ENVIRONMENTAL PROTECTION AGENCY
OKKHK OK KNKOK< K>IKM
REPORT ON
EVALUATION OF INDUSTRIAL WASTE DISCHARGES
CITIES SERVICE OIL COMPANY
LAKE CHARLES OPERATIONS
LAKE CHARLES, LOUISIANA
Prepared By
DIVISION OF FIELD INVESTIGATIONS DENVER CENTER
DENVER. COLORADO
AND
REGION VI DALLAS, TEXAS
OCTOBER 1971
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ENVIRONMENTAL PROTECTION AGENCY
OFFICE OF ENFORCEMENT
Report on
Evaluation of Industrial Waste Discharges
at
The Cities Service Oil Company Plants
Lake Charles, Louisiana
Prepared By
Division of Field Investigations-Denver Center
Denver Colorado
and
Region VI
Dallas, Texas
October 1971
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TABLE OF CONTENTS
Section Page
INTRODUCTION 1
BACKGROUND INFORMATION 2
General 2
Chronology of Contacts 4
CITIES SERVICE BUTYL RUBBER PLANT 6
BACKGROUND INFORMATION 6
Facility Description 6
Water Supply 6
Existing Waste Treatment 6
SAMPLING PROGRAM AND RESULTS 7
DATA REPORTED TO LOUISIANA STREAM CONTROL
COMMISSION 11
PROPOSED WASTE TREATMENT 11
CONCLUSIONS 12
RECOMMENDATIONS 12
CITIES SERVICE OIL COMPANY REFINERY 14
BACKGROUND INFORMATION 14
Facility Description 14
Water Supply 14
Existing Waste Treatment 14
FIRST SAMPLING PROGRAM AND RESULTS 17
DATA REPORTED TO LOUISIANA STREAM CONTROL
COMMISSION 26
PROPOSED WASTE TREATMENT 29
CONCLUSIONS 29
RECOMMENDATIONS 31
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TABLE OF CONTENTS (continued)
Section Page
CITIES SERVICE OIL COMPANY LUBE AND WAX PLANT
(Cit-Con Subsidiary) 32
BACKGROUND INFORMATION 32
Facility Description 32
Water Supply 32
Existing Waste Treatment 32
DISCUSSION OF SAMPLING PROGRAM AND RESULTS 33
DATA REPORTED TO LOUISIANA STREAM CONTROL
COMMISSION 38
PROPOSED WASTE TREATMENT 38
CONCLUSIONS 39
RECOMMENDATIONS 39
CITIES SERVICE OIL COMPANY PETROCHEMICAL AND
ETHYLENE-PROPYLENE PLANT 40
BACKGROUND INFORMATION 40
Facility Description 40
Water Supply 40
Existing Waste Treatment 40
SAMPLING PROGRAM AND RESULTS 41
DATA REPORTED TO LOUISIANA STREAM CONTROL
COMMISSION 44
PROPOSED WASTE TREATMENT 44
CONCLUSIONS 44
RECOMMENDATIONS 45
REFERENCES 46
ii
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TABLE OF CONTENTS (continued)
Section Page
LIST OF FIGURES
LIST OF TABLES iv
APPENDICES
A APPLICABLE WATER QUALITY REGULATIONS A-l
B CUSTODY OF SAMPLES B-l
C BIOLOGICAL STUDY METHODS FOR
PALATABILITY AND SURVIVAL STUDIES C-l
D ANALYTICAL PROCEDURES D-l
LIST OF FIGURES
Figure No. Title Follows Page
Location Map - Calcasieu 2
River Drainage
Effluent & Receiving Water Sampling 10
Locations for Cities Service Oil Co.
Butyl Plant & Refinery
Effluent & Receiving Water Sampling 33
Locations for Cities Service Oil Co.
Lube & Wax Plant (CIT-CON) & Petro-
chemical Plant
iii
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LIST OF TABLES
Table No. Title Fage
1 Description of Effluent and
Receiving Water Sampling Points 8
2 Summary of Analytical Results and
Field Measurements 9
3 Palatability and In-Situ Studies of
White Shrimp in the Lower Calcasieu
River, Louisiana 10
4 Summary of Analytical Results and
Field Measurements From First
Sampling Program 15
5 Description of Effluent and
Receiving Water Sampling Points 18
6 Results of Organic Analysis 19
7 Survival Studies of White Shrimp
In the Lower Calcasieu River,
Louisiana 23
8 Analytical Results of Bottom
Sediment Samples 24
9 Summary of Analytical Results and
' Field Measurements from Second
Sampling Program 27
10 Description of Effluent and
Receiving Water Sampling Points 34
11 Summary of Analytical Results and
Field Measurements 35
12 Analytical Results of Bottom
Sediment Samples 36
13 Survival Studies of White Shrimp
in the Lower Calcasieu River,
Louisiana 37
14 Summary of Analytical Results and
Field Measurements ^2
15 Results of Organic Analysis 43
iv
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INTRODUCTION
Louisiana's second largest industrialized area is located near Lake
Charles in the Calcasieu River Basin in the southwestern corner of the
State. Industries in the Lower Calcasieu area are primarily involved in
the production of chemical, petrochemical, and petroleum products.
These industries discharge waste waters into the Calcaseiu River or
its tributaries - Bayou d'Inde, Bayou Verdine,- Lous ton River, Mill Creek,
and Palmetto Creek. The Rivers and Harbors Act of 1899,- the Water
Quality Act of 1965, and the Water Quality Improvement Act of 1970- are
applicable to the Calcasieu River and its tributaries. [Water quality
regulations established pursuant to the provisions of these Acts are
presented in Appendix A.]
The Division of Field Investigations-Denver Center (DFI-DC), Environ-
mental Protection Agency (EPA), at the request of the Director, Water
Quality Office, Region VI, EPA, undertook a study of the Calcasieu River
Basin in March-April 1971. Specific objectives of the study were to:
1. Compile an up-to-date inventory of industrial waste sources
discharging to the Calcasieu River and its tributaries.
