effluents®
-------
- 22 -
Significance of Data
Characteristics which may Affect Aquatic Life
While bio-assays have shown plant "A", "B&C", and "E" effluents to be
toxic to fish, insufficient information was available to indicate the major
components responsible. The highest toxicity, however, was generally in
effluents with a strong solvent odor. The chemically complex nature of
these wastes and the numerous processes from which they are derived may make
it quite difficult to determine sources of toxic materials. Bio-assays would
be of considerable help in tracing this toxicity to process effluents.
Bio-assays conducted on phenol and ortho-cresol under experimental
conditions similar to that of the effluents gave 96 hour TL^ values of lj.0
and 2i| ppm, respectively. This would indicate that phenol was not toxic to
fish at levels found in the effluents. Other phenolic compounds, especially
some of the chlorophenols, have been reported toxic to fish in concentrations
as low as 0.1 ppm.
While the quantity and nature of the solvents in these wastes are not
known, many hydrocarbon solvents are toxic to fish. Bio-assays with some
solvents gave 96 hour TL^ values for benaene, $6 ppm, for toluene, 5l ppm, and
for xylene, 28 ppm.
Sub-lethal concentrations of phenols and benzene derivatives, such as
chlorobenzene, are known to impart a taste to fish flesh.
Cyanide concentrations in these effluents were at levels which would
not be expected to effect aquatic life.
-------
- 23 -
The high acidity and corresponding low pH values of these effluents
would have a detrimental effect on aquatic life, unless adequate buffering
capacity was available in the receiving water or neutralization was affected
before release. Normally, pH values below 5 May be expected to cause fish
mortality. Even above lethal levels, decreasing the pH may have considerable
effect on increasing the toxicity of certain materials, especially metal salts
and sulfides. For example, larger amounts of metal ions such as copper,
lead, zinc, iron, etc., are in solution at lower pH values. A decrease in pH
of 1 unit may cause a 10 to 100 fold increase in the toxicity of some metals,
likewise, decreasing the pH releases hydrogen sulfide from sulfides and the
toxicity may be greatly increased. Concentrations of H^S as low as 1 ppm
are known to have an effect on aquatic life. A reduction in pH may have an
effect not only on materials released in these effluents but on those
released by other industries and present in the receiving waters.
Color, apparently, has no direct effect on fish. No relationship
could be established between color intensity and toxicity in any of the
effluents. An indirect effect would be possible by a decrease in light
penetration and consequently the productivity in receiving waters.
Oxygen depleting characteristics may have a definite effect on aquatic
life unless adequate volumes of receiving water are available for dilution or
assimilation. Dissolved oxygen concentrations should be maintained at £ ppm
or above in receiving waters for complete protection of aquatic life.
The release of large volumes of effluents at high temperatures which
increase those in receiving waters may have an effect in increasing the
toxicity of some materials, reducing dissolved oxygen, and a direct effect
on some aquatic organisms»
-------
- 2h -
Effect on Receiving Waters
itXl of these effluents were toxic to fish. The dilution -volumes
necessary" to reduce this toxicity to 50 percent mortality of the test fish
(Table 2) would obviously not provide for complete protection of aquatic
life. Liberal application factors must be used, which are based on the
following major considerations?
(1) The bio-assay procedure measures 50 percent mortality during a
relatively short time period in non-renewed solutions. This must be related
to no effect from continuous long tine exposure.
(2) Test data apply directly to the species of fish used. While fathead
minnows are of intermediate tolerance and compare favorably -with many warm
water "game11 fishes, some locally important species of fish and fish food
organisms way be more sensitive. Bio-assays conducted -with a locally important
forage fish, the emerald shiner (Notrogis atherinoides), indicated this species
was approximately twice as sensitive as fathead minnows.
(3) Some effluents may vary in toxicity. A few samples may give an indication
of toxicity "but maximum conditions may be missed. In many situations, maximum
conditions of toxicity are the limiting factor as far as aquatic life is
concerned.
(U) Some conditions which may generally reduce but in some cases increase the
magnitude of the application factor are the loss of volatiles, hydrolysis,
oxidation, precipitation, and changes in water quality characteristics by the
entrance of other effluents.
-------
- 25 -
Based on the best available information an application factor of at
least 3 would be necessary to prevent fish kills and as much as 10 for
complete protection and propagation of fish. It is evident that low seasonal
flow's in the Buffalo River would not provide this necessary dilution! however,
only a small portion of the Niagara River flow would be necessary.
This contribution of toxicity to'the Buffalo River adds to that present
from other industries in the basin. While the toxicity from individual
industrial effluents is substantially reduced in the basin, enough remains
to present a threat to the Niagara River under abnormal conditions. Toxicity
builds up in the Buffalo River during "low flows and then may be rapidly
flushed into the Niagara River. Additional dilution water in the Buffalo River
during low flow periods would minimize this possibility.. As long as large
quantities of unknown toxic materials are entering the Buffalo River basin,
it cannot be stated with certainty that threat to aquatic life in the Niagara
River will be completely eliminated.
Vhile oxygen depleting characteristics of these effluents were somewhat
masked by high toxicity in the bio-assays, depletion of oxygen was observed in
"B&C" and some "Aw samples® As the volume of these effluents may exceed flows
in the Buffalo River during low flows, oxygen depletion would no doubt occur
in the river. This would not significantly affect the Niagara River but may
have an effect in a border zone where the Buffalo River enters Lake Erie.
The possibility also exists that an off-flavor in fish flesh may be
produced by small quantities of phenols, solvents, or other chemicals *
-------
- 26 -
Conclusions
Bio-assays have shown that all samples of Plants HAnt "B&CW, and
WE» effluents were toxic to fish. The toxic components were not identified.
River intake samples were generally non-toxic or had only a slight degree of
toxicity.
The "A" effluent was the most significant from the standpoint of
toxicity contributed to the Buffalo River. The "An and "EM effluents were
equally toxic but the volume of WA" was much larger. The "B&C" effluent
was considerably less toxic.
Neutralization with lime significantly reduced the toxicity of the
"B&CH effluent but had only a slight or no effect on samples of "A" and ttE'1
effluents. Most of the "A" and "E" raw samples remained toxic after dilution
with Lake Erie water to concentrations with pH values which "would be tolerated
by the test fish.
Some oxygen depletion was apparent in concentrations of effluent
during the 96 hour test period. When this effluent was neutralized and
oxygen maintained, very little toxicity remained. Most samples of "A" and
nEn effluent, however, were toxic in concentrations that retained adequate
oxygen for fish support.
These effluents are major contributors of toxicity to the Buffalo liver
and add substantially to that contributed by other industries in the basin.
Seasonal low flows in the Buffalo River do not provide for adequate dilution of
these wastes. Under normal flow conditions, however, little or no effect on
aquatic life in the Niagara River would be expected.
-------
The buildup of toxicity in the Buffalo River basin during low
flows, with the possibility of a rapid release into the Niagara River
under abnormal conditions does present some threat to aquatic life in
the Niagara. Additional dilution water in the Buffalo River during low-
flows would minimize this possibility.
4
As long as large quantities of unknown toxic materials are entering
the Buffalo River basin, the threat to aquatic life in the Niagara River
cannot be completely eliminated. Bio-assays could be used to trace sources
of toxic materials within a plant which would be of help in further reducing
or eliminating the major toxic wastes.
-------
appendix TABLE ai -BIOASSAY DATA
AT juwi* ** TSST TISH - JATHSAD MIHHOVS
H&TIOS&L ANILIKE DIVISION, ALLIED CHIMICAL AND DIE CORPORATION DILUTION HATER - IAKS ffilE
BUTTALO, HEW TOEK
SOURCE AHD
METHOD OF
COLLECTION OF
SAMPLE
DATE OF
COLLECTION
CONCEN-
TRATION
TESTED
PERCENT
NUMBER
OF
TEST
FISH
VOLUME
OF TEST
SAMPLE
LITERS
TIME OF DEATH
PERCENT SURVIVAL
CHEMICAL AMD PHYSICAL DATA
REMARKS
F IRST
FISH
HALF OF
FISH
ALL OF
FISH
24
HOURS
48
HOURS
72
HOURS
96
HOURS
TIME
TEMP.
°c
DISSOLVED
OXYGEN ppffii
P H
TOTAL ALK
(CaC03)
ppm.
TOTAL
ACIDITY
(CaCOj)ppm
VEftSENATE
HARDNESS
ppm.
Plant A
1-26-56
100
5f fluent
6.0
3.0
0
120
300
Ihrk purple
Slight solvent odor
Little turbidity
Low pH
Low S.O.
Possible low D.C.
Dark greenish blue
Burnt rubber odor
Little turbl&lg*
Low pH
Color cbfrnged from
blue to green
So precipitate
24 Hr. D.O. - 3.0
Sffluent
2U-Hr. Compostt
56
2
2
30 min.
30 min.
30 min.
0
0
0
0
Initial
-
4.6
-
-
-
In Let
30 Min.
913O AM 1-26
32
5
10
1 hr.
1.5 hre.
1.5 hrs.
0
0
0
0
Inltlftl
7.2
6.2
36
18
185
Tleh Added.
