r
PB 2 I 6 84 1
WASTE INVESTIGATIONS, SEMET SOl.VAY
DIVISION, ALLIED CHEMICAL AND DYE
CORPORATION, TONAW AN DA, NEW YORK.
PART I. WASTE SURVEY REPORT. PART II.
BIOASSAY INVESTIGATIONS
H. A. Anderson, e t a 1
Robert A. Taft Sanitary Engineering Center,
Cincinnati, Ohio
19 56
r
DISTRIBUTED BY:
National Technical Information Service
U. S. DEPARTMENT OF COMMERCE
5285 Port Royal Road, Springfield Va. 22151
V

-------
VASTS IV7SSTIGATI018
7QB
iihbiatioial joiif commissiov
PART I - WASTE SmVXT HE PORT
PAST II - BIOASStf I WESTItf ATIOHS
HA5UUET PIAST
SfJffiT-SOT.VAT DIVISIO*
AIJ.IZD CHEMICAL ASD DTS COHPORATIOl
TOHAWAHDA, IE* TOM
U. S. OTPAMUHfT OF HEALTH, EDUCATION, AHD WlLfAOT
Public Health Service
Ho'oert A. Taft Sanitary Inglr.eerir-g Centar
Cincinnati, Ohio

-------
/
VASTS IirtSTIGAflOfB
SBOT-SOLVAI DIVISIOI
ALLIED CRXMICAL AID DTI CORPCHATIOI
701AVA1DA, BV TOBI
Introduction
Curing the periods Oct. 28-Hov. 1 and Hov. 7-8, 1956, investigations
were conducted to determine the pollutions! characteristics of Seaet-
Solvay oil-gas generator and by-product coke plant wastes which are dis-
charged Into the Biagara liver.
Fart I of this report cover a study of waste flows and certain pol-
lutional characteristics in relation to plant operations.
Part II covers an investigation of the toxicity to fish of some of
the plant effluents.
Personnel Participating
Semet-Solvay Division
Mr. 1. 0. Briggs
Mr. George Meyers
Nr. Irnest Springer
Mr. tobert Shea
Mr. David Ziomer
Mr. L. A. Angua
Public Health Sarvlce
Bayse H. Black
Croswell Henderson
E. A. Anderson
M. W. Susia^
Superintendent
Aset. Superintendent
Chief Chealst
Asst. Chief Chaatet
Chemist
Oil Gas Generator Plant Foreman
Industrial Wastes Consultant
Aquatic Biologist
Public Health Engineer
Chemist

-------
PART I - WASTE SURVEY REPORT
By R. A. AaderBor.
Purpose
This survey was conducted to determine the current quantities of water
polluting materials In process wastes discharced from the Sexet-Solvpy oil
gas generator rind by-product coke plants into the Si agar a River. Ko previous
data on the wastes from the oil gns generating plant were available ns this
plant began operation subsequent to the cooperative study conducted lr. August
foveaber 19^. Data on oil discharges from this riant was part icu^ai Ly de-
sired. This survey Is a part of an investigation of Boundary Waters being
conducted by the International Joint Commission in conjunction w11n the Sew
fork State Water Pollution Control Board program to achieve the Objectives
for Boundary Water Control Adopted by the International Joint Commission.
Organization of the Survey
This survey was cooperatively conducted by the Senet-Solvay Division and
the I. J. C. Field Unit of the U. S. Public Health S*r vice. It was initiated
by a letter dated Kay 18, 1956, from the lew York State Water Pollution Con-
trol Board to the Semet-Solvay Division sug, est: r-g that a seating of compaiy
and I. J, C. Field Unit personnel be arranged to discuss th? feasibility of
a study, k preliaiinf..*y conference vsb held or, June ? ->nd at a meeting or.
October 16, specific arranfecents were s-p.de for the conduct cf the survey.
Duplicate samples were collected and similar ar^lyees of effluents were
made by company am. I. J. 3. chemists. The company provided laboratory space
for the use of the I. J. C. Unit porsr jiel and all qnnlytical determinat lona
during the October 26 to lovamber 1 period were carried out in the company

-------
laboratory, fhc Hovaaber 7 and 8 analyses were run only by I. J. C. Flela
Unit personnel In the I. J. C. Field Unit Laboratory.
Q2SXRAX IH70RHATI0H
Locatlop of Plant
This plant la located approxitalely 1-1/^ o-ile north of Sher'dan Drive
on River Road, To of Tonawanda, Hew York.
The coke plant produces blast furnace and xetallurgicai coke end a very
Halted quantity of doi&estic coke froi coal obtained from Pennsylvania and
West Virginia fields. Coking is accomplished m Seaet-Sclv?; design hori-
zontal flue typo ovens. By-producto Include gpf., enmonip or tc 39? llqu^
tar, pyridine and light oil. The concentrated amonia liquor is recovered
by neans of the indirect process. Light oil is not refined and separated
into its principal fractions of benzene, toluene and xylene at tr.:s plant.
k flow chart of the coke plant Is shown in Figure 1.
The oil gas generating plant produces ac sil gas which is delivered to
an adjacent plant for the production of certain petrochemical products. Much
of the production and operating features of this plant arc classified as
trade secrets b> the company. Therefore relatively little information on
production processes of this plant is available.
Both the coke and oil gas generator plants are operated 21- hours per
day and ? days per week.
Onwatlng Data
4 total of 195 ovens are pushed per day. During the periods of this
survey dally production was essentially constant at the following rate per
2b hours :

-------
	jpf
M*'"
J Lc_j
IfH *.
u.
-1
4 H
'* * n
SIMPLIFIED FlCW diagram
SI'OWIMG LIQUID WASTES DISCHARGED
SEMET SOLVAK DIVISION
ALLIED CHEMICAL AMD DYE C OR PORAT I 0|i
Fijure I

-------
Coal charge&
Cok produced
Coke oven gas
Tar
Ammonia as 16-3#
liquor
Light Oil
Pyridine
Coking time
Coke oven flue temp.
2,600 tons (Dry BpbIs)
2,000 tons (Dry Basis)
28,0 million cubic feat
21,000 gallons
60,000 lb. (1^)280^ equivalent
7,200 gallona
0
15 houra
1,300 - 1,360* C.
or 2,3?2 - 2,^80* F.
Employees
fha total number of employeee including office personnel is approxi-
mately fcOO. The maximum number on duty during r>ny 21* hour period does r.ot
exceed 26*5. About ^04 of the number are on the day shift with 30# on the
other two shifts.
Water Supply
MwHBMnaBaUBala
All water is obtained from the Klagara River. The pump station la
located adjacent to the river on the south edge cf the Wickwire Spencer
Steel Division property and upstream from the Steel Plant and Senet-Solvpy
waste outfall*. Coarse screens prevent debris from reaching the pump In-
takes. Process water is untreeted. Water for drinking and sanitary use
Is treated by a company water purification plant.