2. Ascertain a) types of treatment presently provided and b) the
quality and quantity of each industrial waste discharge.
3. Evaluate the individual and collective impacts of wastewater
discharges on the beneficial water uses of the Calcasieu River
and its tributaries.
A. Determine abatement proceedings necessary or warranted under
the Rivers and Harbors Act of 1899, the Water Quality Act of
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1965, and/or other applicable local, State and Federal laws.
This report summarizes information pertaining to raw materials, pro-
cesses, waste loads, and treatment needs at the various plants of the Cities
Service Oil Company, Lake Charles, Louisiana, and recommends actions
necessary to protect the quality of the receiving waters. Complete cus-
todial records [Appendix B], for each sample taken during the course of
this Investigation, are on file in the Denver, Colorado, office of the
Division of Field Investigations-Denver Center.
Assistance and support in the conduct of this investigation was pro-
vided by the following EPA entities:
Division of Field Investigations-Cincinnati Center
Analytical Quality Control Laboratory, Cincinnati, Ohio
Enforcement Office, Region VI, Dallas, Texas
Southeast Water Laboratory, Athens, Georgia
The assistance of personnel of the Lake Charles Office, Louisiana
Wildlife and Fisheries Commission, is gratefully acknowledged.
BACKGROUND INFORMATION
General
The total drainage area of the Calcasieu River and its tributaries
equals about 4,000 square miles; measures approximately 120 miles in
length and 55 miles in width; and includes portions of eight different
parishes (population - about 230,000). [See Figure 1.] The Lower Calcasieu
River encompasses the area downstream from a salt water barrier (located
Just north of the city of Lake Charles) to the Gulf of Mexico. The Upper
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TOLEDO BENO RESE
GULF OF MEXICO
Not To Scale
Figure 1. Location Map • Calcasieu River Drainage
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Calcasieu River consists of the fresh water portion of the watershed
extending upstream from the salt water barrier to the basin headwaters.
The River is navigable upstream to Moss Bluff, Louisiana (about
ten miles upstream from Westlake).-' Barges and ships navigate a channel
that has been dredged from the Gulf of Mexico northward along the west
side of Calcasieu Lake to Devils Elbow, thereafter following the natural
river channel, except for two cutoffs, to the Port of Lake Charles.
Thundersqualls and tropical storms with high wind velocities occa-
sionally pass through the area. Prevailing winds are primarily from the
north during months of November through January and from the south during
the remainder of the year. Frosts are experienced from late November to
late February. Average temperatures range from the low 50's (in January)
to the 80's (in July).
The Lower Calcasieu River, Lake Calcasieu, Bayou d'Inde, Bayou Verdine,
and Indian Marais are affected by lunar tides. Passage of a cold front
or high winds may cause wind-dominated tides that produce flooding of
low-lying areas and tributary streams and bayous. As a result of these
events, flow and mixing patterns may be highly irregular.
Brackish inland lakes and marshes that border the main River channel
and the adjacent shallow offshore area support a large commercial and
sport fishery. The area is an excellent spawning and rearing ground for
shrimp, crabs, and various estuarine fish.
In addition to furnishing a location for the propagation of aquatic
life, the waters of the Calcasieu River system and its tributary streams
support other beneficial activities, including municipal and industrial
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water supplies, recreation, irrigation, and navigation.
In conjunction with other chemical plants and petroleum refineries,
the Cities Services Oil Company plants are substantial contributors to the
economy in the Lower Calcasieu River area. Company operations are Involved
in the production of petroleum products, petrochemicals, and butyl rubber.
Chronology of Contacts
The Cities Service Oil Company (P. 0. Box 1562, Lake Charles, Louisiana
70601) has four industrial plants located in the Lake Charles area:
(1) Cities Service Oil Company Butyl Rubber;
(2) Cities Service Oil Company Refinery;
(3) Cities Service Oil Company Lube and Wax; and
(4) Cities Service Oil Company Petrochemical and Ethylene Propylene.
On March 25, 1971, W. C. Blackman, Jr., M. R. Helton, and J. L. Hatheway,
DFI-DC, EPA, net with T. W. Kirby, assistant superintendent for laboratories,
at the Cities Service Oil Company, in order to obtain information for a
waste source inventory. T. P. Harrison, Enforcement Office, EPA, Region VI,
had made arrangements for the meeting. A tour of the four plants was con-
ducted during the March 25 visit. (Mr. Kirby would not permit the investi-
gators to take photographs within the plant property).
Subsequent contact was made with Mr. Kirby on April 15, by R. D. Harp
and Mr. Hatheway, both of DFI-DC, to plan the industrial waste sampling
program being conducted in conjunction with a water quality survey of the
Calcasieu River Basin. Mr. Kirby was informed that the survey information
would be used as the basis for:
(1) Evaluation of Corps of Engineers permits as required under the
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Rivers and Harbors Act of 1899;
(2) Determination of present water quality conditions in the Calcasieu
River and its tributaries;
(3) Evaluation of the Individual and collective impacts of wastewater
discharges on the beneficial water uses of the Calcasieu River
and Its tributaries;
(4) Determination of water pollution control needs within the area;
(5) Abatement proceedings as necessary or warranted under the Rivers
and Harbors Act of 1899, the Water Quality Act of 1965, and/or
other applicable local, State and Federal laws.
Permission to sample all effluent discharges was granted; however,
permission to sample process wastes prior to treatment was not granted.
Pertinent information and results of the investigation of waste treat-
ment and disposal practices at each Cities Service facility are discussed
below.
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BACKGROUND INFORMATION p
a
Facility Description $
w
The Butyl rubber plant operates continuously. Eighty-seven people w
M
are employed in the rubber production operation. The rated plant capacity o
Cd
is 84 million Ibs per year of Butyl rubber, the plant's primary product. c
By-products, such as isobutylene, isoprene, and methyl chloride, are ^
c
Cd
recycled into the production process. The raw materials that are employed w
&
include isobutylene, isoprene, zinc stearate, aluminum chloride, and j2
natural gas. H
Water Supply
Water, for process and cooling purposes, is obtained from one 1,000
gpm (1.44 mgd) well. Boiler feed water is supplied from steam condensate
in the refinery feed.