1*5 hrs.
7.0
6.4
40
12
175
Ill 30 AM 1-26
IS
10
20
3 hrs.
H hrs.
5 hre.
0
0
0
0
Initial
23
7.4
6.6
60
14
160
•5 hrs.
23
6.8
6.8
64
16
155
10
10
20
6-20 hrs.
6-20 hrs*
2U-H0 hrs.
50
0
0
0
Initial
7.6
7.0
76
10
140
U8 hrs.
0.2
7.1
88
8
155
5.6
10
20
2M+S hr<
2U-U8 hri
2U-U8 hrs
100
0
0
0
Initial
7.4
7."
84
6
135
48 hrn.
1.0
7.2
96
8
175
Control
10
20
-
-
-
100
100
100
100
Initial
7-4
8.2
94
2
125
96 hrs.
4.6
7.7
100
6
145
ILoi (Kedi
a Toleran
:e Limit)
• Per cent
concentr*
tion
10
lllOO AM 2-15
32
10
20
30 min.
30 min.
30 min.
0
0
0
0
Initial
25
8.0
3.8
0
70
135
71th Added
30 min.
25
7.5
3.8
0
68
135
3iOOPM 2-15
18
10
20
3-17 hrs.
27-U2 hrs
60
UO
30
30
Initial
8.0
6.0
32
30
135
$6 Hrs.
5.0
7.1
36
10
130
10
10
20
100
100
100
100
Initial
8.0
6.4
64
18
130
96 Hrs.
4.0
7-5
64
6
130
Oontrol
10
20
100
100
100
100
Initial
8.0
8.0
96
2
125
96 hrs.
4.2
7-7
100
2
130
TLa (Med.
an Toler*
ice Limit)
- Per ceo
b concentr
ation
20
16
15
15
Plant A
2-15-56
100
Effluent
8.0
7.2
54
16
305
Same as above
Neutralised
56
5
10
2-20 hrs.
2-20 hrs*
23 hrs.
0
0
0
0
Initial
25
8.0
7.6
70
8
225
Vlth line
23 hrs.
25
3.6
7.4
72
12
230
32
5
10
2^-UOhrs.
2U-^0hrs.
100
uo
20
20
Initial
8.0
7.7
86
4
200
96 hrs.
u.s
7.6
86
10
190
18
5
10
H6 hre.
100
60
60
60
Initial
8.0
8.0
96
4
175
96 hrs.
4.2
7.6
96
8
155
Tin
(Mediae
tolerance
Limit) -
Per cent
conceit tr»
Ion
U2
2k
21
21
-------
appehdix TABLE A2 -BiOASSAY DATA test pish - smhead mibbows
KmOHAJ. AHILISX DIVISIOH, MJ.IED CHEMICAL AND DYE CCEPORATIOa D1XOTIOH VAIER - LAKE SIB
BlWFA10#8Stf YCBK
SOURCE AND
METHOD OF
COLLECTION OF
SAMPLE
DATE OF
COLLECTION
CONCEN-
TRATION
TESTED
PERCENT
NUMBER
OF
TEST
FISh
VOLUME
OF TEST
SAMPLE
LITERS
TIME OF DEATH
PERCENT SURVIVAL
CHEMICAL AND PHYSICAL DATA
remarks
FIRST
FISH
HALF OF
FISH
ALL OF
FISH
21
HOURS
4-8
HOURS
72
HOURS
96
HOURS
TIME
TEMP.
°C
DISSOLVED
OXYGEN ppm.
P H
TOTAL ALK
(CaC03)
ppm.
TOTAL
ACIDITY
(CaCOjJppfi
VEKSENATE
HARDNESS
ppm.
Plant A
2-16-56
100
Effluent
6.8
3-8
0
100
150
Bark Use
Burnt robber odor
Bo turM<y
Dark tilue-greon
Burnt rtibtoer odor
Bo tnrtldity
Ug-HrJ).0. . 2.2
Sliglt precipitate
when neutralized.
lover concentration
not set «p.
Ho reduction in
toxicity Indicated
from neutralization.
Effluent
2^-Hr.Composite
56
2
2
1.5hre
1.5 hre.
1.5 hrs.
0
0
0 _]
0
Initial
-
_
_
-
.
In Lab
1.5 hrs.
7.0
5.8
20
>10
1J0
3:00 PM 2-l6
32
5
10
3-17 toe.
3-17 hra.
3-17 hrs.
0
0
0
0
Initi&l
25
7*2
6.7
50
26
130
Pish Added
17 hre.
25
6.H
7.0
1)8
16
125
3:00 a 2-19
18
5
10
3-17 hre.
26 hrs.
26 hrs.
60
0
0
0
Initial
7-H
7.1
68
16
130
He hrs.
5.*
7-6
7*
8
130
10
5
10
100
100
100
100
Initial
7.6
7.H
10
130
96 hrs.
U.8
7-7
86
6
130
Tim (Med
an Tolera
ice Limit]
- Per cea
; Concent]
ation
20
13-5.
±2.5
12*5
Plant A
3-23-56
100
Effluent
9.0
3.3
0
150
1>»5
Effluent
24-Hr.CoBPOSite
56
2
2
15 ain.
15 sin*
15 Bin.
0
0
0
0
Initial
-
-
-
-
In Lab
15 (Bin.
8.0
3.6
0
92
lUO
9:30 am 2-23
32
5
10
2 hrs.
2 hrs.
2 hrs.
0
0
0
0
Initial
25
7.6
5.8
18
U2
135
t ish Added
2 hrs.
25
7.H
6.1
2>»
32
135
Ui 30 AM 2-23
18
5-
10
28-U6 hrs
28-U6 hri
28-U6 hrs
100
0
0
0
Initial
7.6
6.8
56
22
135
U6 hrs.
2.2
7.2
60
20
125
10
5
10
2>(-UShr«
100
60
60
60
Initial
7.6
7.2
7»
10
130
96 hrs.
5.2
7.6
80
U
140
5.6
5
10
55-72 hre
100
100
80
80
Initial
1A
7."»
&
6
130
96 hrs.
U.2
7.6
92
It
lMO
Control
5
10
100
100
100
100
Initial
7.*
8.2
98
0
IS
96 hre.
5.0
7.7
102
u
130
TIa (Medlx
n Tolernn
:e Limit)
• Per cent
Concentre
tion
£
11
u
u
Plant A
2-25-56
100
Effluent
8.U
7."
58
20
330
Sane as above
Seatrallied
56
5
10
6-Z1 hr»
6-.-1 hrs
6-21 hrs
0
0
0
0
Initial
25
7.8
7.8
80
12
250
with line
.21 hrs.
25
6.0
7."»
80
1U
2U0
32
5
10
6-21 hrs
6-21 hrs
6—21 hrs
0
0
0
0
Initial
7.6
8.0
92
8
195
21 hre.
7-5
90
12
190
-------
appendix TABLE A3 -B10ASSAY DATA
BUIOftL ANILINE DIVISION, ALLIED CHEMICAL AND DIE
BUFFALO, HEW YOBK
CORPORATION
TEST FISH - W.THEM) KIHNOVS
DILUTION WATER ft LAKS EBIS
SOURCE AND
METHOD OF
COLLECTION OF
SAMPLE
DATE OF
COLLECTION
CONCEN-
TRATION
TESTED
PERCENT
NUMBER
OF
TEST
FISh
VOLUME
OF TEST
SAMPLE
LITERS
TIME OF DEATH
PERCENT SURVIVAL
CHEMICAL AND PHYSICAL DATA
F IRST
FISH
HALF OF
F |SH
ALL OF
FISH
24
HOURS
48
HOURS
72
HOURS
96
HOURS
TIME
TEMP.
°C
DISSOLVED
OXYGEN ppm.
P H
TOTAL ALK
(CaC03)
ppm.
TOTAL
acidity
(CaCOjJppm
VERSENATE
HARDNESS
ppm.
Plant A
3-14-56
100
Effluent
6.8
5.8
24
30
130
Effluent
24-Br .Composite
56
2
2
3-15 hrs
3-15 hre
3-15 hrs
0
0
0
0
Initial
-
-
-
-
-
In Lab
2:00 PM 3-14
32
5
10
3-15 hrs
3-15 hrs
3-15 bore
0
0
0
0
Initial
23
8.0
7.3
64
12
120
fish Added
16 hrs.
24
7-4
7.3
66
12
120
5:00 PM 3-lU
18
10
20
3-15 hrs
3-15 hrs
20 hre
0
0
0
0
Initial
8.4
7.6
74
6
115
20 hrs.
7.4
7.8
76
8
125
10
10
20
3-15 hre
24 hre
44 hre
50
0
0
0
Initial
8.4
7.8
80
4
115
44 hrs.
5-2
7.5
84
6
120
5.6
10
20
100
100
100
100
Initial
8.1*
8.0
84
4
120
96 hra.
5.0
7-7
86
6
120
Control
10
20
100
100
100
100
Initial
8.4
8.0
90
2
115
96 hre.