-------
- 6 -
PUOT WASTES
Sewers
411 process wastes, septic-tank-treated sanitary wastes from the cen-
tral locker room and curface run-off froa the coke plant drain to a two foot
wide rectangular cress section sever located along the west edge of the plant
area. This sewer discharges into a sump nt the northwest corner of the prop-
erty.
Oil gas generator plant wastec drain into a 30 inch dlpmeter sewer which
runs m a westerly direction and discharges into the above sump. Untreated
sanitary wastes from the office are discharged directly to tlie sump.
The msp dlsfcharges into a sewer extending in a westerly direction which
crosses Hiver Rood on an overhead bridge. The sewer section crossing the road
consists of 2k inch diameter cr>et iron pipe. It discharges into a sewer on
Vlckwire Spencer Steel Division property which carrl* the combined steel
plant and Semet-Solvay wastes to the liagara Biver.
Coke Plant Wastes
Liquid wastes of this cok* plant which are signif leant fro & the ct Mid-
point of content of polluting materials or volute are;
Quench water. A relatively large volute of water used to cool the in-
candescent coke. The settling basins for removal of coke fines froc the quench
water w#re relatively full of fines at the time ol this survey and therefore
were not removing the maximum quantity of cuspended solids from the sewered
quench water.
Cooling Water. A large volume of water used for indirect cooling of re-
circulating and distilled nmronla liquor, wash oil, light oil compressed gas.
This water Is normally uncontaminated but may contain significant quantities

-------
of polluting materials m the event of lepks in the coils or tubes.
Ammonia Still Waster. The liquor resulting from steom stripping ammonia
from raw ammomacal liquor. This waste is normally a principal source of
phenols, cyrnides and ti.iocyanates in wastes from this type coke plant.
Light oil and wash oil decanter water. Light oil decanter water Is the
water decanted from the cooled light oil after separation from the wash oil by
direct steam distillation. Wash oil decanter water is the water decanted from
the wash oil after the above separation. At this plant the light oil and
wash oil decanter water pass through a common muck tank and are discharged to
 The sack tank provide* for further
the sewer through a corner, pipe.
" decantat ion to that any oil ^tioh
Oil Sas Generator Plant Wattes
may accomodate mj be removed.
Tar Separator Zffluent: This is an intermittent overflow of excess water
from the tar or oil separator. The influent to the tar separator consists
of one stream of tar containing water froc. the oi 1 gas generator and two
streams from the two direct type oil gas cooling towers. Dett-rgent is
added ta this water to reduce the surface tension accomplishing unproved
separation of the tar. This water is cooled in indirect coolers and recir-
culated to the oil gas generator and oil gas coolers. With proper operation
there appears to be very little build up of water and overflow of wastes
from this separator. However, during the first day of the survey there was
a significant overflow of oil or tar containing wastes froc this separator.
Plant officials discovered that this excessive overflow w?s due to a valve
having been left open on a make up water line to the separator. This waa
corrected before the second day sampling and piping changes to prevent the
possibility of a recurrence were in pro.-ress before the survey was completed.
Any overflow which occur* is discharged into the cooling water collecting

-------
bam of the indirect coolers cooling the recirculating water to the o;i
gas coding towere.
Sas Holder Water Seal Overflow. This 1b an intermittent overflow cf
oil or tar containing water from the water seal of the oil generator gas
holder. Source cf this water is condensate from the gas cooling ir. the holder.
It also discharges into the indirect ccoling water collecting "casir..
Indirect Cooling Vater
This water, which has been used for- indirect cooling of the water recircu-
lated to the oil gas generator and oil g; e cooling towers nccounts for almost
all the volus* of tr.e oil gas generator plant wastes. It is uncontR:-;r.nted ex-
cept in the evert of breaks ir. the tubes permitting oil gas cooling tower water
to enter it. So Leaks were observed during the survey.
SURVEY METHODS
Saople Collection
Uniform portion sasoles of all effluents studied were collected r.ourly
over an eight hour period beginning at 8:00 AM. Samples for pher.c.. analysis
were preserved with CuSOi. and samples for cyanide determinations were pre-
served by adding sufficient HaOH to provide a pH of U or above. For the
oil determination a ^ oz sample was collected hourly and poured into a
glass stoppered one liter bottle. In the analysis for oil content :>oth the
k oz. and liter bottles were rinsed with solvent to recover any on clinging
to the inside of the bottle.
Separate samples were collected for oil determination by Seiaet-Solvay
and U.S.P.H.S. analysts. In the determination of other constituents al'
analysts used portions of the same samples. The number of effluents samp-
led was limited by the capacity of the analysts to complete the desired

-------
determinatlone within 2^ hours of sample collection, During the period from
10-26 to ll-i inclusive samples of intake water, oil rns generator plant ef-
fluent, coke plant efficient and combined coke and oil gas generator plant
effluent were collected daily. Oil gas holder effluent and tar separator ef-
fluent were collected on one day during this period.
On Nov. 7 and 8 samples were collected from the coke quenching station,
combined light oil and wash oil decanter, ammonia still #1, ammonia still #2,
oil gas holder overflow, oil gas generator plant, coke plant and combined
coke and oil gas generator plant effluents for phenol, cyanide and bioassay
analyses. Results of bioassay analyses are reported in Part II.
Analytical Methods
Analysis for cyanide, oil, phenol and pi were made by methodu adopted as
official methods for Boundary Water qufility by the Board of Technical Advisors
to the International Joint Commission. Acidity, alkalinity, and solids deter-
mination were m?de by procedures according to those fiiven in "Standard Methods
for the ExAnination of Water, Sewage and Industrial Wastes" published by the
American Public Health Association.
flow Measurements
The discharge volumes of coke plant wastes, oil <:as generator plant wastes
and coaMned oil .as generator ana coke plant wastes were measured by a Price
current meter. Measurement of the coke plant wastes were mode in the rectangu-
lar cross section sewer at a point approximately 15 feet upstream from the
point of discharge into the sump. A Friez water stage recorder was installed
on this sewer during several days of the survey. The charts obtained Indicated
essentially constant and equivalent flows during all 2k hour periods checked.
It is believed that the flow measurements of this waste are accurate within
the limits of five per cent.

-------
- 10 -
Oil gas generator plant waste flow was measured In a manhole approxi-
mately 125 feet upstream from the outfall discharging Into the sump. The
Frier water level recorder Indicated that flows fluctuated somewhat over
short Intervals of time (approximately 10 minutes), but hourly averages were
uniform over 2^ hour periods of time. Because of this fluctuation, the
measurements are somewhat lees accurate than those of the coke plant sewer.
The volume of the combined plant effluents was measured In a tee in the
2U Inch cast Iron sever pipe at a point on Vlckwlre Spencer Division prop-
erty Just upstream from where the pipe goes underground. The high flow vel-
ocity In this sewer resulted In considerable turbulence when the current
meter was Introduced. Current reter determination under these conditions
may be expected to be somewhat lower than the actual flow.
The combined light oil and wash oil decanter wastes were coasured by
timing the discharge of a known quantity with a stop watch. The volume of
ammonia still wastes was calculated from the measured feed volume and steam
Introduced.

-------
- 11 -
RESULTS
Ploy Meaeureaente
Iffluent Oi|	Type Pf Htftl.	tlSM.
Oil Gas Generator Plant 10-18-56	Large Price Current Meter 2.737* #
Oil Gas Generator Plant 10-31-56	"   * 2.19
11-1-56
	 "  lUOQ M	m - i. -	1,^63
11-1-56
"   * 3:^5 PM	Snail "  " 1.62
	- .  11-1-56	I*rge   	1.52
Average	1.73
Coke Plant Sever 13-18-56	Large Price Current Meter 11.5*
	 " 10-30-56	*   " 11.
	* " H-l-56	  "11.1
Average	11.25
Combined Ccke and Oil Gas Generator Plants (bus of individual	13.0
measurements)
Combined Coke and Oil 10-30-56	Large Price Current Meter 12.1
Gas Plant Effluent
   10-31-56	  " *12.05
Average	12.1
lo.l Ammonia Still 11-7-56	Calculated from Input	0.153
oil Ammonia Still II-8-56	  	0.137
Average	0.1^5
Vo.2 Ammonia Still 11-7-56	Calculated from input	0.1M)
to.2 Ammonia Still ll-e-56	"  "	0.117
Average	0.129
Combined Light and 11-7-56	Timed a Measured Volume	0.03?
Wash Oil Decanter	II-8-56
   1H3C AM	 " " "	0.0^2
II-856
*	  y.k*, pk	- " - "	0.036
Average	0.038