Existing Waste Treatment
Oily wastewaters from the Butyl plant are discharged to the oxidation
pond at the Cities Service Oil Company refinery. Once-through cooling
water, other wastewater, and blowdown from a cooling tower are discharged
to the Lower Calcasieu River without treatment.
The effluent, from a commercial chromate recovery process, is — ac-
cording to Company information — essentially free of chromate, although
it may contain zinc on the order of 2-3 mg/1 as zinc stearate.
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SAMPLING PROGRAM AND RESULTS
Aliquots (125 ml) of the effluent were composited every two hours for
24 hours, commencing at 7:35 a.m., April 21, 1971. Samples were taken
from the outfall ditch near the Lower Calcasieu River [Figure 2]. A grab
•
sample was collected, at 3:40 p.m., April 17, for oil and grease analysis.
Shrimp survival studies were.conducted in the Lower Calcasieu River in the
vicinity of this discharge. Water and sediment samples were collected in
the Lower River upstream and downstream from the point of industrial dis-
charge. [The sampling points are described in Table 1, their locations
shown in Figure 2.]
[Analyses of the effluent and stream samples are listed in Table 2.]
During the 24-hour sampling period, pollutant loads discharged included 6
Ibs of chromium; 2,470 Ibs, chemical oxygen demand (COD); 410 Ibs, total
organic carbon (TOC) ; 2,160 Ibs, suspended solids; and 100 Ibs of oil and
grease.
Survival studies using white shrimp were conducted (following methods
outlined in Appendix C) in situ at industrial site stations CR-2.1 and 4.2
and at the Control Stations (Cr-11.2 and 1) [Figure 2]. Total mortality,
within 24 hours, of the shrimp at CR-4.1 and 4.2, precluded taste and odor
studies. After a similar 24-hour exposure period, shrimp mortalities at
the Control Stations were 10 and 20 percent, respectively [Table 3].
Although it is not known which constituents or combinations of constituents
in the River caused total mortality at stations CR-4.1 and CR-4, it is
clear that the stream quality at this location is toxic to native shrimp.
[See Table 3.]
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TABLE 1
DESCRIPTION OF EFFLUENT AND RECEIVING WATER SAMPLING POINTS
Station
Number Description and Remarks
CSC-1 Samples collected from the drainage ditch at a point just before
it empties into the Lower Calcasieu River (ditch parallels the
north fence of the Cities Service refinery plant).
CR-1 Lower Calcasieu River near Calcasieu Landing (upstream of intra-
coastal waterway) near Channel Marker 92 (Control Station).
CR-A Lower Calcasieu River upstream of Cities Service refinery effluent
and downstream from the Butyl rubber plant effluent.
CR-4.1 Lower Calcasieu River, northwest shore, at discharge of the Butyl
rubber plant.
CR-4.2 Lower Calcasieu River, opposite the Butyl rubber plant.
CR-5 Lower Calcasieu River near Channel Marker 108.
CR-11.2 Lower Calcasieu River, south shore, south of Clooney Island just
west of Lake Charles (Control Station).
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TABLE 2
SUMMARY OF ANALYTICAL RESULTS AND FIELD MEASUREMENTS-'
Sta
CSC-1
CR-4
CR-5
Sta
CSC-1
CR-4
CR-5
Conductivity Temp b/
Flow j)H uir.hos/cm °C TOC COD-
r°d ranpe rpnpe comp range mR/1 Ibs/cl/y mg/1 Ibs/day
1.70 7.2-9.8 1,000- 2,300 22- 29 410 170 2,470
3.500 30.5
7.1-8.3 13.000 24-24 9.4, 12£/
6.8-8.6 13.400 23-24 9.4, 13£/
Cadmium Chromium Mercury Copper Lead
me/1 ir.n/1 Ibs/day UR/1 me/1 mR/l
<0.05 0.40 6 <0.1 <0.02 <0.1
. Solids
total susp Oil & Grease
mR/1 Ibs/day mc/1 Ibs/day me/1 Ibs/day
1,480 21,000 152 2.160 7 100
8,610 14
8,980 . 16
a/ Analytical procedures are outlined in Appendix D.
b_/ COD rrilyses were performed when TOC values exceeded 20 mg/1.
c/ Two composites taken (morning and afternoon).
so
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10
TABLE 3
PALATABILITY AND IN SITU STUDIES OF WHITE SHRIMP IN THE LOWER
CALCASIEU RIVER, LOUISIANA
a/
96-Hour Shrimp Survival Study-
Station
CR-11.2
(Control)
•
CR-5
CR-4.2
CR-4.1
CR-1
(Control)
Exposure
Time
Initial
24-hour
48-hour
72-hour
96 -hour
Initial
24-hour
48-hour
72-hour
9 6 -hour
Initial
24-hour
Initial
24-hour
Initial
24-hour
48-hour
72-hour
96-hour
Number
Alive
10
9
8
8
5
10
6
4
3
1
10
0
10
0
10
8
8
8
5
Dead
0
1
2
2
5
0
4
6
7
9
0
10
0
10
0
2
2
2
5 .
Percent
Survival
100 '
90
80
80
50
100
60
40
30
10
100
0
100
0
100
80
80
80
50
a/ April 20-24, 1971
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LA. 1O8
r
HERCULES PLANT
I |
H
Z
<
J
Q.
h
3
m
CITIES SERVICE OIL CO.
REFINING
CR-3
CR-4.2
CR-3.1
Not To Scale
Figure 2. Effluent & Receiving Water Sampling Locations lor Cities Service Oil Co. • Butyl Plant & Refinery
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11
Control Stations, CR-1 and CR-11.2 [Table 1], are located in the
Lower Calcasieu River so as to have the least possible contamination from
industrial wastes. Station CR-1 is located downstream from industrial
discharges and closer to the Gulf of Mexico than are all the other
stations. Station CR-11.2 is located upstream of most industrial dis-
charges and has water with lower salinity levels than has Station 1.