5.8
7-8
92
6
115
TLd (Medi
an Tolerai
ce Limit)
- Per cen
; concentr
ition
10
Is5
1*5
Plant A
3-21-56
100
Effluent
6.6
3-0
0
155
185
Effluent
24-Hr.Composite
32
2
2
6-18 hre
6-18 hre
6-18 hre.
0
0
0
0
Initial
..
-
-
.
-
In Lab
18 hrB
6.8
6.7
40
14
145
10:00 AM 3-21
18
5
10
3-15 hrs
23 hre
24-39 hrs
40 •
0
0
0
Initial
24
8.2
6.7
62
22
130
?ieh Added
39 hre
24
0.6
6.9
56
16
140
5:00 PM 3-21
10
5
10
24-39 hrs
44 hrs
47 hre
100
0
0
0
Initial
9.0
6.9
72
14
125
47 hrs
3.6
7-2
?2
14
135
5.6
5
10
24-39 hrs
100
80
80
60
Initial
9.0
7.4
82
6
125
96 hrs.
5.6
¦ 7*U
82
8
120
Control
5
10
100
100
100
100
Initial
9.0
8.1
90
2
120
96 hre.
5-S
7-3
92
6
120
TZa (Medi
in Toleran
ce Limit)
• Per cen'
concentrj
tion
16
I
I
6.2
Plant A
32
2
2
1 hr
1 hr
1 hr
0
0
0
0
Initial
-
-
-
-
-
Same as above
1 hr
7.2
6.1
-
-
-
Shiners
18
2
2
3 hre
3 hrs
5-18 hre
0
0
0
0
Initial
8.2
5-7
-
-
-
(Notropie
18 hre
4.4
7.2
-
-
-
atherinoidee
10
5
10
5-18 hrs
5-18 hrs
22 hrs
0
0
0
0
Initial
23
8.2
7.1
-
-
-
used ae
22 hrs
24
5.2
7.6
teet fieh
5.6
5
10
5-18 hre
29 hrs
80
20
20
20
Init ial
8.2
7.3
-
-
-
96 hrs.
6.2
7.8
86
4
125
Control
5
10
ioo
100
100
100
Initial
9.0
8.1
-
-
-
96 hrs.
6.2
7.6
96
4
120
TLm (Mudi
m Toleran
ce Limit)
- Per cen
concentri
tion
I
<4.5
REMARKS
Greenish-blue
faint solvent odor
Slight turbidity-
Bo pH effect
Bright green
Sweetish solvent odor
Slight tiMbUity
Ho pH effect
Black precipitate
when «ater added
Lov D.O.
48 hr. D.O. - 3.4
24 hr. D.O. - 2.4
(J1 <3
-------
appehdix TABLEAU -BIOASSAV DATA
I TEST 71 SB - FAIHSU) MIHHOWS
i HATIOKAL ANILINE DIVISION, ALLIED CHEMIGA.N AND DYE CQRPGRATIOH DILUTION J/KTSi - T-AKT2 £RIs
BUFFALO, NEW YORK
SOURCE AH?
METHOD OF
COLLECTION OF
SAMPLE
DATE OF
COLLECTION
CONCEN-
TRATION
TESTED
PERCENT
NUM3ER
OF
TEST
FISh
VOLUME
OF TEST
SAMPLE
LITERS
TIME OF DEATH
PERCENT SURVIVAL
CHEMICAL AND PHYSICAL DATA
REMARKS
FIRST
FISH
HALF OF
FISh
ALL OF
FISH
24
HOURS
48
HOURS
72
HOURS
96
HOURS
TIME
TEMP.
°C
DISSOLVED
OXYGEN ppm.
P H
TOTAL ALK
(CaC03)
ppm.
TOTAL
acidity
(CaC03) pprti
VERSENATE
HARDNESS
ppm.
Plant A
6-21-56
100
Effluent
-
7.8
iuu
10
135
Cork Green
Taint Solvent Odoar
Bo turbidity
2* hr„ B„C. - 6.0
Low D.0«
Some reduction
in toxicity when
oxygen maintained
Effluent
S-Er.Composite
32
5
10
5 hrs.
7 hrs.
8 hrs.
0
0
0
0
Initial
23
5.2
8.0
110
6
135
7 AM - ^ PM6-21
8 hra.
23
3.8
8.0
110
6
135
Fish Added
18
5
10
8 hrs •
8-23 hrs.
8-23 hrs.
0
0
0
0
Initial
6.0
8.1
100
5
135
10 AM 6-22
23 hrs.
0.8
7.U
110
8
130
10
5
10
8-23 hrs-
all hrs.
^8 hre.
ho
0
0
0
Initial
6.U
8.1
100
3
135
U8 hrs.
Ks
7.8
98
4
130
5.6
5
10
S-23 hrs.
60
60
60
60
Initial
7.0
8.1
100
3
135
96 hre.
6.0
7-8
100
k
130
Control
5
10
100
100
100
IOO
Initial
7.8
8.2
!*
0
135
96 hrs.
4.8
7-7
96
k
130
TLsi (Mediaj
. Toleranc
3 limit) -
Per cent
Joncentral
ion
Xa5
6.2
6.2
iiS
Plant A
6-21^56
18
5
10
5-2>thrs.
5-2Uhre.
5-2Uhre»
0
0
0
0
Initial
23
-
-
-
-
-
£ffluent
ek hrs.
23
5-0
7.8
10H
8
Same ae above
10
5
10
28-1*5 hr»
100
60
60
60
Initial
_
_
-
-
- 130
Oxygenated
96 hrs.
6.8
8.1
104
2
Fish Added
5-6
5
10
5-2>t hrs
80
SO
80
80
Initial
_
_
_
1
J-*
11:00 AM 6-23
96 hre.
5.0
7.8
100
2
135
c?/
-------
APPENDIX TABLE B1 -BIOASSAY DATA
NM!I011AL aniline division, allied chemical and dye corporation
BUFFALO, HEW YORK
TEST FISH - FATHEAD MINNOVS
DILUTION WATER - UKB KRIS
SOURCE AHP
METHO* OF
COLLECTION OF
SAMPLE
DATE OF
COLLECTION
CONCEh-
7RAVI0N
TESTED
PERCENT
NUMBER
OF
TEST
FISH
VOLMME
OF TEST
SAMPLE
LITERS
TIME OF DEATH
PERCENT SURVIVAL
CHEMICAL AND PHYSICAL DATA
FIRST
FISH
HALF OF
FISH
ALL OF
FISH
2H
HOURS
1*8
HOURS
72
HOURS
96
HOURS
TIME
TEMP.
°C
DISSOLVED
OXYGEN ppm.
P H
TOTAL ALK
(CaC03)
ppm.
TOTAL
ACIDITY
(CaC03)ppm
VERSENATE
HARDNESS
ppm.
Plants BAG
1-18-56
100
Effluent
0
2.6
0
380
740
Effluent
24-Hr. Compoeitt
32
10
20
2 hre.
3 hrB.
3 hre.
0
0
0
0
Initial
24
3.8
4.6
10
90
250
In Lab
3 hra*
23
3.6
*.7
•
70
240
2:00 PM 1—18
2 4
5
10
100
100
100
100
Initial
5.2
5.9
26
60
200
Fish Added
96 hre.
2.8
5.7
20
20
200
5*. 30 PM 1-1S
18
10
20
100
100
100
100
Initial
5-2
6.0
30
35
190
96 hre.
5.2
6.8
20
6
ISO
Control
10
20
100
100
100
100
Initial
7.3
8.0
96
2
128
96 hrs.
6.8
7.8
100
4
130
TLm (Hedi
ph Tolera
ce Limit)
- Per cen
concentr
ition
28
28
28
28
Plants B & C
1-19-5&
100
Effluent
_
2.4
Effluent
24~Hr.Composite
32
2
2
30 min.
30 min.
45 min.
0
0
0
0
Initial
23
-
-
-
-
-
In Lab
1 hr.
23
3-4
3.4
-
-
-
3:00 PM 1-19
18
2
2
100
100
100
100
Initial
.
_
_
-
_
Fieh Added
96 hre.
-
-
-
-
-
U:30 PH 1-19
10
2
2
100
100
100
100
Initial
-
-
-
-
-
96 hre.
-
-
-
-
-
?I» (Hedi
\n Toler&i
ce J*iait)
- Pe»- cen
concentr
ition
24
£
24
24
Plants B & C
1-19-56
75
?
4
6-21 hrs
6-21 hrs
30-* bra
50
0
0
0
Initial
23
3.*
7.0
64
20
650
Effluent
44 hre.
23
0.2
6.8
60
20
680
Same as above
56
5
10
6-21 hrs
30-4^ hra
80
20
20
20
Initial
4.6
7.1
72
20
580
Neutralised
~
96 hre.
-
-
-
-
-
With lime
32
5
10
100
100
100
100
Initial
5.8
7.3
80
10
400
*'ls& Aaaea
12:-W PM 1-21
96 hw.
-
-
-
-
-
iLm (Hedi
in Tolerai
ce Limit)
- Per cen
concentr
.tion
15
46
46
46
Plant* B & C
2-14-5&
100
Effluent
2.0
2.9
0
660
200
Effluent
24-Hr.Composite
32
5
10
30 m n.
1 far.
1 hr.