-------
- 12 -
	trial run measurement* sad* before the survey and not included in the
average*.
#	During thia period there wa* an abova-normal discharge from the tar
separator due to addition of excess make-up water.
fha average* of the flow neaaureoents of each effluent were uaed in the
calculations in thia report. The combined coke and oil ga* plant flow used
in the calculation* la the on* obtained by summing the measured individual
plaat waste flow*. Condition* for aeasuring the combined effluent war* such
that the valaa obtained wai expected to be *oewhat low. It should be noted
that the variation between the mim of the individual effluent measurements
and the combined effluent was less than 10)1.
AIXLTTICAl RIStJLTS
The result* of the waste determination* are presented in Tables 1 through
5.
Tha analytical result a reported are those of the I.J.C. Held Unit lab-
oratories.. The chemical determination of the two laboratories were in sub-
stantial agreement. The reported net concentration of materials in the waste
is tha concentration found in the wastes less the concentration found in the
intake water. The net value is assumed to be the quantity contributed by the
plant. The quantity present in the Intake water was significant only in the
case of oil and solids determinations.
Oil and Ither Bxtractable Material
The oil content of the oil ga* generator plant varied from 3*0 to 8.0
ppa on the three day* of sampling with normal operations. The effect of

-------
- 13 -
adding excess aake-txp water to the tar separator on October 28 Is Indicated
by the IS ppa of oil la the effluent on that date. This is more than twice
the aaoust of oil discharged to vast* on the other days saapled.
the concentration of oil in the cola plant effluent varied from 2 to 8
pja -iid la the coabined plant effluent varied from 2 to 12 ppn. The value
of 12 ppa In the coabined efficient on October "1 Is higher than the concen-
tration in either of the separate plant efflueats. Seaet-Solvay analysts
found 5 ppa In their sanple. It appears that the sample analysed by the
I. J, C. chemist any not have been representative.
Coaparlson of the results of this survey with the 19W survey Indicates
relatively little change in the total quantity of oil discharged to waste.
Phenols
Of particular Interest is the gradual daily increase of phenols in both
the coke plant and combined plant effluents from the first day (10-28) to the
last day (11-1) of the five day survey. During this period, routine plant
control analyses of the Seaet-Solvay laboratory showed that the concentration
of phanols In the weak aniLonla liquor feed to the still was lower than usual
and also increased towards the end of the survey.
As part of the bioassay study, phenols were nleo run on these effluents
on 11-? and 11-6. They were significantly higher, Indicating that the in-
crease continued during the Interla between the samplings.
Plant officials reported that their routine analyses hrve shown marked
gradual Increases or decreases of phenol concentration in the aononia liquor
feed to the still. Coking teaperature and other operations known to affect
phenol concentrations in aaconia liquor feed as well as in the waste do not

-------
- 14 -
vary efficiently to explain the change is qu?ntity of phenols. It It be-
lieved that the result obtained in this survey indicate that the phenols
discharged vary significantly. The plant chemists are concerned with this
phenomena and are attempting to find the reason for it. The average dally
quantity of phenols found in the coke plant wastes during the period 10-28
to 11-1-56 (l4io lbs.) was significantly lover than the 2909 lbs. found during
the 19^ survey. The 21?0 lbs. of phencle found on 11-7 and 11-6, 1956 is
somewhat higher.
Hienols in the oil gas generator plant effluent ranged from 5.8 to 26.9
pounds per day which is considerably less than the coke plant discharge.
Suspended Solids
It was possible to make suspended solids determinations on only one day
of this survey, too isuch confidence can not be placed on a single analysis
but it is interesting to note that the quantity of suspended solids found in
the wastes in 1956 is narkedly lower thrn during the 19**8 study. There is
no known reason to expect such a reduction.
Cyanide
Cyanide deterslnations of less than 3.01 ppm are reported as 0 in this
report. The maxima; concentration of cyanide found in the coke plant efflu-
ent during the 10-28 to 11-1 period was 0. )2 ppm as compared to 2.6 ppm max-
ims concentration found during the 19^*8 survey and 1.5 ppm found on Iove-
ber 8.
The quantity of cyanide in the ama.or.ia still wastes and light oil de-
canter water was significantly higher on 11-8 thon on 11-?, the only two
days this determination was made. The quantity in the total coke plant

-------
15 -
wastes was alto significantly higher on 11-8 which tends to substantiate
that the increase actually occurred and the variation found was not due to
error in saspliag or analysis of an individual saasple. The reason for the
marked increase is not known.
Alkalinity, Acidity, and pS
The change in alkalinity, rcidity, and pH of the effluents as coapared
to the intake mater is not extreue.

-------
- 16 -
Source
TABLE 1
AIALYSIS Of OIL AID PHISOL OOST11T
07 IVTAZE VATS AID F.FTLUKHTS
Flew
gd
PHHOL
OIL
Grog
JSL
ppm lb/day pp lb/opy Srostpps let ppa
let
Discharge
lb/day
Intake 10/28
I1agara 10/29
SItit 10/30
10/31
11/1
AVERAGE
far	10/28
Separator
Effluent
Oil Oae 11/1
Holder 11/?
Overflow 11/8
AVERAGE
n/?ae
Oil Gas
Generator
Plant
Effluent
10/28
10/29
10/30
10/31
11/1
AVERAGE
11/7
11/8
AVERAGE,
11/746
Quanch
Water
11/7
3
2
1
	1
1.0
428.0
425.0
.018
 059
.000
.0^3
.000
.02**
6.3
Light and 11/?
Vaah Oil 11/8
Decanter
Water
AVERAGE,
11/71B
Aaaonia 11/7
Still #1 11/8
A7ERAGI,
11/718
0.038
0.038
1.5
8.3

86.0

85

17.6
17.6




139


25.4







24.5




139


24.9

1.73
18*
260*
15*
216 
1.4*
1.4
20.2
1.73
7
101
5
72
1.5
1.5
21.6
1.73
_
-
-
-
1.0
1.0
14.4
1.73
8
115
7
101
0.4
0.4
5.8
1.73
3
^3
2
29
1.6
1.6
23.1
1.73
6
66.3
4.7
67
1.18
1.2
16.8
1.73





2.0
28.9
1.73





2.0
28.9
1.73





2.0
28.9
1.5
H*5
8.8
10.1
0.153
0.137
0.145
742
8^5
793
3.64
2.79
3.21
947
964
955

-------
Source
- 17 -
TABLE 1 (Cont'd)
analysis o? oil and ?he::cl :o*rrt:;!
or i it ate  .'Ax's ai;d ;:stlukhts
P H E I 0 L
OIL
Dat# flow
grgt
	9*1 	
1956 agd ops lb/day ppm lo/day Oroea ppm Vet ppc lb/day
JUL
Vet
Discharge
AjKonia
Si 111 #2
11/7
11/8
A7ZHAGK,
11/716
O.lkQ
0.11?
0.128
900
791
8^5
1050
770
910
Total
Aauconla
Still
AVX8AG2
Cok#	10/26
Plant	10/29
Effluent 10/30
10/31
11/1
ATXRAOZ
11/7
11/8
A7ERAGX,
11/748
Con.bined
Oil.Oae,
Generator
and Col
PlpDt
A7XRA0I
0.273
10/28
10/29
10/30
10/31
11/1
81*5
I865
11.25
5
U69
2
188
13.0
13.0
1220
11.25
6
563
h
376
13.*
13.k
1257
11.25
8
750
6
563
Ik. 9
lk .9
1399
11. 2S
3
281
2
188
16.7
16.7
1568
11.25
2
188
1
94
17.1
17.1
160k
11.25
k.8
*51
3
282
15.0
15.0
lklO
11.25




23.6
23.6
2210
11.25




22.7
22.7
2130
11.25




23.1
23.1
2170
13.0
11*
1193*
8*
867*
11.6
11.6
1258
13.0
k
*33
2
216
11.6
11.6
1258
13-0

-
-
-
12.8
12.8
1389
13.0
12
1300
11
1193
13.9
13.9
1508
13.0
2
216
1
108
lk. 9
lk. 9
1618
13.0
6
650
k.7
508
13.0
13.0
1406
13.0




20.0
20.0
2160
 lot Included In the averages.