DATA REPORTED TO LOUISIANA STREAM CONTROL COMMISSION
The Louisiana Stream Control Commission approved (December 16, 1970)
the discharge levels of certain materials based on data submitted by the
Cities Service Oil Company for its Butyl plant. A summary of the infor-
mation from the Commission files is as follows:
Quantity of Discharge: 0.9 cfs
Temperature: 65-87°F.
Turbidity: 25-60 JTU
True Color: 20-30
Organic Materials (oil) : 17 Ibs/day - 3 ppm
Inorganic Materials: 4300 Ibs/day - 900 ppm
Toxic Materials:
Chromium 0 Ibs/day - 0 ppm
Zinc 4 Ibs/day - 1 ppm
Mercury 0 Ibs/day - 0 ppm
Dissolved Oxygen: 50% Saturation
PROPOSED WASTE TREATMENT
The Company's laboratory personnel are presently experimenting with
new treatment processes; no schedule for upgrading treatment has been made
known. The intent, according to Mr. Kirby, is to reuse treated wastewater
as cooling make-up water in the Butyl plant.
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12
CONCLUSIONS
1. The present discharges of heavy metals, carbonaceous materials,
suspended solids, and oil and grease, constitute violations of Section 407,
Rivers and Harbors Act of 1899 (33 USC: 401-413).
2. The stream near the effluent discharge is toxic to native shrimp.
3. An effort is being made to develop and implement a suitable treat-
ment and reuse scheme, but no implementation schedule was made known to the
EPA investigators.
RECOMMENDATIONS
It is recommended that:
1. The Office of Enforcement, EPA, in cooperation with appropriate
State and local authorities, monitor progress toward implementation of
suitable treatment processes at The Cities Service Oil Company Butyl
Rubber plant.
2. If a schedule for implementation of suitable treatment is not in
effect by June 1, 1972, consideration be given to initiating appropriate
abatement actions against the Company for the discharge of chromium;
carbonaceous materials; suspended solids; and oil and grease to the
Calcasieu River, a navigable stream.
3. When a suitable schedule is implemented, the Office of Enforcement,
EPA, monitor progress toward completion, and take appropriate action at any
time that the Company falls behind the schedule.
4. The Corps of Engineers permit, to be issued, limit concentrations
of BOD; COD; TOC; of suspended solids; oil and grease; heavy metals; and
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13
complex organics to levels consistent with best available treatment and
with the water quality standards for the Lower Calcasieu River.
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14
BACKGROUND INFORMATION
Facility Description
en
The plant operates continuously. The production work force Includes gj
approximately 1000 employees.
o
The refinery produces propane; propylene; o-xylene and other aromatic p
o
chemicals; aviation gas; motor gas; jet fuel; kerosene; diesel fuel; fur- §
nace oil; carbon black feed; residual fuel; cokp; and feed stocks for
lubes, waxes, and petrochemicals. §
M
2!
Crude oils, light hydrocarbons (to butane), diethylglycol, and pyrro-
lidine are the raw materials used in the operation. Others, used in the
process, include sodium hydroxide, calcium chloride, corrosion inhibitors,
oxidation inhibitors, and tetraethyl lead.
Water Supply
Water for the refinery is obtained from the Calcasieu River for non-
contact cooling (360 mgd). Seven wells, each rated at 1,000 gpm (1.44 mgd),
provide process water, cooling water, and boiler feed.
Analyses of the river intake water [Table 4] indicate that it contained
0.2 ug/1 mercury; 0.1 mg/1 lead; 9 mg/1 TOC; and 31 mg/1 suspended solids
on the day of sampling.
Existing Waste Treatment
Once-through cooling water from the power plant as well as oily wastes
from the refinery and the Butyl rubber plant are treated in a 28-acre
oxidation lagoon. It discharges to a second pond that was dredged in
Indian Marais. The second pond's outlet, to the Lower Calcasieu River
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TABLE 4
SUMMARY OF ANALYTICAL RESULTS AND FIELD MEASUREMENTS
FROM FIRST SAMPMNG PROGRAMS'
Flov^/
Sta
rv.c!
P»
ranee
Conductivity
p mhos /cm
range
comp
Temp
°C
°c
TOC
COD^
Solids
total
Ib/dav mg/1 Ib/dav me/1 Ib/dav
Oil & Crease
me/1 Ib/day me/1 Ib/day
ausp
CSC-2 ?90 7.3-8.2 14,000-18,000 13,600 32-37 15
CSC-2A 290 7.3-8.3 14,500-17,000 13,000 32-34 230
CSC-3 58 7.0-7.9 13,000-16,000 12,800 33-36 13
CSC-4 400 7.1-7.8 15,000-20,000 13,600 23-25 9
CR-3 7.1-8.0 14,850 25-25 9.8,
CR-4 7.1-8.3 13,000 24-24 9.4.
36,300
9.220 22.3 X 10° 38 92,000 5
12,100
557,000 520 1.26 X 106 9,850 23.9 X 106 220 533.000
6,300
30,000
8.710 4.2 X 10 27 13,000
9,760 32.6 X 106 31 103.500
9.580 9
8.610 14
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TABLE 4 (continued)
SUMMARY OF ANALYTICAL RESULTS AND FIELD MEASUREMENTS
FROM FIRST SAMPLING PROGRAM
Sta
CSC- 2
CSC-2A
CSC-3
CSC-4
CR-3
CR-4
Cadmium
tm»/l
<0.05
<0.05
<0.05
<0.05
<0.05
Chromium
mR/1 Ib/day
0.02 48
0.14 340
<0.01
<0.01
<0.02
Mercury
PR/1
0.2
1.0
0.3
0.2
4.6
Ib/day
0.4843
2.422
0.1443
0.6680
Coj'j>er
mR/1 Ib/day
0.04 97
0.11 266
0.04 19
<0.02
<0.02
Lead
mR/1
0.2^
4.08/
0.2^
0.1*'
<0.1
Aluminum
Ib/day mR/l
485
9,690
95
335'
<0.5
NHi as N
ms/1 Ib/day
10.1 24,500
at Analytical procedures are outlined in Appendix D.
b/ Flow data, provided by T. W. Klrby, compare with information collected from Louisiana Stream Control Commission files.