0
0
0
0
Initial
25
5.6
3.8
0
I85
150
In Lab
1 hr.
25
5.*
3.7
0
140
155
10:00 AH 2-lU
24
10
20
1.5 hre.
3 hrs.
4 hrs.
0
0
0
0
Initial
5-4
4.9
6
90
150
Fieh Added
4 hrs.
4.8
4.5
10
68
150
4:00 PM 2-14
18
10
20
45 hre.
72 hrs.
100
70
50
10
Initial
6.2
5.8
28
85
150
96 hrs.
2.0
6.7
20
12
150
10
10
20
1+8 hrs.
72-90 hre
100
90
60
10
Initial
6.6
6.5
56
40
145
96 hre.
3.0
7.1
56
140
Control
10
20
100
100
100
100
Initial
7-6
8.1
98
1
125
96 hrs.
4.6
7.8
100
6
125
TLm (Medi
in Tolerai
ce Limit)
- Per cen
concentri
tion
21
i2
18
<10
remarks
Dark red orange
Faint solvent odor
Slight turbidity
Lov pH
Dark red
Faint solvent odor
Slight turbidity
Lov pH
Lov D.O.
Sobs precipitation
when neutralised
vith lime
Dark red-orange
Ho odor
Slight turbidity
Lov pB
4g hr.D.O. - 1.4
Aerated after 48 hre»
Aerated after 48 hrs.
\3 9~~
-------
appendix TABLE B2 -BIOASSAY DATA
NATIONAL ANILINE DIVISION, ALLIED CHSMICAL ASP SYS COBPOBATIQN
BUFFALO, HEW YORK
TEST FISH - PATHEAD MINNOWS
DILUTION WATS - LAKB ERIE
SO'JPCE AN?
ME HOn OF
COLLATION OF
SAMPLE
DATE OF
COLLECTION
CONCEN-
TRA 1 1 ON
TESTED
PERCENT
NUMBER
OF
TEST
FISH
VOLUHF
OF TFS,
SAMPLE
LITERS
—
T 1 ME OF DEATH
P—
PERCENT SURVIVAL
CHEMICAL AND PHYSICAL DATA
FIRST
FISH
HALF OF
FISH
ALL OF
FISH
24
HOURS
48
HOURS
72
HOURS
96
HOURS
TIME
TEMP.
°C
DISSOLVED
OXYGEN ppm.
P H
TOTAL ALK
(CaCOj)
ppm.
TOTAL
ACIDITY
(CaC03)ppn
VERSENATE
HARDNESS
ppm.
Plants B & C
2-14-56
100
Effluent
7.0
Effluent
Same B8 above
75
2
2
3 hrs
3 hrs
U hrs
0
0
0
0
Initifl
U.6
7-2
US
12
5>t0
Neutralized
U hrs.
5.0
7.2
50
It
520
With line
56
5
10
26->»5 hTB
U5-U8 hrs
Us hre
100
0
0
0
Initial
25
5.6
7-6
6U
8
1*30
Pis i Added
U8 hrs.
25
7.3
6U
8
UU5
xl.jOAM 2-15
32
5
10
53 hrs
53-71 hrs
72 hrs
100
IOO
0
0
Initial
6.0
7.7
su
8
315
72 hrs.
U.6
7-5
git
6
310
Control
5
10
100
100
100
100
Init* al
8.0
8.0
96
2
125
96 hrs.
U.2
7.7
100
u
130
TLm (Medi
in Toleraj
ce Limit)
- Per cen'
Coneentn
tion
65
]£2
Plants B & 0
2-21-56
100
Effluent
2.0
3.2
0
350
280
Effluent
2U-Hr.Composite
56
2
2
1 hr-
1 hr.
1.5 hrs
0
0
0
0
Initial
-
-
-
-
-
In Ie-b
1.5 hrs
2.6
3.6
0
175
235
9t 30 AM 2-2,
32
5
10
5 hrs
7 hrs
7-21 hrs
0
0
0
0
Initial
25
5.6
5-7
8
85
180
Pish Added
21 hrs
25
u.u
5.5
6
55
200
12:00 N 2-21
18
5
10
2U hrs
77-93 hrs
80
80
80
Uo
Initial
6.U
6.U
3"
3"
170
96 hre
3.2
7.3
38
g
155
10
5
10
100
100
10l
100
Initial
7.6
6.8
6U
2l*
ito
96 hrs
3.8
7.5
66
8
its'
Control
10
20
100
100
100
100
Initial
8.U
8.1
100
1
130
96 hrs
U.2
7.7
102
1*
125
TLm (Medi^
in Sol.riq
se lait)
- Per cen
Concentr*
tion
22
22
2g
16
Plants B & C
2-27-56
Same as above
100
Effluent
7.0
Neutrali?ed
With lime
56
5
10
2U-U2 hri
U3 hre
100
HO
Uo
uo
Initial
25
5.8
7-2
52
20
390
Pish Added
96 hrs
25
6.8
7.7
6g
6
385
3:00 PM 2-21
28
5
10
100
100
100
100
Initial
6.6
7 a
72
g
255
96 hrs
1.6
7.U
86
6
265
Control
10
20
100
100
100
100
Initial
8.U
8.1
LOO
1
130
96 hrs
U.2
7.7
102
H
125
TLm (Hedi
?n Tolerai
ce Liaits
- Per cen-
Concentr*
tion
>5i
iil
iiZ
iil
REMARKS
Dark brown
Precipitate formed
when neutralised
Aerated after 2U tire.
Aerated after 2U fare.
Dark ozei^e-red
No oftor
Slight turbidity
low pE
Sn»ll aaount of
brown precipitate
Low U8 hr.D.O. - 0.6
Aerated after U8 hre.
72 hr.D.C. - 2.4
i33
-------
appendix TABLE B3 -BIOASSAY DATA
NATIOHAL AHILISS DIVISIOH, ALLIED CH2HICAL AHD BIS
BOTEALO HXtfTQBI
COBPORATIOH
TEST FISH - CATHEAD MINNOWS
DILUTION WATER - LABS EBIS
SOURCE AND
METHOD OF
COLLECTION OF
SAMPLE
DATE OF
COLLECTION
CONCEN-
TRATION
TESTED
PERCENT
NUM3ER
OF
TEST
FISH
VOLUME
OF TEST
SAMPLE
LITERS
TIME OF DEATH
PERCENT SURVIVAL
CHEMICAL AND PHYSICAL DATA
FIRST
FISH
HALF OF
F ISH
ALL OF
FISH
24
HOURS
U8
HOURS
72
HOURS
96
HOURS
TIME
TEMP.
°C
DISSOLVED
OXYGEN ppm.
P H
TOTAL ALK
(CaC03)
ppm.
TOTAL
ACIDITY
(CaC03)ppm
YERSENAE
HARDNESS
ppm.
Plants B & C
3-13-56
100
Effluent
0
2.9
0
810
*80
Effluent
2U—Er.Compos ite
32
5
10
15 min
30 min
30 min
0
0
0
0
Initial
23
2.U
3-*
0
200
210
In Lab
30 min
23
2*0
3.5
0
190
210
10; 00 AM 3-13
IS
10
20
2 hrs
3 hrs
U hrs
0
0
0
0
Initial
U.U
4.5
u
100
180
Fish Added
U hrs
U.2
M
It
105
IgO
3:00 PH 3-13
10
10
20
-
-
-
100
100
100
100
Initial
23
5.6
6.1
3*
52
160
96 hrs
2U
6.0
TA
2U
6
155
5.6
10
20
-
-
-
100
100
100
100
Initial
6.6
6.6
60
28
150
96 hrs
3.6
7.4
5>>
6
140
Control
10
20
-
-
-
100
100
100
100
Initial
8.0
8.1
96
1
125
96 hrs
U.2
7-7
9lt
H
120
TLm (Med:
an Tolerai
ce Limit)
- Per cen
. Concentr
ition
13.5
13.5
13.5
13-5
Plant8 B & C
3-13-56
100
Effluent
-
6.7
18
1050
Effluent
Same &e above
56
2
2
35-^7 hrs
35-)!7 hrs
35-U7 hrtj
100
0
0
0
Initial
23
-
-
-
-
-
neutralized
U7 hrs
2U
3.8
6.9
70
&
b50
With Lime
32
5
10
Us hrs
_
_
100
so
so
60
Initial
2.6
6.7
5>»
36
3«5
Fish Added
96 hrs.
6.0
7-1
5>»
20
415
12:00 H 3-19
IS
5
10
-
-
-
100
100
100
100
Initial
U.6
7.2
78
18
295
96 hrs.
3.6
7.2
84
10
275
Control
10
20
-
-
-
100
100
100
100
Initial
7-8
8.3
92
2
115
96 hrs.
6.2
7=6
100
6
130
TLm (Medi
in Tolerai
ce Limit )
- Per cen
. Concentr
ition
>56
32
J5
Plants B & C
3-21-56
100
2
2
Effluent
-
2.5
0
600
300
Effluent
2U-Br.Composite
32
5
10
2 hrs
2 hrs
2 hrs
0
0
0
0
Initial
23
-
-
-
-
-
In Lab
2 hrs.