-------
- 18 -
SHET-SOLVAY
TAB LI 2
ACIDITY, ALKALUITT, CTAIID1 AID pH
AHALYSES OT INTAKE VATIH AID Z77LU9TS
Cyanide Alkalinity Aciuity
Date flow		 	 	
Bourc*
1956
mgd
PPa
ib.per day
PP
PP
pH
Intake
10/28

0



7.1
Hiagara
10/29

0

8^
1
-
River
10/30

-

-
-
-

10/31

-

-
-
7.3

11/1

-

-

7.7
AVYRAOX

0

8k
1
7.3
Tar
10/28

0



7.1
Separator
11/1





7.7
Effluent







A7ERAGI

0



l.k
Oil Gas
11/1

0




Holder
11/7

0




Overflow
11/8

1.30




Oil Gaa
10/28
1-73
0
0
-
10
7.3
Oenerator
10/29
1.73
0
0
8^
-
7.**
Plant
10/30
1.73
0
0
-
-
-
Xffluent
10/31
1.73
0
0
-
-
7.2

11/1
1.73
0
0
-
-
7.3
ATS AOS
1.73
0
0
6k
10
7.3

11/7
1.73
0.03
0.390
-
-
-

11/8
1.73
0.0
0.0
-
-
-
AYJRAOI
1.73
0.02
0.20
-
-
-
Quench
11/7

0.38




Vater







Light and
11/7
.038
3.88
1.2



Vaeh Oil
11/8
.038
116.0
36.8



Decanter







Vater







AVXRAOl
.038
59.9^
19.0



Aaconia
11/7
0.153
2.60
3.3



Still #1
11/8
0.137
^1.0
U6.7



AVE? AO*
0.1^5
21.8
25.0




-------
-19-
SWET-SOLTAT
TAB 12 2 (Cost>d)
ACIDITT, ALIALI1ITT, CTUIDI AID pi
AIAXTSIS OF I IT AH WAHf? AID IFFMfclTS


CyanIda
Alkalinity
Acidity

Sat*
Flow



	 

Sourca 1956

PP
lt>.per day
PP
PP
pfl
Aanonia 11/7
o.i4o
2.4o
2.8



Still #2 11/8
0.117
5.00
4.9



AVXRAQl
0.128
3-70
3.8



Total






Aaron la






Still






A7XRMI
0.273

28.8



Cole Plant 10/28
11.25
0.01
0.9

_
7k
Effluent 10/29
11.25
0.0
0.0
86
12
7.1
10/30
11.25
0.0
0.0
-
-
-
10/31
11.25
0.02
1.9
-
-
7.1
11/1
11.25
0.01
0.9
-
_
7.8
ATESAGI
11.25
0,01
0.7
-
-
7.3
11/7
11.25
0.23
21.0
-
-
-
11/8
11.25
1.50
141.0
-
-
-
A7ERA0I
11.25
0.86
81.0
-
-
_
Combined 10/28
13.0
_


_

Oil Oaa and 10/29
13.0
0
0
88
10
7.5
Coke Plant 10/30
13.0
-
-
-
-
-
Effluent 10/31
13.0
-
-
-
-
6.8
11/1
13.0
-
-
-
-
7.7
AVZSAGK
13.0
0
0
88
10
7.3
11/8
13.0
1.40
157.0
-
-
-

-------
- 20 -
TABIC 3
HALTS13 07 SOLIDS COITXKT 07 IOTAH VAfTO JBD E77LDZ5TS
StJSPXSDlD SOLIDS	TOTAL SOLIDS
Data flow Cone, la una Pleeh. Iba/day Cose, In x>xm Pjech.lbf/fog
Source 1956	Orost Vet Oroas Set Orott let Cross Vet
Intake 13/2$	10	2U6
91agara
River
Oil Oat 10/29 1.73 31 21 kU7 303 352 106 5080 1530
Oeaerator
Iffluent
Coke 10/29 11.25	3^ ^130 . 3190 520 27** <46800 25700
Plant
Effluent
Combined 10/29 13.0 36 26 3900 2820 U92 ZU6 53200 26?00
Oil Oae
and Coke
Plant
Effluente

-------
- 21 -
TABU b
SUMMARY Of T QJMITITI OF COSSTITUHTS II VAS'fZS
OIL
PHPOL
CTAlIJl
SCSPXIDID



Lb a. per

Lb t.per

Lbs.per

Lba.per

Lbs.per



1000

1000

1000

1000

1000



tone

tons

tons

tons

tons

Lbs
.per
dry
Lb a.per
dry
Lba.per
dry
Lb .per
dry
Lba.per dry
Source
Period 2* Hn.
coal
21* Ire.
coal
2k Hre.
coal
2h Bra.
coal
2# Bra.
coal
Light and Wash Oil
Iot.?-8


3.21
1.1
18.5
6.6




Decanter Water











Ajunonia Still Vo.l
Iov.7-0


955
3^1
25.0
8.9




Ammonia Still Bo.2
Iov.7-8


910
325
3.9
l.J




Total Anconla Still
Iov.7-8


1665
667
28.9
10.3




Coke Plant Iff luent
10/28toll/l
282
101
1^10
5C*
7-5
2.7
3190
11^0
25,700
9190

Hov.7-6


2170
775
81.0
28.9




Oil 0a Plant
10/28toll/l
6?

16.8
6.0
0.0
0.0
303

1,530

Zffluent
*ov.7-8


28.9
10.3
0.2
0.1




Total Vasts
10/28toll/l
508
181
1^06
522


2820
1010
26,700
9550

Sov.7-8


2160
771
151.0
5lhQ




\

-------
22 -
TABU 5
COMPARISON or GROSS WASTI LOAD II KOTOS PIB DAT Wfl 19*8 StJHflf
S222ce
OIL
PHPOL
CYAIIDH
StSFZlDXS
WW
TOTAL
9QUSS
*ot. 10/28- lov. 10/28- 11/7-8 lov, 10/28- 11/7-6 lov. 10/26- ov. 10/28-
Dec. 11/1 Dec. 11/1	Dec. ll/l	Dec. ll/l Dec. ll/l
1948 1956 1948 1956 1 956 1948 19e'> 1956 19^8 1956 19^*8 1956
Aamonla Still Vaete
1,95-
1,865 61.3
28.8
Coke Plant Xffluent
578 ^51 2,009 1,410 2,170 120.2 7.5 81.0 9,920 4,130 45,800 40,700
Oil Oae Oenerator Plant
- 86.3
16.7 28.9
0 0.20
447
508
Total Vas.e Discharged
578 650 2,009 1,406 2,160 120.2
9,920 3,900 45,800 53,400

-------
PABT II - BIO-AS SAT IlflSfIGATIOIS
By Croswell Henderson
Parpc
MImmLmmbb
This section of the report covers an Investigation of the toxicity
to fish of certain process sM final effluent* of the Seaet-Solvay Division
by-product coke and oil gat generator plants.
By-product coke plant wastes contain mom ches^cal cospounds which are
known to he toxic to aquatic life In low concentrations. Some of these
chealcals, whon olxed with, or under the influence of other non-toxic com-
ponents of the effluent or receiving water, nay exert as entirely different
toxicity from that of pure cospounde. Bio-assayb were Bade to evaluate
directly the toxicity of these chemically complex wastes.
Organisation of Study
Bio-assays were Bade on samples of effluents collected on Voveaiber ?
8, 1956. Seet-Solvay and Public Health Service personnel collaborated
In collecting 8-hour composite eaoplec. fhe Public Health Service perforued
bio-assays in laboratory spnce provided by the lational Aniline Division -
Allied Chealcal and Dye Corporation in Buffalo. Plant operations, effluent
flows, and other information pertinent to the bi^-at*/ studies are con-
tained in Part I of this report.
Bio-Assay Methods
Bio-assays were nsde essentially by the method recoasended by the
Toxicity Subcoaalttee of the Federation of Sewage and Industrial Wastes
Associations (Sewage and Industrial Vastes, Vol.23. No.11, 1300, Sov.l951)
fhls aethod consists of preparing Tariova concentretione of effluent in a