£/ COD analyses were performed when TOC values exceeded 20 mg/1.
d/ Two co-.posites taken (morning and afternoon) .
e/ No interference from calcium detected.
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17
(Station CSC-2A), is equipped with a steel curtain that extends approxi-
mately three feet below the water surface. This curtain functions as a
skimmer to prevent the discharge of floating oil and is hinged to a cat-
walk so that it can pivot with the direction of flow of the water. When
there is barge traffic on the River, the curtain is observed to pivot with
flows moving from the waterway upstream into the second pond. Flow through
this system is approximately 288 mgd [Figure 2].
Condenser cooling water is discharged without treatment directly to
the Lower Calcasieu River. This discharge amounts to approximately 57.6 mgd.
FIRST SAMPLING PROGRAM AND RESULTS
Aliquots (250 ml) were composited every four hours, commencing at
7:55 a.m., April 21, at four sampling stations in the refinery [Figure 2].
[Description of these stations and of the stream stations sampled is pro-
vided in Table 5.] A grab sample for oil and grease analyses was obtained
at CSC-2 at 3:15 p.m., April 17. On April 21, at 11:00 a.m. another grab
sample was taken, at Station CSC-2, for organic analysis. [Analytical
results and field measurements recorded are listed in Table 4.]
Analysis of the upper pond effluent was carried out to determine com-
plex organics [Table 6]. Normal aliphatic hydrocarbons identified in the
effluent sample represent a portion of the oil and grease discharged by
the Company refinery. High concentrations of phenolic compounds were
also observed in the effluent. In these concentrations (as dischareed from
the refinery), the compounds are toxic to aquatic life and may have a detri-
mental effect on the receiving waters.
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18
TABLE 5
DESCRIPTION OF EFFLUENT AND RECEIVING WATER SAMPLING POINTS
Station
Number Description _
CSC-2 Effluent from the refinery lagoon at the outlet structure,
approximately 1,000 ft from the Lower Calcasieu River.
CSC-2A Samples collected at the point where the effluent from the
refinery enters the Lower Calcasieu River.
CSC-2B Samples collected at mid-depth at center of second pond dredged
from Indian Marais.
CSC-2C Effluent from two small ponds, which are part of the refinery's
treatment, that are located on the south side of Indian Marais.
Effluent enters Indian Marais just upstream of second pond.
CSC-3 Samples collected from the power plant effluent before it
enters the Lower Calcasieu River (Dock C). Flow is approxi-
mately 40,000 gpm.
CSC-4 Cooling water supply to the refinery (approximately 200,000 gpm).
Samples collected at the forebay of the pump house, (source
• Lower Calcasieu River).
CR-1 Lower Calcasieu River near Calcasieu Landing (upstream of intra-
coastal waterway), near channel marker 92 (Control Station).
CR-3 Lower Calcasieu River at Channel Marker 106, downstream from the
main effluent of the Company refinery.
CR-3.1 Lower Calcasieu River, east shore opposite the main refinery
discharge.
CR-3.2 Lower Calcasieu River, west shore at industrial discharge of
the refinery.
CR-3.3 Lower Calcasieu River, east shore, and opposite Cities Service
main refinery discharge.
CR-4 Lower Calcasieu River upstream of Cities Service refinery
effluent and downstream from the Company Butyl rubber plant
effluent.
CR-11.2 Lower Calcasieu River, south shore, south of Clooney Island just
west of Lake Charles (Control Station).
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19
TABLE 6
RESULTS OF ORGANIC ANALYSIS
Compound Concentration Load
Identified (mg/1) Ib/day
Dodecane 0.031 79
Heptadecane 0.022 53
Hexadecane 0.026 66
Nonadecane 0.013 33
2-Methylnaphthalene 0.013 33
o-Cresol 0.120 300
Octadecane 0.017 A3
Pentadecane 0.030 76
Phenol 0.200 510
Tetradecane 0.039 99
Tridecane 0.042 107
Undecane 0.027 69
1-Methylnaphthalene 0.005 12
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20
At the time sampling was being planned, the DFI-DC investigating team
indicated to officials of the Company that, since the second pond had been
dredged from a natural tributary (Indian Marais) and is subject to tidal
action, the discharge from the first pond (CSC-2) should be considered to
be the point of discharge and, therefore, the point to be sampled. These
officials claimed that the second pond constitutes a segment of the treat-
ment process, and that the flow past the curtain into the Lower Calcasieu
River (CSC-2A) should be sampled. Since the dispute could not be resolved,
it was finally agreed that both points would be sampled — the dispute to
be resolved after consultation with respective legal staffs.
Substantial differences in quality were found to exist between the
two sampling points [Table 5]. Calculated loads discharged, during the
24-hour period, at CSC-2 included 36,300 Ibs of total organic carbon (TOC);
92,000 Ibs, suspended solids; 12,100 Ibs, oil and grease; 48 Ibs, chromium;
12
0.48 Ibs, mercury; 97 Ibs, copper; 485 Ibs of lead; and 1.7 X 10 calories
of heat. Calculated loads discharged at CSC-2A, during the 24-hour sampling
period, included 1,260,000 Ibs of chemical oxygen demand (COD); 557,000 Ibs,
TOC; 533,000 Ibs, suspended solids; 340 Ibs, chromium; 2.42 Ibs, mercury;
266 Ibs, copper; and 9,690 Ibs of lead.
Because the curtain caused the materials to be discharged at depths of
at least six feet in the Lower Calcasieu River, oil and grease were not
measured at CSC-2A; however, oil rises in widely dispersed patches well
downstream from the curtain. Thus, it was not possible to obtnin a rep-
resentative sample with the eauipment at hand.