23
6.0
3-2
0
1*5
200
10:00 AM 3-21
IS
5
10
3-I5 hrs
3-15 tars
3-15 hrs
0
0
0
0
Initial
7.2
6
80
170
Fish Added
15 hT8.
3.0
5.0
10
50
170
5:00 PM 3-21
10
5
10
-
-
-
100
100
100
100
Initial
23
8.U
6.3
1*2
42
150
96 hra.
2U
U.2
7.0
1*0
6
1U5
5-6
5
10
-
-
-
100
100
100
100
Initial
g.s
6.8
60
24
135
96 hrs.
5.6
7.3
66
6
135
Control
5
10
-
-
-
100
100
100
100
In', tial
9.0
8.1
90
2
120
96 hrs.
5.8
7-3
92
6
120
TLm (Medi
Pn Tolerai
ce Limit)
- Per cen
Concentr*
tion
13.5
ik5
1
REMARKS
Dark orange-red
faint burnt rubber oda
Slight turbidity
Low pE
Low pH
US hr.D.O. - 1.2
Oxygen added
after US hrs.
Heavy dark brown
precipitate when
lime added.
Oxygen addtfl
after 2*1 hrs.
Dark orange—rod.
Ho odor.
Slight turbidity.
Low pH
tj?y
-------
appendix TABLE b4 -BIOASSAY DATA
HATIONfcL AHILIHS DIVISION, ALLIED CHEMICAL AHD DTK CQBPO&AIIC®
BUFFALO, NSW YORK
IB9f FISH - FATHSAD MIHHOVS AHD SKIHKRS
DILOTIOH VAT SB - UKS BRIE
SOURCE AMD
METHOD OF
COLLECTION OF
SAMPLE
DATE OF
COLLECTION
CONCEN-
TRATION
TESTED
PERCENT
NUMBER
OF
TEST
FISH
VOLUME
OF TEST
SAMPLE
LITER?
TIME OF DEATH
PERCENT SURVIVAL
CHEMICAL AND PHYSICAL DATA
FIRST
FISH
HALF OF
FISH
ALL OF
FISH
24
HOURS
48
HOURS
72
HOURS
96
HOURS
TIME
TEMP.
°C
DISSOLVED
OXYGEN ppm.
P H
TOTAL ALK
(CaC03)
ppm.
TOTAL
ACIDITY
(CaC^Jppm
VERSEMATE
HARDNESS
ppffl.
Plants B & C
3-21-56
32
2
2
30 mi- .
30 min.
30 min.
0
0
0
0
Initial
-
-
-
.
•
Affluent
30 min.
5.6
3.1
-
-
-
Same as above
18
2
2
2 hrs.
2 hrs.
2 hre.
0
0
0
0
Initial
-
.
_
•
-
Shiners
2 hrs.
6.2
5.0
_
_
•
(Hotropis
10
5
10
3-18 tare.
3-18 hrs.
26 hrs.
20
0
0
0
Initial
23
7-2
6.3
-
-
-
atherlnoides)
26 hrs.
24
2.6
6.7
-
-
-
Fish Added
5.6
5
10
26 hrs.
100
60
60
60
Initial
7.8
6.8
-
-
-
2:00 PH
96 hrs.
3.0
6.9
62
8
135
Control
5
10
100
100
100
100
Initial
9.0
8.1
-
-
-
96 hrs0
6.2
7-6
96
4
120
TLm (Kedi
m Tolerax
se Limit)
- Per cent
cone en tn
tion
8
6.2
6.2
6.2
Plants B & C
6-20-56
100
Effluent
-
2.6
0
420
520
24»Hr .Sosposi te
32
5
-
: l_r
1 hr.
0
0
0
0
Initial
4.6
3-8
0
60
250
In lab
1 hr.
4.4
3.8
0
60
250
3:00 PM 6-20
18
5
10
100
100
100
100
Initial
23
5.2
6.0
22
25
200
Fish Added
96 hrB.
23
7.0
6-7
14
6
190
11:00 A« 6-21
10
5
10
2U-U6 hrs
100
80
80
80
Initial
6.4
6-7
50
15
155
96 hrs.
5.*
7.0
50
8
165
5.6
5
10
100
100
100
100
Initial
7.0
7.1
68
8
140
96 hre.
5.*
7.3
78
6
155
Control
10
20
Initial
7.8
8.1
94
0
135
96 hre.
4.8
7.7
96
4
130
Sla (Med.
.an Tolera
ice Limit]
- Per cpr
fc concenti
ation
24
24
24
24
REMARKS
low pH
Possible low D.O.
24 hr J).0. - 2*8
Dark orange-red
SveetiBh odor
Ho turbidity
Low pH
US hr. D.O. -2.0
Added oxygen
to IS and SO
after 48 hOOto
24 hr. D.O. - 4.4
-------
apfkndix TABLE ci -BIOASSAY DATA
NATIONAL ANILINE DIVISION, ALLIED CHEMICAL AND DYE CORPORATION
BUFFALO, NEW YOBK
TEST FISH - FATHEAD MINNOWS
DILUTIOH WATER - IAKB ERIE
SOURCE AND
METHOH OF
COLLECTION OF
SAMPLE
DATE OF
COLLECTION
CONCEN-
TRATION
TESTED
PERCENT
NUMBER
OF
TEST
FISh
VOLUME
OF TEST
SAMPLE
LITERS
TIME OF DEATH
PERCENT SURVIVAL
CHEMICAL AND PHYSICAL DATA
FIRST
FISH
HALF OF
f ISH
ALL OF
FISH
21
HOURS
18
HOURS
72
HOURS
96
HOURS
TIME
TEMP.
°C
DISSOLVED
OXYGEN ppm.
P H
TOTAL ALK
(CaC03)
ppm.
TOTAL
ACIDITY
(CaCOjJppm
VERSENATE
HARDNESS
ppm.
Plant E
1-24-56
100
Effluent
23
0
1.9
0
770
240
Effluent
2^-Hr.Composi t
)
32
10
20
1^ min.
15 min.
15 oin.
0
0
0
0
Initial
6.6
2.6
0
185
160
In Lab
15 min.
7.2
2.6
0
190
160
2:00 PH 1-2U
18
10
20
30 min.
30 min.
1*5 Bin.
0
0
0
0
Initial
7.6
3.0
0
100
145 ¦
Fish Added
U5 min.
7.6
3.0
0
100
145
11.00 am L-25
10
10
20
2 hrs.
2 hrs.
3 hrs.
0
0
0
0
Initial
8.0
5.1
8
36
140
3 hrs.
7.^
5.0
6
44
140
5-6
10
20
7 hrs.
30 hrs.
U8 hrs.
60
0
0
0
Initial
23
7.8
6.3
^2
26
130
kS hrs.
23
3.0
6.8
50
10
135
3.2
10
20
72-96hre
-
-
100
100
100
80
Initial
8.0
6.8 J
68
20
125
96 hrs.
7.*
78
4
l4o
Control
10
20
-
— ^
-
100
100
100
100
Initial
8.2
8.2
96
1
125
96 hrs.
5.2
7-7
106
4
150
Tim (Med
.an Tolera
ice Limit)
- Per cei
t concent!
ation
6.2
U.2
*+.2
^.0
Plant E
1-2^-56
18
2
2
1 hr.
1 hr.
1 hr.
0
0
0
0
Initial
-
-
-
-
-
Effluent
1 hr.
7.*
7.9
90
2
325
Same as above
10
2
2
3—16 hrs
3-16 hrs
16-2U hrs
0
0
0
0
Initial
-
-
-
_
Neutralized
2** hrs.
0.8
7.*
98
12
240
With lime
5.6
2
2
72-96 hre
-
100
100
100
50
Initial
23
-
-
-
-
-
Fish Added
96 hrs.
23
7.S
116
4
220
U;00 PM 1-25
3.2
2
2
_
_
100
100
100
100
Initial
_
_
_
_
96 hrs.
7.5
86
4
170
Tim (Med
.an Tolera
ice Limit)
- Per cez)
t cone em r
ation
1=3
lz5
^6
Plant E
2-15-56
100
Effluent
23
9.^
3.0
0
280
150
Effluent
2U-flr.Composite
56
2
2
1 hr.
1 hr.
1 hr.
0
0
0
0
Initial
-
-
-
-
In Lab
1 hr.
-
-
-
-
-
1:30 PM 2-25
32
10
20
k hrs.
+-16 hrs.
U-l6 hrs.
0
0
0
0
Initial
8.2
M
2
66
130
Fish Added
16 hrs.
7.*
5.0
4
36
130
k :30 PM 2-15
18
10
20
-
-
-
100
100
100
100
Initial
25
8.0
6.1
40
3>»
130
96 hrs.
25
3.8
7.3
41*
6
140
10
10
20
-
-
-
100
100
100
100
Initial
7-8
6.5
70
22
130
96 hrs.
3.6
7.^
72
4
135
Control
10
20
-
-
-
100
100
100
100
Initial
8.0
8.0
96
2
125
96 hrs.
b.2
7-7
100
- 4
135
TIo (Med
an Tolera
ace Limit)
- Per cer
t Concenti
ation
24
2U
2b
2U
!