-------
- 2k -
elected dilution water, adding the teet fish and observing their reactions
o*er a definite timi period. For ease in the plott ing and interpreting of
results it it desirable to sake up test solutions with the percentage of
effluent In a logarithmic series as 10, 56, 3.2, 1.8, 1.0, etc.
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, 10, and 1.0 per
cent effluent). Two fish were added to 2 liters of each concentration in
6-1/2 Inch diameter, 1 gallon widemouth flacs bottles. Observation for rela-
tively short time periods Indicated test concentrations necessary for the
full scale experiments.
In full scale bio-assnya, 10 fish are normally used for each test con-
centration. Five fieh are added to 10 liter duplicate samples in 5 gallon
wideaouth glass bottles, 10 Inches In diameter. In these tests, however, dup-
licates were not used, fhe bio-assay results are based on single samples con-
taining 5 fish in 10 liters. The intermediate concentrations tested were do-
pendent upon information obtained from the exploratory tests. For example,
If fish were klllod in concentrations above 10 per cent and not affected in
concentrations of 1 per cent, intermediates were set up within this range
(e.g. 10, 5.6, 3.2, 1.8, and 1.0 per cent concentration of effluant).
The dilution water used was raw lake Erie water obtained at the Buffalo,
lew fork, water plant. This water was hauled into the laboratory, allowed to
come to room taper at ure, 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 follows: Dissolved oxygen 7.6-8.2 ppm; pi 8.0-6.2;
total alkalinity (CaCC^) 9*+-100 ppm; total acidity (CmCQj) 0-1 ppm; ver-
aenate hardness (CaCO^) 120-135 ppa

-------
- 25 -
The tent fish uaed were fathead minnow* (Fimephalea proaelca), ranging
In length froc 2 to 2-1/2 inches and In weight fro 1 to 1-1/2 grams. Thee
fish were obtained In uniform lote froc the lewtown, Ohio, Fish Hntchery and
accll*ated to laboratory condition!. This specie la of Intermediate toler-
ance to chemicals comparable to bate, sunfiah, perch, and other warm water
species, and will tolerate fairly low oxygen condition* (1-2 p.p.m.).
The bio-assoya were made at ordinary laboratory temperatures which were
within the range from 22* to 25 C. and compare favorably with oexinua summer
water temperatures In thle area.
The teats are designed ao that generally no oxygenation or aeration la
needed. Abaorption of atmospheric oxygen by the exposed water surface la
noroally adequate for fish requirement a during the test period. However, in
some of the blo-asaaya, high oxygen demand efflaenta caused oxygen depletion,
When necessary, diaaolved oxygen was maintained by bubbling pure oxygen
throurh the teat solution by mesne of a suitable arrangement of valvea and
email tubing. The rate (60-180 bubbles per minute) was adjusted to maintain
adequate oxygen for fluh survival with minimum agitation in order to prevent
the loss of volatile materials.
Physical and chemical determinations (temperature, dissolved oxygen, pi,
alkalinity, and Uardness) were made on each concentration initially, after
fish mortality, or at the completion of the test. This was done primarily to
detect low D.O. levels so they could be controlled and to differentlnte be-
tween fish mortality due to oxygen deficiency or acidity and toxic proper-
ties.
Effluence were normally brought into ths laboratory In the afternoon
Immediately following collection and exploratory testa were set up at once.

-------
- 26-
Observatlors aade the following morning furnished information on the toxicity
of the mtei essential for settling tip the full teals tests.
Fish reactions were observed over a 96 hour period, ftm the sortality
in different concentrations, Z1*, <6, and 96 hour TL^ (Median tolerance
limit) values were obtained. The sedian tolerance limit Is the concentration
of effluent in dilution water that kills Just 50 per cent of the test fish.
These values were obtained by straight line graphical interpolation from
points representing per cent survival of fish and log concentrations of ef-
fluents which bracketed the 50 per cent point.
The $6 nour TLg, was used to compute the dilution ratio, which Is the
ratio of a unit volume of effluent to dilution water which produces n 50 pi>r
lent mortality of the test fish. This ratio times the effluent flow gives
the dilution voluse or the total flow or volume of receiving water required
to reduce the toxicity of the effluent to where a 50 per cent aortallty of
the test fish is produced. The following formula may be ueed for directly
cooputing this dilution volume:
100 - Tlfc
	x Iffluent Flow  Dilution Volume
The dilution voluces represent conditions which would cause direct in-
jury to fish upon short time exposure and are a direct comparative measure
of toxicity. Liberal application factors must be applied to thess results
for complete protection of aquatic life. Theeo factors are based on the fol-
lowing major considerations:
(1) The bio-assay procedure measures 50 per cent mortality during a rela-
tively short time period in non-renewed solutions. This must be related to

-------
- 27-
concantrations having no effect during contlnuous Ion.- tins# exposure.
(2)	Test data apply directly to the species of fish used. While fathend
ainnov* are of intermediate tolerance and coop are favor-uly with i^any ro
water "gaoe" fishes, soae locally important species of fish and fish food
organisms may be s.ore sensitive, Blo-aecsye conducted on other coke plant
wastes with a locally important forage fish, the emerald Ehinor (Motrople
atharlnoldes). indicated this specie* vac approximately twice as sensitive
as fathead altinows.
(3)	Some effluents may vary in toxicity. A few samples uty give an indica-
tion of toxicity "but maxiBum conditions say be liaaed. In i&any situations,
maxima conditions of toxicity are the lls.it in,- factor as far cs aquatic
life is concerned.
(k) Some conditions which any generally reduce but in eon
-------
Source
Coablned
Sewer (Oil
Oat Genera-
tor and Coke
Plant 
Data
1956
11-7
11-8
llacara Rivar 11-?
iDtaks
Oil gas gen- 11-7
orator plant
	11-e
Oil ," holder 11-7
overflow
Coke Plant
11-8
11-7
TABUS 6 - PHYSICAL AID CHWICAL DATA
SZKET-SOLTAT IFJKJIITS
.Description
Color,odor,ate.
Grayish tan
Oil and aedicinal
Slightly turbid
Dissolved
Oaygan
ppn
0.2
Colorless
lo odor
Clear
Grayish-tan
Strong medicinal
and coal gat
Slightly turbid
Rusty brown
Coal gas odor
Very turbid
Grayish tan
Strong medicinal
Slightly turbid
1m1*
0.0
0.2
0.0
fc.8
PH
7.8
7.7
7.6
7.2
?.b
6.5
8.2
Alkalinity
(CaCO,
PP
80
94
90
82
88
120
92
Acidity
(CaCO 3)
ppa
a
12
10
12b
Hardness
(CaCO*.)
PP>
195
150
1*5
150
150
70
iao
Phanols
PP
20.0
2,0
2.0
25.1*
Zk.S
23.6
Cyanide
PP
l.to
.03
0
0
10
0.23
a>

-------
TABU 6 (Cont'd) - PHYSICAL AND CHXhICAL DATA
SXMET SOLVAT ZTTUJEWTS
Data	Dascrlptlon
Source	1956	Color,odor,etc.
Dissolved
Ojgrgcn
ppu
Altaiinity Acidity Hardness
(CaCO ) (CaC03) (CaCO ) Fhanoia Cyan ld
PP	PP	PP	pp	PP
Coka Plant
11-8
Primary and 11-7
Secondary In-
direct COA
Coolart
Coka Quench 11-7
	11-8
Light oil and 11-7
vaeh oil
decant er
	11-8
Ho.l Amaonla
Still (Pro-
ducing "B"
liquor)
11-7
Oray	6.6
Medicinal
Turbid
Colorless	5.^
Faint coal gas
Clear
Black	6.2
Faint copl fas
Turbid
	5.6
Whitish, emulsified 0.0
Strong co.tl gas
Turbid
Grayish ten	0.0
Strong coel gas
and medicinal
Turbid
Soma emulsified oil
Dark brown
Medicinal
Clear
0.0
0.6
7.7
8.6
8.U
8.2
8.1
9.1
68
100
86
80
22U
206
860
20
185
150
160
22.7
1.5
Uo
2350
1.5
0 155
25	11.5
7^2
0.38
3.88
8.8 116.0
2.6