The cause of the differences in the concentrations at the two points
-------
21
is not clear. Possible causes include unknown discharge(s) to the second
pond; unobserved discharges from Indian Marals; tidal action causing
buildup in the lower ponds or scouring of bottom materials by flood tides
passing beneath the curtain; and the elimination of interfering substances
within the lower pond. The possibility of sampling error is discounted
because various parts of the analyses and standards were carefully rechecked.
Moreover, concentrations of TOG, suspended solids, lead, and mercury were at
least five times greater at CSC-2A than at CSC-2. Also, all concentrations
measured were higher to some degree at the outlet from the second pond.
If analytical or sampling errors were involved, such a pattern would not
have prevailed.
Based upon the contention by Company officials that Station
CSC-2A is most representative of the discharge by the refinery, the net
loads discharged during the 24-hour sampling period were calculated by
adding loads from stations CSC-2A and CSC-3, and by subtracting the intake
loads at CSC-4. (Flows used in calculating the loads were furnished by
Company officials.) The loads thus calculated include 533,000 Ibs of TOC;
443,000 Ibs of suspended solids; 340 Ibs, chromium; 1.9 Ibs, mercury; 285
Ibs, copper; and 9,400 Ibs of lead. As indicated earlier, discharges
of oil and grease were not determined at CSC-2A. The load discharged
at CSC-2 during the 24-hour sampling period was 12,000 Ibs. The discharges
12
also added 12 X 10 calories heat.
Survival studies, employing white shrimp, were conducted in situ at
industrial sites Stations CR-3, 3.1, 3.2, 3.3, 4.1, and 4.2 and at 11.2
and 1 [Figure 2] following methods outlined in Appendix C. A 100 percent
-------
22
shrimp mortality at all industrial site stations within a 24-hour exposure
period, precluding taste and odor studies. Shrimp at Control Stations
CR-11.2 and CR-1 [Figure 2] had 24-hour mortalities of 10 and 20 percent,
respectively [Table 7].
A sediment sample, collected below the main discharge (station CR-3.2),
was composed of black soft sediment having a strong petrochemical odor
[Table 8]. Almost 20 percent of the sample was volatile materials. An
organic sediment index (OSI) of 2.8 indicates an organic sludge undergoing
decay and decomposition. The sediment also contained 5.4 vg/g of mercury.
-------
23
TABLE 7
SURVIVAL STUDIES OF WHITE SHRIMP IN THE
LOWER CALCASIEU RIVER, LOUISIANA
96-Hour Survival Study
Station
CR-11.2
(Control)
CR-3.3
CR-3.2
CR-3.1
CR-3.0
•
CR-1
(Control)
Exposure
Time
Initial
24-hour
48-hour
72-hour
96-hour
Initial
24 -hour
Initial
24-hour
Initial
24-hour
Initial
24-hour
Initial
24-hour
48-hour
72-hour
96-hour
Number
Alive
10
9
8
8
5
10
0
10
0
10
0
10
0
10
8
8
8
5
Dead
—
1
2
2
5
0
10
0
10
0
10
0
10
0
2
2
2
5'
JL/
Percent
Survival
100
90
80
80
50
100
0
100
0
100
0
100
0
100
80
80
80
50
a/ April 20-24, 1971
-------
TABLE 8
ANALYTICAL RESULTS OF BOTTOM SEDIMENT SAMPLES
Station
CR-1
CR-3.2
Station
CR-1
CR-3.2
Date
4/22/71
4/22/71
Nitrogen
0.189
0.318
Water
Depth .
Time Feet
1145 2.0
1330 30.0
Type5' Odor5/ Volatiles
of bottom of bottom %
Soft mud None 7.6
Black, Petro- 19
soft chemical
sediment
Organic
Carbon
%
2.76
8.88
Organic .
Sediment Sediment Mercury-
Index Type
0.52 II
2.8 III
VR/R
<0.2
5.4
aj General appearance and odor at time of collection.
b_/ Results based on dry weight. Samples dried at 35°C for two days.
N>
-------
25
SECOND SAMPLING PROGRAM AND RESULTS
This section summarizes the results of the second sampling program
of Cities Service Oil Company refinery.
As noted in the section titled "First Sampling Program and Results",
discrepancies connotating differences in quality were perceived between
two sampling points, CSC-2 and CSC-2A [Table 4]. Because of these dis-
crepancies a second survey was conducted on October 22 and 23, 1971.
On October 21, 1971, T. P. Harrison, Enforcement Office, EPA, Region VI
contacted officials of Cities Service Oil Company refinery to make arrange-
ments for the re-sampling program. On October 22, 1971, J. L. Hatheway,
L. R. Walz, and H. W. Boyle contacted Stan Gilliard of the refinery to
outline and make arrangements for the second survey. Mr. Gilliard was
cooperative and agreed to the re-sampling survey as well as to the addition
of station CSC-2B. He also informed Mr. Hatheway that effective September 19,
1971, the refinery began discharging "sour water"* at a rate of 325 gpm to
a deep well.
Aliquots (125 ml) were composited every two hours commencing at
12:15 p.m., on October 22, 1971, at six sampling stations in the refinery
[Figure 2]. [Description of these stations is provided in Table 5.]
At stations CSC-2A and CSC-2B the samples were collected at a point below
the steel curtain and at mid-depth, respectively. The samples collected
from the lower pond (CSC-2B) consisted of a composite of two grab samples.
On October 23, grab samples for oil and grease analysis were obtained
* "Sour water" is a trade term that identifies a process waste which con-
tains high concentrations of hydrogen sulfide, ammonia, and phenols.
-------
26
at stations CSC-2A and CSC-2 at 10:30 and 10:40 a.m., respectively. At
the request of Cities Service Oil Company personnel, all collected
samples were divided and a portion given to them; the remainder was for-
warded to EPA laboratories for analysis. [Analytical results and field
measurements of the second sampling program are listed in Table 9.]