REMARKS
Light orange.
Very strong solvent
odor (chlorobentene).
Ho turbidity.
Lov pH
Low pH
When neutralized,
light brown precipi-
tate forme which
settles reflguyy.
Possible low D.O.
Light pink.
Slight solvent odor.
So turbidity
Possible low pH
C3 c
-------
appekdix TABLE C2 "BIOASSAY DATA test fish - fathead kxhhohs
BATIOHAL AHILIKB DIVISIOH, ALLIED CHEMICAL AID DYE CCSPCBATIOB WttBXOE KATffi - USB ffilS
BUFFALO, H2V TQBK
SOURCE AND
METHOD OF
COLLECTION OF
SAMPLE
DATE OF
COLLECTION
CONCEN-
TRATION
TESTED
PERCENT
NUMBER
OF
TEST
FISH
VOLUME
OF TEST
SAMPLE
LITERS
TIME OF DEATH
PERCENT SURVIVAL
CHEMICAL AND PHYSICAL DATA
REMARKS
FIRST
FtSH
HALF OF
FISH
ALL OF
FISH
24
HOURS
48
HOURS
72
HOURS
96
HOURS
TIME
TEMP.
°C
ISSOLVED
OXYGEN ppm.
P H
TOTAL ALK
(CaC03)
ppm.
TOTAL
ACIDITY
(CaCOj)ppn
VERSEHATE
HARDNESS
ppm.
Plant E
2-17-56
100
Effluent
7.0
2.7
0
1(80
125
Light dirty orange.
Paint solvent (sweet)
odor.
Slight tovbldity*
Low pH
Low pfi
Low pH
Heavy light colored
precipitate when
Effluent
24-Hr.Composite
56
2
2
15 min.
15 min.
15 min.
0
0
0
0
Initial
25
-
-
-
-
-
In Lab
l^ min.
-
2-9
-
-
-
2i00 PM 2-17
32
2
2
15 min.
15 min.
15 min.
0
0
0
0
Initial
-
•
_
-
-
71eh Added
15 min.
-
3.3
-
-
-
1:^5 PM 2-lg
18
5
10
30 min.
1 hr.
1 hr.
0
0
0
0
Initial
7-*
u-3
0
60
125
1 hr.
7.2
4.4
0
40
125
10
5
10
4 hrs.
4-22 hrs
4-22 hrs
0
0
0
0
Initial
7.1»
6.6
40
28
125
22 hrs.
6.0
6.9
1*
20
125
5.6
5
10
28-42 hrs
**8-66 hrs
Us-66 hrs
100
60
0
0
Initial
25
7-6
7.0
66
20
125
66 hrs.
25
5.2
7.2
6s
6
125
3.2
5
10
-
-
-
100
100
100
100
Initial
7-6
7.3
80
10
125
96 hrs.
3.2
7.5
90
6
135
TLm (Med;
an Tolera:
ce Limit)
- Per cen
; Concentr
;tion
Id
6.g
4.2
4.2
Plant £
2-17-56
100
Effluent
25
6.8
7 4
30
It
650
Effluent
Same &8 above
IS
5
10
3 hre.
U hrs.
4 hrs.
0
0
0
0
Initial
7.4
7-9
82
4
as
Light tan.
Paint solvent odor.
Some turbidity.
Low pH
Low pH
Neutralized
4 hrs.
7.2
7.8
84
6
220
With lime
10
5
10
4-22 hrs.
4-22 hrs.
25 hrs.
20
0
0
0
Initial
7.4
8.0
90
4
175
Pish Added
25 hra.
4.6
7.6
92
X
180"
li4fi PM 2-IS
5.6
5
10
34-4h hrs
48-66 hrs
72 hrs.
100
so
0
0
Initial
25
7.6
s.i
94
2
165
72 hrs.
25
4.6
7.5
98
6
165
-------
appeMX TABLE: 03 -BIOASSAY DATA
NATIONAL ANILINE DIVISION, ALLIED CHEMICAL AND DYE CORPORATION
BUFFALO, NEW YOHX
TEST PISH - FATHEAD MINNOWS
DILUTION WATER - LASS SKIS
SOURCE AHD
METHOD OF
C0LIECT10N OF
SAMPLE
DATE OF
COLLECT ION
CONCEN-
TRATION
TESTED
PERCENT
NUMBER
OF
TEST
FISH
VOLUME
OF TEST
SAMPLF
LITERS
TIME OF DEATH
PERCENT SURVIVAL
CHEMICAL AND PHYSICAL DATA
FIRST
FISH
HALF OF
FISH
ALL OF
FISH
24
HOURS
48
HOURS
72
HOURS
96
HOURS
TIME
TEMP.
°c
DISSOLVED
OXYGEN ppm.
P H
TOTAL ALK
(CaCOg)
ppm.
TOTAL
ACIDITY
(CaC03)ppfli
VERSENATE
HARDNESS
ppm.
Plant £
2-21-56
100
Effluent
9.0
7-3
90
8
1150
Effluent
Same as above
32
5
10
2 hre.
4 hrs.
6 hrs.
0
0
0
0
Initial
7.4
7.8
76
4
400
Neutralized
6 hrs.
7.0
7.5
76
4
405
With lime
18
5
10
24 hre.
48 hre.
-
80
40
40
40
Initial
25
8.6
7.6
90
6
310
Fish Added
96 hrs.
25
5.t
7.8
94
6
290
3:00 PM 2-21
10
5
10
U-18 hrs©
-
-
80
80
80
80
Initial
8.U
7.7
96
4
220
96 hre.
4.4
7.8
100
4
235
TLm (Kedi;
n Toleran
:e Limit)
• Per cent
Concentre
tioa
22
16
l£
16
Plant E
3-13-56
100
Effluent
8.8
2.6
0
960
135
Effluent
24 Er.Composite
32
2
2
15 min.
15 min.
15 min.
0
0
0
0
Initial
-
-
-
-
.
In lab
15 min.
8.0
3.0
0
475
135
10:00 AM 3-13
18
5
10
1 hr.
1 hr.
1 hr.
0
0
0
0
Initial
8.2
3."
0
150
130
Fish Added
1 hr.
8.2
3.H
0
130
130
9t00 PM 3-I3
10
10
20
3-17 hr1?.
3-17 hrs.
3-17 hrs.
0
0
0
0
Initial
8.2
U.l
0
64
130
17 hrs.
7.8
4.0
0
46
125
5-6
10
20
-
-
-
100
100
100
100
Initial
23
8.2
6.1
36
3"»
125
96 hrs.
24
3."
7-1
36
6
135
Control
10
20
-
-
-
100
100
100
100
Initial
8.0
8.1
96
1
125
96 hrs.
It.2
7-7
94
4
120
TLm (Med
an Tolera
ice Limit;
- Per cen
I Concents
ition
hi
LI
Ia5
Plant £
3-13-56
100
Effluent
9.7
90
0
1130
Affluent
Sane as above
18
5
10
8-20 hrs.
-
-
80
80
60
60
Initial
23
7.»
8.3
90
2
305
Neutralized
96 hrs.
24
4.2
7-5
90
10
325
With lime
10
5
10
56-68 hrs.
-
-
100
100
80
80
Initial
7-6
8.3
90
2
235
Men Added-
12:00 Noon 3-19
96 hrs*
4.8
7-6
96
8
235
TLm (Medj
an Tolera
ce Limit)
- Per cen
; Concentr
ition
>A§
>1£
>AS
Plant S
>20-56
100
Effluent
4.4
2.3
0
1200
180
Effluent
24-Hr.Composite
32
2
2
30 min.
30 min.
30 min.
0
0
0
0
Initial
-
-
-
-
-
In Lab
30 min.
6.8
3.0
0
33"
135
10s 00 AM 3-20
18
2
2
6-21 hrs.
6-21 hrs.
6-21 hrs.
0
0
0
0
Initial
-
-
-
-
-
?ish MU..
21 hrs.
7.>»
4.1
0
140
140
U:00AM 3-cO
10
2
2
6-21 hrs.
6-21 hrs.
6-21 hrs.
0
0
0
0
Initial
-
-
-
-
-
21 hr*.
8.2
>t.7
2
44
130
5-6
2
2
48 hrs.
48 hrs
-
100
50
50
50
Initial
23
-
-
-
-
-
96 hrs.
24
6.0
7.0
24
4
130
TLm Ue<
ian Toleri
nee Limit
- Per ce
tt Concent
ration
M
REMARKS
Large amount of a
light flocculent
precipitate*
Dirty blue gray.
Strong solvent odor.
Slight turbidity.
Low pH
Low pH
Low pH
Dark brown flocculent
precipitate which
settles rapidly.
Toxicity may have
teen reduced on
standing.
Pink.
Sweetish solvent odor,
No turbidity.