-------
TABU 6 (Cont'd) - PHYSICAL AID CHIMICAL DATA
3*T SOLVAI EITLOX1T8
Source
Sat*	Deecrlptlon
1956 Color,odor.etc.
Platolved
Oxygen
ppn
pH
Alkalinity Acidity Kardneae
(CaCO^) (CaCO^) (CaCO^) Phenol* Cyanide
ppa
PP
ppa
PP
PP
lo.l Amoonla
Still (Pro-
due ing B"
liquor)
11-e
Dark brovn
Medicinal
Turbid
0.0
11.0 1^60
1000
8^*5
1*1.0
*0.2 Auonia
Still (Pro-
ducing orude
liquor
11-7
Dark Brown
Medicinal
Clear
0.0
8.7
890
1560
900
2.U
11-6 Dark brown	0.0
Medicinal and coal gae
Turbid
11.9 1590
5300
790
5.0
o

-------
p8, alkalinity, and hardness were quite high in the ammonia still effluent*
tout In other effluent* vers not greatly different from intake waters. Phenols
were by fur the highest In ammonia still wastes and would be expected to
contribute to the toxicity of these effluents. Cyanides were highest in the
light oil and wash oil decanter waste and ammonia still wastes, fhe reason
for the large difference in cyanides in the light oil and wash oil decanter
waste and the Vo. 1 am&onin still waste on successive days is not known.
toxicity to Fish
k suacary of bio-assay results showing the comparative toxicity of the
different effluent samples to fish is shown in Table ?. The data on which
these results are based are shown In the Appendix at the end of this report.
Twenty-four, ^8, and 96 hour Tl^ values and dilution volumes were computed as
described In the section on bio-assay methods.
The results of the bio-assays on the samples taken on two successive
days lndlcnted most of the effluents were reasonably uniform In toxicity.
The frentest variation *rs in the lo. 2 a&sonla still waste, which wna con-
siderably lees toxic on the second day.
There were no major differences in 2\ U8, and 96 hour TLg values for
any of the effluent samples indicating little or no accumulative effect on
fish or else a loss of toxicity in a relatively short time period.
The samples of final combined (coke plant and oil gas generator) sewer
effluent and coke plant effluent were toxic to fish. Little or no toxicity
was apparent in the saroles of oil gas generator plant effluent when adequate
oxygen was maintained in the test concentrations. The combined effluent was
somewhat less toxic on the second sample even though toxicity in the coke

-------
- ->Z -
TABLE 7 - SJHMAST OF 6I0ASS'-Y DATA
3SKET SOLVAT IfFlOESTS
Source
Combined Sever
Bale
1956
11-?
11-0
AftRAOI
Effluent
flow
gd
TLm (Medlnr. Tolerance Liult)
(Per Cent Concentratlcn
2It Hr. ^ Hr. 96 Br.
13.0
23
37
30
22
37
29
22
37
29
Dilution
Voluae
mgd
31.9
Ilagara River Intake 11-?
100* aurr, 100* wxrr. 100* aunr.
Oil Oae Oenerator 11-7
Plant
11-6
ATZRAG2
1.75
100* aurv. 100* but*. 100* butt.
100* aurr. 100^ aurr. 100* aunr.
100* butt. 100# aurr. 100< aurv.
0.0
Oil Oaa Bolder
Overflow
11-?
11-6
A7XRACZ
Intermittent
fc.2
5.6
^.9
2
5.6
i.9
h.Z
5.6
k.$
Coke Plant
11-?
11-8
AVERAGE
11.25
2U
Zk
Zh
22
2k
23
22
2k
23
37.7
Coke Qae&ch
11-7
11-8
ATERAOl
0.90
0.90
100!f aurr.
100
100
100*
100
100
100* aurv.
100
100
Indirect Coolera 11-?
100* eurr.
100< aurr. 100* but*.

-------
TABU
- 33 -
7 ( Cont'd ) - SUiJATT C. BTCASSAT DATA
SMR S0L7AT EFFWLBTS
Iffluent	Tl_ (Median Tolerance Limit)	Dilution
Oat*	flow (Per Cent Concentration)	Voluae
Source 1956	agd 2k Hr.	*<8 Hr.	96 Br.	agd
Vo.l Aaaonia Still 11-7	1.20 0.90 0.90
Vo.l Aaaonia Still 11-6	0.75 0.75 0.75
AY*RA0*	0.1^5 0.96 0.6 3 0.93	16.7
Vo. 2 Aaaonia Still 11-7	0.80 0.80 0.80
o. 2 Aaaonia Still 11-6	2.U0 2.10	2.10
AVERAGE	0.129 1>5 I.U5 l.i45	8.8
Light Oil and 11-7	0.35 0.35 035
Vaah Oil
Decanter 11-6	0.2U C.22	0.22
AHRAOS	0.30 0.29	0.29	1 3-1

-------
plant effluent remised the ease. Indications are that there was a possible
antagonistic action between the coke plant effluent and the oil grc generator
plant, thus slightly reducing the toxicity In the combined waste. This dif-
ference may, however, be due to differences in sanpling (the samples were
hourly grabs coaposited over an 8 hour period).
Only one process effluent, the gee holder overflow that enters the oil
gas generator plant was tested. While this eaiqplc was moderately toxic, the
volume wae evidently small enough so as to have no effect on the total oil gas
generator effluent.
Among the process effluents from the coke plant, the light oil and wash
oil decanter waste was the most toxic to fish as Indicated by the lowest
value. Yastcs from both ammonia itills had a hi^i degree of toxicity with
the Ho. 1 still somewhat the most toxic.
Coke quench we*~~s were only Blightly toxic. In one sample there was no
fioh mortality during the test period but the fleh were badly affected. In
the other sample half of the fish succumbed.
Ho toxicity was indicated in the indirect cooling waters which sake up
by far the largest volume of wastes from the coke plant.
Biagara Hiver intake waters were not toxic.
Significance of Data
4 schematic diagram showing the toxicity of procesp wastes and the per-
centage contribution of toxicity of each to the final effluent is shown in
Figure 2.
The TI^ values are averages for the two samples taken. Th dilution
volumes were computed from the 96 hour XLg and the effluent flow values given,
in Part 1.

-------
TOXICITY
CONTRIBUTED
QUENCH WATER
INDIRECT COOL IW HATER
NO. I AMNOM1A STILL
13%
NO. 2 AM40NIA STILL
23>
INTAKE
0.129 agd
LIGHT OIL I WASH OIL DECANTER
0.038 mgd
COKE PUNT EFFLUENT
11-25^ fB>9d
TOTAL
(COKE PUNT PROCESS EFFLUENTS)
DV - 38.6
OIL GAS GENERATOR PLANT
75 njd
GAS HOLOER OVERFLOW
INTERMITTENT FLOW
COMBINED EFFLUENT
13.0 \ /
TOXICITY
TOXICITY
TU-I-W
M-8.8
TOXICITY
TO RIVER
SCHEMATIC DIAGRAM SHOWING TOXICITY OF WASTES
DISCHARGED TO SEWER
SEMET SOLVAY DIVISION
ALLIED CHEMICAL AND DYE CORPORATION
FIGURE 2

-------
- 36-
As em be readily seen from this dln.jrfis. prpetlcwlly all of thp toxicity
wae contributed by the light and wash oil decanter waste sad the ammonia
still wastes.
Bio-assays conducted on eoee cheolcul compounds tinder slmllcr experi-
mental conditions to those of the effluents gave 96 hour TX^ values as fol-
lows!
96 hour SLa
Chemical	ppm	
Phenol	fcO
O-cresol	2i>
Cyanide (CI)	0.24
Ammonia (5)	7.0
Sulfide (H2S)	1.4
Benzene	56
Toluene	51
Xylene	28
The maxlsram values for these conponenta in the effluents (Tnble 6)
would indicate that phenol was not responsible for the toxicity in the com-
bined sewer or coke plant effluents. Other phenolic compounds, however,
here been reported toxic in concentrations as low as 0.2 p.p.a. Phenols
would account for some of the toxicity in ammonia still wastes.
Ob the basis of the one sample analyzed cyanides could be responsible
for the toxicity in the combined sewer effluent. The two coke plant samp-
les, while of the saae toxicity, varied considerably in cyanide content. Is
the second sasple cyanide could account for most of the toxicity.