During the 24-hour period, waste loads discharged from the refinery
were calculated by adding loads from stations CSC-2A and CSC-3, and sub-
tracting the intake loads at CSC-4. Flows used in calculating the loads
were furnished by Company officials and compare with information in
Louisiana Stream Control Commission files. The daily loads calculated
include 25,000 Ibs of COD; 3000 Ibs, suspended solids; 16 Ibs, chromium;
12
134 Ibs, copper; 167 Ibs, lead; 12,000 Ibs of oil and grease, and 11 X 10
calories of heat.
DATA REPORTED TO LOUISIANA STREAM CONTROL COMMISSION
The Louisiana Stream Control Commission approved (December 16, 1970)
the discharge levels of certain materials based on data submitted by the
Cities Service Oil Company for its refinery. A summary of the information
from the Commission files is as follows:
Quantity of Discharge: 535 cfs
Temperature: 68-102°F
Turbidity: 25-60 JTU
True Color: 60
Organic Materials (Oil): 17,300 Ibs/day - 6 ppm
Organic Materials (BOD): 98,400 Ibs/day - 34 ppm
Inorganic Materials:* 100,000 Ibs/day - 37 ppm
* Incoming River water would contain as much as 53,000,000 Ibs/day
of dissolved solids, to which the above would be added.
-------
TABLE 9
SUMMARY OF ANALYTICAL RESULTS AND FIELD
FROM SECOND SAMPLING F
I FIELD MEAS
ROGRAMS/
UREMENTS
Station
CSC-2
CSC-2A
CSC-2B
CSC-2C
CSC-3
CSC-4
Flow^/
nsd
290
290
290
58
AOO
Conductivity
umhos/cm
ran^e
18,000-21,000
18,500-22,000
22,000
16,000-22,000
18,000-23,000
Temp
°C
ranee
35-38
31-35
35
35-39
25-26
TOG
1HR/1
<5
<5
<5
89
<5
<5
COD
IKR/I
190
140
120
52C
110
110
Ibs/day
459,000
339,000
291,000
53,000
367,000
Solids
total
HIR/1
-
14,500
14,700
14.300
14,000
14,300
Ibs/day
35.1
35.6
6.78
47.7
X106
X 106
X 106
X106
susp
TOR/1
50
40
40
160
80
40
Ibs/day
121,000
97.000
97,000
39.000
133,000
ISJ
-------
TABLE 9 (continued)
SUMMARY OF ANALYTICAL RESULTS AND FIELD MEASUREMENTS
FROM SECOND SAMPLING PROGRAM
Station
CSC- 2
CSC-2A
CSC-2B
CSC-2C
CSC-3
CSC-A
Oil and Grease
Cadmium
Chromium
m«/l Ibs/day mg/l Ibs/dav mR/1 Ibs/day
9 22,000 <0
5 12,000 <0
<0
0
0
<1 0
.01
.01
.01
.02
.02
.01
0
0
0
0
10 0
33 0
.03
.03
.03
.44
.02
.02
73
73
73
.
10
67
Copper
ire/l
0
0
0
0
0
0
.10
.16
.14
.33
.10
.09
Ibs/dav
242
387
339
48
. 301
LeadS/
B1K/1
0.
0.
0.
0.
0.
0.
19
14
08
63
06
06
Ibs/dav
459
338
194
29
200
a/ Analytical procedures are outlined in Appendix C,
b_/ Flow data, provided by T. W. Klrby, compare with information collected from Louisiana Stream Control
Commission files.
£/ No interference from calcium detected.
CO
-------
29
Toxic Materials:
Chroraate 80 Ibs/day - 0.03 ppm
Phenol 1,205 Ibs/day - 0.45 ppm
Zinc 117 Ibs/day - 0.13 ppm
Mercury 0 Ibs/day - 0 ppm.
PROPOSED WASTE TREATMENT
Towers are being constructed at the Cities Service Oil Company refinery
that will permit recirculation of cooling water. Operation of the cooling
facilities will reduce flow through the ponds by approximately 130 mgd.
As noted earlier, EPA investigators were not permitted to sample the
process wastes entering the pond system. As a result, the present treat-
ment capability could not be determined. Since the detention time will
remain short, reduction of the flow through the system by 130 mgd cannot be
expected to increase materially the treatment efficiency. The proposed
additional wastewater treatment consists principally of in-plant process
control and primary treatment for the residual.
At the time of the first EPA investigation, sour water was included
with the wastes treated in the pond system. A deep well system (4,900 ft)
had been constructed and was being used for disposal of sour water at the
time of the second investigation. The Cities Service Oil Company refinery
has been issued a permit by the mineral division of the Louisiana Department
of Conservation to operate this disposal well. The quantity and quality of
the sour water produced is not known but the disposal well is rated at
800 pgm (1.15 mgd}.
CONCLUSIONS
From the data obtained during the second sampling program, October 7.1
and 23, 1971, the discharged waste loads, as measured at stations C5C-2
-------
30
and CSC-2A, are comparable. Waste loads at both these stations are very
comparable to those measured at station CSC-2 during the first sampling
program. The reason for the discrepancy between measured waste loads at
CSC-2 and CSC-2A during the first survey is not readily apparent. Operation
of the disposal well appears to have contributed to the reduction of waste
loads discharged to the River.
1. The waste loads determined at stations CSC-2 and CSC-2A in the
second survey confirm the waste load measurement at station CSC-2 in the
first survey.
2. The refinery discharges carbonaceous materials; suspended solids;
chromium; mercury; copper; lead; phenols; and heat to the Lower Calcasieu
River, in violation of Section 407, Rivers and Harbors Act of 1899 (33 USC:
401-413).
3. Observations of receiving waters, the discharge of oil and grease
at station CSC-2A (12,000 Ibs/day) , and the character of the bottom deposits
in the Lower Calcasieu River in the vicinity of the refinery substantiate
that oil and grease in objectionable quantities are being discharged by the
refinery into the River.
4. River water near the refinery discharge is toxic to shrimp, one
of the native forms of aquatic life found in the Lower Calcasieu River.