Low pH
Low pH
Low pH
-------
appendix TABLE C4 -bioassay data
NATIONAL ANILIilE DIVISION, ALLIED CHEMICAL AND DY3 CORPORATION
BUFFALO, NEW YORK
TEST FISH - FATHEAD MIBBOVS AND SEINERS
DILUTION WATER - LAKE EBIS
source; and
METHOD OF
COLLECTION OF
SAMPLE
DATE OF
COLLECTION
CONCEN-
TRATION
TESTED
PERCENT
NUMBER
OF
TEST
FISh
VOLUME
OF TEST
SAMPLE
LITERS
TIME OF DEATH
PERCENT SURVIVAL
CHEMICAL ANO PHYSICAL DATA
FIRST
FISH
HALF OF
FISH
ALL OF
FISH
24
HOURS
48
HOURS
72
HOURS
96
HOURS
TIME
TEMP.
°C
DISSOLVED
OXYGEN ppm.
P H
TOTAL ALK
(CaC03)
ppm.
TOTAL
ACIDITY
(CaC03)ppin
VERSENATE
HARDNESS
ppm.
Plant E
3-21-56
100
Effluent
23
10.4
2.5
0
680
185
Effluent
24-Hr•Composite
18
2
2
2 hrs.
2 hrs.
3 hrs.
0
0
0
0
Initial
-
-
-
-
-
In lab
3 hrs.
8.2
4.5
4
85
145
10:00 AM 3-21
10
5
10
3 hrs.
3-15 hrs.
3-15 hrs.
0
0
0
0
Initial
8.6
5.9
20
52
125
Fish Added
15 hrs.
7.6
5-9
28
30
125
5:00 AM >21
5-6
5
10
3-15 hrs.
24 hrs.
>4-39 hrs.
20
0
0
0
Initial
9.0
6.7
52
28
125
39 hrs.
4.6
6.9
50
12
125
3.2
5
10
_
-
-
100
100
100
100
Initial
23
9-0
6.9
68
18
125
96 hro.
24
5.0
7.3
74
8
120
Control
5
10
-
-
100
100
100
100
Initial
9.0
8.1
90
2
120
96 hrs.
5.8
7-3
92
6
120
TLm (MedJ
an To lersj
ice Limit)
- Per cen
; Concentr
it ion
M
4.2
4.2
U.2
Plant E
3-21-56
10
2
2
1 hr.
1 hr.
1.5 hrs.
0
0
0
0
Initial
-
-
-
-
-
Effluent
1.5 hrs•
7-6
5.8
-
-
-
Same ae above
5.6
5
10
2 hrs.
2 hrs.
3 hrs.
0
0
0
0
Initi&l
-
-
-
Shiners
3 hrs.
8.0
6.5
-
-
-
(Notroplc
3-2
5
10
4 hrs.
4-19 hrs.
4-19 hrs.
0
0
0
0
Initial
23
-
-
-
-
-
atherinoidee)
19 hrs.
24
5.2
7.1
-
-
-
Fish Added
Control
5
10
-
-
-
100
100
100
100
Initial
-
-
-
-
-
1:00 PM >22
96 hrs.
6.2
7.6
96
4
120
TLm (Med
an Tolerej
ice Limit)
- fer cen
b Concentr
it ion
/ 2.k
< %£
<; 2.4
Plant E
6-20-56
100
Effluent
23
-
2.6
0
245
210
Effluent
24-Hr.Composite
32
5
10
1 hr.
2 hrs.
3 hrs.
0
0
0
0
Initial
7.6
4.8
6
52
150
In Lab
3 hrs.
7.6
4.8
6
52
150
3:00 PM 6-20
18
5
10
7 hrs.
-
-
60
60
60
60
Initial
23
8.0
6.1
36
26
135
Fish Added
96 hrs.
23
4.8
7.1
4o
8
145
11; 00 AM 6-21
10
5
10
-
-
-
100
100
100
100
Ini tial
8.0
6.6
62
14
135
96 hrs.
4.8
7-3
70
4
135
5.6
5
10
72 hrs.
-
-
100
100
80
80
Initial
8.2
6.9
74
10
135
96 hra.
5.8
7.6
82
4
135
Control
10
20
96 hrs.
-
-
100
100
100
90
Initial
7.8
8.2
94
0
135
96 hrs.
4.8
7.7
96
4
130
TLm (Med
an Tolera
ice Limit}
- Per cen
0
0
a
0
1
'H.
sttion
20
20
20
20
REMARKS
Pink
Strong sofr eat odor
No turbidity
Low pfi
Heavy pink preclpltat*
In all lover concen-
trations.
With mortality at
this pH valua»0£*^
trelization would
not be expected to
decrease toxicity*
All fish died in eox>»
centratlons set up.
Complete survival in
the next lower con-
centration (l.S^)wotid
give a TLm valtae of
2.1
Light dirty orange
Solvent odor
Sligit turbidity
Low pfi
-------
APPjamix TABLE D1
-BIOASSAY DATA
HATIOBMj AHILIBB DIHSIOH, ALLXSD CHEMICAL AHD DYE CQRPQRATIOH
BOT7AI0, HEW YORK
TEST FX SB - FATHEAD MIHSOWS
DILUTION WATER . LAK8 EBIB
SOURCE aNP
METHOD OF
COLLECTION OF
SAMPLE
DATE OF
COLLECTION
"IH/Tl! .
THAT 1 OH
TESTED
PERCENT
NUMBER
OF
TEST
FISH
VOLUME
OF TEST
SAMPLE
LITERS
TIME OF DEATH
PERCENT SURVIVAL
CHEMICAL AND PHYSICAL DATA
FIRST
FISH
HALF OF
F ISH
ALL OF
FISH
24
HOURS
48
HOURS
72
HOURS
96
HOURS
TIME
TEMP.
°C
DISSOLVED
OXYGEN ppffli
P H
TOTAL SLK
(CaC03)
ppm.
TOTAL
ACIDITY
(CaCOg)ppm
VERSENATE
HARDNESS
ppm.
Mixed A,3 & C
„>-i
100
Affluent
23
4.0
2.6
0
320
230
and X Effluents
Plant A 3-lW
32
2
2
15 min
15 Hill
15 nin
0
0
0
0
Initial
-
-
-
-
-
B & 0 >13
15 sin
6.2
4.2
0
75
155
a 3-13
18
5
10
2 hre
2-16 hrs
2-16 hre
0
0
0
0
Initial
6.2
6.0
30
135
Mixed 3:00 P*3-lt
16 hre
5.6
6.3
22
20
130
volume released
10
5
10
2—l6 hrs
2-16 hre
_
40
4o
Uo
40
Initial
2^
7.6
6.5
58
2*»
110
96 hrs
24
5.4
7-5
5l»
6
135
Fish Added
5.6
5
10
-
-
_
100
100
100
100
Initial
8.0
6.9
7U
14
1»
5:00 P)| 3-16
96 hrs
5.0
7-6
70
6
135
Control
5
10
-
-
-
100-
100
100
100
Initial
8.6
8.2
90
1
115
96 hrs
5.8
7-7
96
It
125
Hid (Med
an Tolera
ice Limit)
Per cent
'oncentrat
Ion
3
2
3
a
Mixed A, B 4 C
3-21-56
100
Bffluent
24
4.4
2.6
0
Uoo
280
and S Bffluents
All Collected 3-23
32
2
2
1 hr
1 hr
1 hr
0
0
0
0
Initial
-
-
_
-
-
Mixed 3;0C?M J-2]
1 hr
6.8
*•3
0
70
180
in proportion to
18
5
10
2-14 hrs
15 hrs
20 hrs
0
0
0
0
Initial
7.2
6.2
36
ItU
150
volume released
20 hrs
6.4
6.0
30
30
150
Pish Added
10
5
10
_
-
100
100
100
100
Initial
24
8.2
6.7
60
26
135
S:30PM >21
96 hrs
24
4.0
7-2
56
8
1>K>
5.6
5
10
-
-
-
100
100
ICO
100
Initial
8.4
6.9
76
16
130
96 hro
5.0
7-t
f*
6
130
Control
5
10
-
-
-
100
100
100
100
Initial
9.0
8.1
90
2
120
96 hrs
5.8
7-3
92
6
120
TLm (Hedj
an Tolere
ice Limit)
- Per cen
. Concentr
Ltion
AM
fixed A, B & 0
6-21-56
100
Bffluent
23
-
5.5
&
100
325
ind S Bffluents
A. - 6-21
32
5
10
2-20 hrs
2-20hrs
2-20 hrs
0
0
0
0
Initial
5.0
6.5
62
30
185
B & C, £ 6-20
20 hrs
1.2
7.0
6U
16
190
1ixed is OOPM 6-23
IS
5
10
2-20 hrs
2-20 hrs
24-42 hrs
20
0
0
0
Initial
6.0
6.8
7*
16
170
Ln jr oportioa
42 hrs
3.2
7-2
78
8
170
Do volume release
1
10
5
10
2-20 hrs
72-90 hre
-
80
60
60
uo
Initial
23
6.8
7.1
82
8
150
Fish Added
96 hrs
23
5.2
7.6
90
k
135
2:00 PK 6-23
5.6
5
10
48 hrs
-
-
100
80
80
80
Initial
7.4
7-3
92
6
135
96 hrs
5.2
7.6
88
4
130
Control
10
20
96 hrs
-
-
100
100
100
90
Initial
7.8
8.1
9U
0
135
96 hrs
4.8
7.6
96
u
130
T1a (Medi
an Tolerai
ce Limit)
- Per ce
at Concent
ration
£3s5
11
11
M
REMARKS
Dark brownish porple
3veetish solar ent odor
Some turbidity
Low pH
With mortality at
pH 6 to 6.5. Bctv*
tralization would
not "bo expected to
greatly reduce
toxicity*
Dark broim
Solvent odor
Sua 11 amount of
precipitate
Low pB
With complete Mor-
tality at pH 6.2,
neutralisation would
not be expected to
reduce toxicity.