-------
k similar situation prevailed. In the light and wash oil decanter ef-
fluent. While cyanide vat present to an extent In one sample which would
ore than account for the toxicity, the other sample, almost as toxic, had
a such lover cyanide content. Phenols and cyanides together could appar-
ently account for most of the toxicity in the aamonla etlll wastes. One
sample, hover#r, In which cyanide vas extremely high, was not much more toxic
than the others. The above differences appear to bear out the thought that
toxicity cannot be directly determined from chemical Information.
Daring this study, pE values of moat of the effluent samples verc at
levels vhlch vould not be expected to have any adverse effect on aquatic life
generally, pH values below 5 and above 9 may have a direct lethal effect.
Within these limits, however, a chcnge In pB may have an effect by Increasing
or decreasing the toxicity of various chemicals to fish. The toxicity of
metals, cyanides, and sulfides may be increased by a decrease In pB vhlle the
toxicity of ammonia Is greater et hitler pB values.
Dissolved oxygen values vere at levels which would definitely affect
aquatic life (Table 6) In some of the effluent samples. Oxygen depleting
characteristics may have a definite effect on aquAtlc life unless adequate
volumes of receiving water are available for dilution or asslmilatIon. Low
oxycen may also tend to lncraase the toxicity of certain chemicals (e.g.
cyanide). 7or adequate protection of aquatic life, dissolved ojygen concen-
trations ehould be maintained at 5 p.p.m. or above in waters receiving toxic
materials.
Oil may mix with other organic materirl, settle to the bottom in the
form of a sludge, and have an adverse effect on bottom fish food organisms.
Small, sublethal quantities of oils, gasoline, phenols, and various

-------
- 38 -
solvents, especially benzene derivptlv.-e, t.re known to Impart a taste to fish
flesh.
lift water temperatures nay have an effect in Increasing the toxicity of
ob* materials, reducing dissolved oxygen, pcd a direct effect on son* orcan-
isms.
Color and turbidity apparently hpve no direct effect on fieh. An indi-
rect effect may be possible by a decrease in light penetration and consequently
the productivity. Suspended materiel* ty settle out and have an ax'ver:e ef-
fect on bottom food organisms and fish spnwning.
CONCLBSIOIS
While two days samples are not adequate for a complete picture of the
variation in toxicity of effluents fro.x a cocplcx industry, the toxicity values
on successive days were in fairly close reeaier.t . The following conclusions
are based entirely on the samples taker..
The combined sewer (oil gas generator and coke plant) effluent wac toxic
to fish. The dilution water estimated for safety to aquatic life (10 x dilu-
tion volume), approximately ^50 cfe, is only p fraction of the flow in the
Vlagara River.
The oil gas generator plant effluent was non toxic but had a marked
oxygen depleting effect.
The coke plant effluent was slightly more toxic then the combined efflu-
ent. Prant'celly all of this toxicity was contributed by the light and wash
oil decanter waeto and the ammonia still wastes. The coke quench water was
only slightly toxic find the indirect cooler water non toxic to fish.
Is some of the samples phenols and cyanides could epparently account

-------
- 39-
for aott of the toxicity. There was, however, such lose difference in the
toxic?tf of eiailar effluent SMtples than the vide variation la cyanldee
wouli Indicate.

-------
-y's
1J

1
^ I
2|i
l-I
!?3
Jas
0
1
o
*ri
11
il


*
j

*<
.

i
i.
i
;1
 *
1!
5 o

i
?
i

1
I5
u
J #


1
islj
ips

1
s
J

1!

1

\
<
i
t
j|H|i
!
i i
it
4}
11
H
1 k
j!

ih


#s



$
J




i
>
i
'

*
,





|
*
i

R






d
r	








s=i
5 If







*





i

1











1
















f 3
# c

*





o





'









-





















t
*
V
4,1 r
s ^
8

8.



*
*


*

i
i
i

*

,



8



<

*
*



M
















*
M
-
(w
*
*
f.

<


T

,
i
,


i
,



2

2

<
M

















-
S 1



M

o

*







M

,





,

Mtf

m

















i

* 
3 2




*

t

,







o

fv
1
**
O
m
i




<>












 w
w O
J;


R






ft

i
m
ft
%
3

i
3
*

,



a
3


*

|
l
i
.s
2


















a
|
a

3
a

i
>c
3
a

ft
IV
J


I
*




I
I

i





t
3
2





a

a

i
*
I
m
I
s
5
*
1
*



I
3










1 2




o



2

si



-



a

I

Kl

8



o

|



!
1

i

8

fi

1





5



o

c

8

151



o

o

8

8

RJ



8

o

8


\
|

8

8

8

i
1




' II
ag
m
X*
m.
*-
; 1
M.


o

o

S

M



o

o

8

8

=j

8

I

o

8


1
?

8

8

8

i
I




til

U "
**" O





s

|

53



o

c

I

8



8

8

ft

|


"i
1

8

i

i

j
1




3
s
9
o


5


>








k



a
R
 ^ - 


o



o

i
i







o



i
h

O

O

O

Q


i
o
k
t

#v

m

-

i
I
*





*
  "l *
 o  -
 "*


**





	r
t



-

*

^ 

*,

>
i


r>









s


*v

*

H

4
1
3






*  2 
 i H!! *
O  ^ w


*

A

*

1
t


1

*

I*

*

2

i
j

*

g

*
1

*

91


I
t
1

s

*

*

1
a
1





a

<3
I
3

A







1
j

*
4









J
1
2

.
a
}








3
2
3


1
1





I
1





^ o
* o m
** 2
-   5
=  *
S  5
i
i
l


\
i

1
*
#-
2
e
a
/
1

1

3
3
9
5



1
a
1
1
#
i
t
m

i
m
*
3
e
8
*
i
i
i
c
3
e
r





i
|
o
i
3
J
i
i

3
R
R
*
S
M
m
t

2
e




i
!
o
i
s
s
1
i
m
i

5
z
8
*
*

a
3
f
8





-------
t -ttGASStr 0ftT*
mae-4- *t amisa
uum cumiui am3 m ccvouna
9 n* * n> <*
SiUtiN mtm - &* Bri*
S3UiCf *?
mma* of
:6iiicTie (if
stunt
e*T! of
mumm
>U~
tiinsi
Tisriu
*ceri
iUMM
0
H$T
* tin
tClUMf
sr ? r 51
5**m
ti*rts
f|*| Of {tfl
PflCCt* UltiiAl
CMHUU  Mt|
IP*.
TOlit
Atltlff
(e^iN^
vtraatn
m*mu
i*.
* Ptet
h-m*
iOO
-








UftiiMI
I*

t.T
Jt
0
tao
Stops rir.
wt4,
%f wUr.
) fl* 4mn4. *-*
ifnwi


















 hr.MSNNiu



10
7 iwa.
r*?7 kn.
7-*? *.
0
0
0
0
:uiii
22
*.r
t.f

0

U Uk











?? *.
*2
0,0
7.?
.
*
.
(0.0.-i.h)
5 lU?

IC
10
10
>* a*..
-
-
100
c
10
90
!UU1

f,0
1.?
*
0

r**











H ^ri.

19-*i
7.7


-
Owm all!.
pi; calar.
L0^ *

10

io
-
-

190
IOC
100
100
illlUl

T>
o

0













^ br.

*,6
7.7


-


Vm tft
km Talar
* U*it
- !> :m
\ Cc.cyati
Ulaa)
Jt

3?
ii


























oai n*i
U*##
100
.








VftMII
z:

t.6

0
ii)
 ffUMl


















 If.lMMll*

V

10
* u-.
? NT.
7-* lure.
0
0
0
0
lltttol
77
T,^
.h

0
m
* ** U 7 tra.
(P.O.-4.M
tti,Mlairta4 all
apiMvixHia.
HfHl 



5o ni U/i

ii

10

-
.
100
100
100
100
UltUi

7.1
>
90
0
1*0
riik **ii











$6 Ir*.