Dark red-orange
Sweetish solvent odor
Possible low D.O.
With mortality at
pH 6.8,neutralization
would not be expected
to reduce toxicity.
4^
-------
appendix TABLE b-i -BIO ASS AY DATA test fish - fathead whfows
HATIOHW. AHILISE DIVISION, ALLIED CHEMICAL AKD DYS COBPORATION DIUITI0H "* UKB ERIS
BUFFALO, SEW YORK
SOURCE AMD
METHOD OF
COLLECTION OF
SAMPLE
DATE OF
COLLECTION
CONCEN-
TRATION
TESTED
PERCENT
NUMBER
OF
TEST
FISH
VOLUME
OF TEST
SAMPLE
LITERS
TIME OF DEATH
PERCENT SURVIVAL
CHEMICAL AND PHYSICAL DATA
REMARKS
FIRST
FISH
HALF OF
FISH
ALL OF
FISH
24
HOURS
48
HOURS
72
HOURS
96
HOURS
TIME
TEMP.
°C
DISSOLVED
OXYGEN ppin.
P H
TOTAL ALK
(CaC03)
ppffl.
TOTAL
ACIDITY
(CaCOgJppa
VERSENATE
HARDNESS
ppffl.
Biver Intake
1-18-56
100
10
20
40 hra.
-
-
100
90
90
70
Initial
20
8.0
6.7
72
30
216
Brown.
Paint oil and sewage
odor.
Slight turtiidity.
Light grayish tee.
Faint sewage odor.
81ight turbidity.
Light grayish tan*
Faint sewage odor.
Slight toflMfety.
Light grayish tan.
Gasoline and sewage
odor.
Slight turbidity.
Light grayish tan.
Faint gasoline odor.
Slight turbidity«
8-Hr.Composite
96 hrs.
23
5.H
7-3
68
225
In Left
56
5
10
-
-
-
100
100
100
80
Initial
23
7.8
6.9
80
16
186
2:00 PM 1-18
96 hTB*
23
6.2
7.6
80
U
180
Fish Added
Control
10
20
-
-
-
100
100
100
100
Initial
7.3
8.0
96
2
128
PM 1-18
96 bra.
6.8
7-8
100
4
130
io ti* y
ilue OjS
S
A 96 hX8.
River Intake
2-14-56
100
10
20
-
-
-
100
100
100
100
Initial
IS
11.0
7-3
80
6
135
8-Hr.Composite
96 Hre.
25
4.0
7-6
80
6
135
In X^b
56
10
20
-
-
-
100
100
100
100
Initial
23
9.2
7.5
92
4
135
10:00 AM 2-Ih
96 Hr>.
25
5.0
7.7
90
6
130
Fish Added
Control
10
20
-
-
-
100
100
100
100
Initial
25
7.6
8.1
98
1
125
5:00 PM 2-11+
96 Hre.
25
4.6
7.S
100
4
130
ffo TLo 7a
ue - lOOjt
survive
n 96 hrs
Elver Intake
2-16-56
100
10
20
-
-
-
100
100
100
100
Initial
25
7.6
7.6
6U
4
110
8-Hr .Composite
96 Hre.
25
2*6
7.6
70
6
115
In La*
2:00 FN 2-16
Fish Added
3 j 00 PM 2-19
Io V
ilue - IOC
i survival
in 96 hri
River Intake
2-21-56
100
10
20
5-24 hra.
-
-
90
90
90
90
Initial
25
9.0
7-5
66
6
125
8*Hr.Composite
96 hre.
K6
7.2
6*
6
125
In lab
56
10
20
100
100
100
100
Initial
8.4
7.7
80
6
125
11:30 AM 2-21
96 hre*
5.U
7.5
84
4
125
Fish Added
Control
10
20
100
100
100
100
Initial
8.4
8.1
100
1
130
9:00 AM 2-22
96 hra.
5.0
7.6
102
4
130
Ko Tim Va
Lue - 90^
survival i
1 96 hTB*
Biver Intake
3-13-56
100
10
20
80 hra.
-
-
100
100
100
90
Initial
2**
10.0
7.5
72
4
115
8-Hr.Composite
96 hrs.
5.0
7.4
72
6
110
In Lato
56
5
10
100
100
100
100
Initial
9.0
7.7
80
2
115
2:00 PM 3-13
96 hrs.
5.8
7.6
82
6
120
Fish Added
Control
10
20
100
100
100
100
Initial
8.0
8.1
90
1
125
9:00 am 3-1U
96 hrs.
5.4
8.0
94
4
125
No Va
lue - 903&
survival i
1 96 tars.
&
-------
appsndix TABLE E2 ~BIOASSAY DATA test fish - fathead minnows and shiners
NATIONAL ANILINE DIVISION, ALLIED CHSWICAL AND DYE CORPORATION DILUTION tOTfii - LAKE 2RIS
BUFFALO, NEW YORK
SOURCE AND
METHOD OF
COLLECTION OF
SAMPLE
DATE OF
COLLECTION
CONCEN-
TRATION
TESTED
PERCENT
NUMBER
OF
TEST
FlSh
VOLUME
OF TEST
SAMPLE
LITERS
TIME OF DEATH [ PERCENT SURVIVAL
CHEMICAL AND PHYSICAL DATA
REMARKS
F IRST
FISH
HALF OF
FISH
ALL OF
FISH
24
HOURS
48
HOURS
72
HOURS
96
HOURS
TIME
TEMP.
°C
DISSOLVED
OXYGEN ppm.
P H
TOTAL ALK
(CaC03)
ppm.
TOTAL
ACIDITY
(CaCOgJppm
VERSENATE
HARDNESS
ppm.
River Intake
3-21-56
100
5
10
-
-
-
100
100
100
100
Initial
23
10.8
7-2
86
12
155
Grayish tan
Faint gasoline odor
Slight turbidity
Same as above
Dark Brown
Faint solvent odor
Low D.O.
Same as above*
No reduction in
toxicity vhen
oxygenated.
8-Hr .Composite
96 hrs.
5.2
7-4
90
6
155
In lab
56
5
10
-
-
-
100
100
100
100
Initial
9.4
7.5
88
6
l40
10}00 AM
96 hrs.
5.6
7.5
92
8
135
Fish Added
Control
5
10
-
-
-
100
100
100
100
Initial
9.0
8.1
90
2
120
7:30 PM "5-21
96 hrs.
5-3
7.3
92
b
120
No TLm V
Llue
100J& Surv
Lval in
hrs.
Xiver Intake
>21-56
100
5
10
72 hrs
-
-
100
100
80
80
Initial
23
9-6
7.1
88
10
160
Same as above
96 nrs*
4.4
7.6
96
6
155
Shiners
56
5
10
100
100
100
100
Initial
9.0
7-4
90
&
150
(Notropis
96 hrs.
4.8
7.7
98
4
130
atherinoides
32
5
10
100
100
100
100
Initial
9.0
7.7
90
4
135
Fish Added
96 hrs.
5-0
7-7
10>t
4
130
10:00 AM >22
Control
5
10
100
100
100
100
Initial
9.0
8.1
90
2
120
96 hrs.
6.2
7-6
96
4
120
No XL m
felue
80# Surv
:val in #
hrs*
River Intake
6-21-56
100
5
10
2 hrs
4 hrs.
4 hrs.
0
0
0
0
Initial
23
0.4
6.8
72
30
250
8-Hr,Composite
4 hrs.
0.0
6.5
62
35
205
In Lab
56
5
10
29-48 hrt
100
80
80
80
Initial
4.4
6.8
76
12
200
7-3 PM 6-21
96 hrs
4.6
7.3
78
6
185
Fish Added
32
5
10
29-48 hrs
100
80
80
80
Initial
6.0 ¦
7.1
80
9
170
11:00 AM 6-22
96 hrs.
5-4
7.7
8>»
4
160
Control
10
20
96 hrs
100
100
100
90
Initial
7.8
8.2
Sk
0
135
96 hrs.
4.8
7.7
96
4
130
TLm (Medi
tn Toleran
ce Limit)
• Per cent
Concentre
tion
IS
12
12
12
Same as above
'6-21-56
100
5
10
3 hrs
4 hrs
29-48 hrs
20
0
0
0
Initial
23
4.U
-
-
-
-
Oxygenated
48 hTB.
5.6
7.4
9U
8
225
56
5
10
7-22 hrs
SO
80
80
80
Initial
-
-
-
-
-
96 hra.
7.6
7.8
80
4
175
32
5
10
7-22 hrs
80
80
80
80
Init ial
-
-
-
-
-
96 hrs.
7.0
7.9
84
4
160
------- |