!>.*
7.fc



uiooAa W)

n 
-5
	
0

VIM M4t











! W*

7.0
"J



itoo rm u/f

.*
K
10
*~U *ra.
%-U Ira,
*-li kr*.
0
0
0
0
Uli*4

7.*
.?

0













IB tare.

fc.f
a






5
10
*-! *ra.
-
-
4-0
lo
6
io
liiilit

7A
*-3
y>
0













fO to*.








at
5
10
-
-
-
100
m
100
i**
laiiui

7.0
t-5
90
0
1%0












H hr*

k.l
7.7





-* (ft*
Ui falar
c# 1LM \
- fm Ca
i (raw
>ttw)
MS
J3



























UlM 0*1
u-*
100
-








irnwi
m
0.0
.l
to*
*
e
ft 1 


















f lr^ap*ti

1.0
5
10
p Sl.
1 tr.
1 if.
0
0
0
0
(altial
n
6.?
9c
0

fifth MM











I in.

i>
1.0



ill*} Ml 11/9

.j:
5
10
9 ftr.
ft Iff*.
fc-t* Mr*.
0
0
0
0
Saftttal

7>
(.}
*>
0













Jfc Mr*.

5.^
?.*





.14
5
10
IMI Irt
.
_
100
0
as
0
IftltUl

7,4
1,1

0
m












10 to*.


7,4





ft* im
Lua al*r
* Uai%
 Vr
i Cticair
>*)
5.A
6.W
e.o
0,7t








-------
TA8L J *0*0 ASSAY DATA
uum eiaucx * pri cwa;ia
im rim . *uus ninow
si*0RCi :* - uo cut
J?uri **
ttf T *0" 0*
:viiiMic pr
**MU
0t? o*
coulee*
COaCfk-
ItiT10*
TISTIO
nta m
 UMf*
tilt
* It*
or mi
u ?fM
!
f*C 0* CUT* , CtC!"t SUffil
C(MiCiL * MfJlCit OAU
tift
f Isf
r i sm
f tS*
*U 0*
r i !,
2*
*0WS
1
nfluts
75
*0u$
9*
*0M1
* l*t
fcm.
c
5U1W.[J
M-
f 1
fBiit til!
(CC0,)
tOTii
4C!?!?*
(CCd||fpi
ftttmn
mtmn
6.l ***.->;-
n-T->
14-0
-








vriMii
?;
0,0
^,1
*0
0

Shirk kr Bit.
H id .
0
0
0
0
-

-
.
.
-
*
^r*ni oi 1 or.
?yr.i
V>
0
m
}i 

0
110












9* U-t,

-
-
-

-


Cobl rai

JO
-

-
100
IOC
I ex
1>
tkll t*l

?a
f.J

0















-
-
-
.



n- cm
ft
 IM) 
P*if C*t
CoitMtr*
.leiO
i.ro
0.90
0,90



























S*.i la#ti
l !--*
100

-







RSflua>N
%
0,0
11,0
1*0
0
kogo
ItUl {?r4te4


















*S* M,f

i.t

10
1 nr.
1 n.
\lt hr*.
0
0
0
0
litlUl

fe.t

100
0
ICC
F Lr.vt^oiu*











If Ma.
.r
6.6
*S
-
-
-
la U*

1.0

1C-
M' fcf#.
Ml Lr*
."Mi hi-.
0
0
0
(S



i.f
1<*
0
m
*>;OQ f* lift











tl tr*.


f.
-
-
-
Pi* A4**

.**
s
10
.
-
-
1Gb
100
100
100


?,r
,(
*
0

*|00 /* 11/9











9$ hr.



-
-



tu (m|
( Mr
v U*,l
- Fir Cm
CMc*tr
ties)
O.i*
"* '1*"
2J1
0Ji


























 *,. MMIU
u-?-*
i
-
-







f' lull
7?
0.0
.T
f^O
0
mo
tliii.




















?*

i
1* aifi.
I* at*.
1^ **,
0
0
0
n


-
-
-
-
.
Im i#t


















*i *o r* n/?

1.0

10
.'1? iv*
?~M hrm.
-
.V

?c
?0



t,k-
*
0
14*
rut uw











16 kr.

*.?

-
-
-
tivni n/i



LO
-
-

100
100
100
ion
UMlAl

?,?
4>
*
0













^ Kr .

3?
?:f 
-
-
-


V
>
10
-
.
-
too
IOC
ion
}1C
!; i*i

T.fr
.*
*
0
1*5












ffc wi.

-
-
-
.
-


n {im
ia ftltA
<~ Mm
ft* :*

Ue>
0_ff
2fi
ojm
&g>
































































































































































-------



?le ae^
* j->f * ;
 jr^Xt t t>.l* ^| *t)
 jet* 
V.
_
-
-
-
t*v'
** *












091
0

<**#


ruit[
9)T
>;t
GOT
OCI
-
"
.
01

OOT

*t2


























r<
r7
r7

{<

.5 **4 -

U*{ u*
pm) *u


-
-
,
ri


r* Tfe












at
0
sot
/
ri


301
oot
JCt
act

-

01

*



-


r*t

'-ft fS













0

*'i
l-L

!**!*!
oot
oot
jut
x\


-
wf
s
c*t


-
.
.

r o

*'4 *













0

1*1
y?


oot
oc*
oOl
OCT
-
"
"
ot

i*!

^ /ft *4 01 "


















r*p %%$
-
-
"
-
-

-
0
0
0
cn

ir%
 Al V

e
*'2

f 'ft M 00K




0*0

 *T











|
-
-
-
-
-

-
V
0
0
0

Ctn
M itH


:<

Mi4M>M| *#<;


















TTH
oo;
0
0fc<.t
t"T
-J'O









-

OCT
%--H
^iy f 8i
(linn
tSMlW
bNMlM
-{lojtu
Ufll 3*
me
 II
c'emi
lit iwfli
 i
** aBilO
oi*ioa
**ii
J*f(
SlftO*
n
^ #^0
Jf
S lfl0*
unow
S J
JO Hf
0 .DM !
v*f Jjincs
fli t? ivjtaio
ii|3iN j *ifl0 10 Jul,
n m  itiwrtc
!* mvu  rii i*i
*uncAr- tic * tvtimi:? ^rrr*
4?ieutB inr^-twti
*1*0 A*SS*0T8- " 3118*1 nauiT





-------
*
-ftllT
U#t
-

-
J
"
s^T
f-in
Mill 'jWHlf





































f/M Mi Jl, 'u


















r-TTf t* 14








*>
t)|








l/u C\ N









W f.j.t
Jkv*
(V, U-J
; .* - ;
-J: *< -
iii- -
U4 e; . .


%? 3I


















, JW y







'>.!
- .1
>,l
X'




<


tic


















TX
Oil
!
o>f
r:
i"


Kf, f
'*>K
j.:


-

>

*51

pv*




























s*"

(t .

i;- j*4 
. -ni -.n-
j* !-; *
""I*. fi





















-


-
.



 A
 I


-



. T

Ci/*t *! ^r-












'Jiv ,v





f'i.V "l'./

-
-
.
.




>
>.
-
i,
V

1's

l/*.T 'I 'S




y<

'is. t











~

.

-
.



-
U
a

" _

*

C*

 U*ei %"jrt 3



















-
"
*
*
o*0
-









-
'<0!

T?t5 mm*
tSMlM
nwmi*
moo*
mi

1*101
 i
moo
)iioccia
*0
"JS
Ii i
smcM
9*
SnO"
It
Stna*
I*
Sl*iO*
> i
JC T*
( 
15
' 1
, I t * }
JldMS
ii ii iZ
IwM-**
" t
. 4 j i
jf
a if *
; 11 s \.
 n9;
*0' ; jpio;
if >lfi
)1nS
k
J- .'. *il
.ht Ijfc'CI
VlV0 1V2U4M ? 193I01O
ttAIat J * 4118 tO J*'.
J
ftlTH)i
tm *ttt - && Ktifitia
wain cwnm - My mi
f*urrD3 tia sit TTrjcL rm
WW **SS*Ot-
t TWA I!*s*n

-------