5. Cooling facilities, which will reduce flow through the pond system,
are under construction. The pond system will continue to be used for treat-
ing the remaining waste streams and constitutes primary treatment even
though ponding is no suitable treatment for refinery wastes.
6. Operation of the disposal well, if continued, nay result in
-------
31
tions in the amounts of ammonia and sulfides and other substances now dis-
charged to the pond system. Such disposal is contrary to EPA policy guide-
lines and previous regulatory practice.
RECOMMENDATIONS
It is recommended that:
1. Consideration be given to initiating appropriate abatement actions
against the Lake Charles Refinery of the Cities Service Oil Company for
discharges of carbonaceous materials; suspended solids; chromium; mercury;
copper; lead; phenols; and heat to the Calcasieu River.
2. The appropriate Federal District Court be requested to enjoin
the Cities Service Oil Company from use of the disposal well because such
practice is contrary to the public interest and may endanger public water
supplies.
3. The Corps of Engineers permit, to be issued to this refinery,
limit the discharge of BOD; COD; TOG; suspended solids; oil and grease;
heavy metals; complex organics; and heat to levels consistent with best
available treatment and with the water quality standards for the Lower
Calcasieu River.
-------
Facility Description
32
BACKGROUND INFORMATION O
•J
. «
Ownership of this plant is divided as follows: approximately two- n
<
thirds by Cities Service Oil Company and one-third by Continental Oil o
Company, thus the name Cit-Con.
This lube and wax plant operates continuously. Of the 454 persons
employed at the plant three are involved in water pollution control
activities. Finished products are liquid paraffin wax; vacuum gas oil; g
w
wax slabs; finished neutral oil; finished light intermediate neutral oil;
finished heavy oil; soft wax by-product; finished bright stock; and amor-
phous wax.
The primary raw material is topped crude. Rated plant capacity
is 30,000 barrels per day of feed, of which 9,500 barrels are lube stock.
Water Supply
Water for use in this plant is obtained from a series of four wells, g*
each of which is rated at 1,000 pgm (1.44 mgd) . Approximately 1,000 gpm
(1.44 mgd) are used for non-contact cooling and 2,000 gpm (2.88 mgd) for
process water. Water is also used to slurry fine clay employed as a de-
coloring agent, to disposal pits.
Existing Waste Treatment
Wastewater discharges from this industry are treated in a large oxida-
tion pond where gravity separation and skimming of oil and grease are pro-
vided. The wastewater flow is approximately 3.32 mgd, of which 0.43 mgd is
cooling water. The oxidation pond has a retention time of about 70 days.
Effluents from this pond and the clay pits discharge to an open channel tbnt
-------
33
subsequently enters Bayou d'Inde [Figure 3].
DISCUSSION OF SAMPLING PROGRAM AND RESULTS
Aliquots (125 ml) of the plant effluent were collected every two hours
and composited over a 24-hour period commencing at 7:15 a.m. April 21.
[Description of sampling stations is provided in Table 10.] The plant
effluent samples were taken at a railroad bridge (CSC-6), located approxi-
mately 500 feet downstream of the oxidation pond [Figure 3]. At this
sampling point the effluent from the clay slurry pits was thoroughly mixed
with the pond effluent. A grab sample was collected, at 4:40 p.m. April 17,
for oil and grease analysis. [Results of the effluent sampling are shown
in Table 11.]
During the 24-hour period of sampling the lube and wax plant discharged
410 Ibs of TOG; 60 Ibs, NH.-N; 630 Ibs, suspended solids; and 190 Ibs of oil
and grease.
Shrimp survival studies were conducted in Bayou d'Inde at station
CR-6.1 [Figure 3] and at Control Stations following methods outlined in
Appendix C. Sediment samples were collected upstream of the lube and wax
plant and at Station CR-6.2 [Table 12].
Survival studies with shrimp indicate that total mortality occurred
within six hours [Table 13]. The lack of oxygen in the water or the
toxicity from either industrial wastes or noxious gases (released from
the sludge-covered bottom) was considered as cause of death. The 100
percent mortality precluded taste and odor tests. During this time span,
at CR-11.2 and CR-1, shrimp mortalities were 10 and 20 percent, respectively,
-------
34
TABLE 10
DESCRIPTION OF EFFLUENT AND RECEIVING WATER SAMPLING POINTS
Station
Number Description and Remarks
CSC-6 Effluent from oxidation pond of lube and wax plant, collected at
railroad bridge approximately 500 feet downstream from pond.
CR-1 Lower Calcasieu River near Calcasieu Landing (above intracoastal
waterway) near channel marker 92 (Control Station).
CR-6.1 Bayou d'lnde downstream from Cit-Con, and Cities Service petro-
chemical plant.
CR-6.2 Bayou d'lnde upstream of Cit-Con, and Cities Service petrochemical
plant.
CR-11.2 Lower Calcasieu River, south shore, south of Clooney Island just
west of Lake Charles (Control Station).
-------
TABLE 11
SUMMARY OF ANALYTICAL RESULTS AND FIELD MEASUREMENTS-2/
Sla
Flow
PH
range
Conductivity
Umhos/cm
range
composite
Solids
TOC
Temp
°C _
range tng/1 Ibs/day mg/1 Ibs/day mg/1 Ibs/day mg/1 Ibs/dav
total
SUSP
NHi as N
CSC-6
2.91
7.2-8.6
460-
540
510
26-29
17
410
361 8,800
26
630
2.35
60
Sua
mR/1
Oil
&
Crease
Ibs/dav
Cadmium
ma/1
me/1
Chromium
Ibs/dav
Mercury
UR/1
Lead
me/1
Copper
mjj/1
CSC-6
190
<0.05
0.07
<0.02
aj Analytical procedures are outlined in Appendix D.
!•*»
Ln
-------
TABLE 12
ANALYTICAL RESULTS OF BOTTOM SEDIMENT SAMPLES
Station
CR-6.1
CR-6.2
Station
CR-6.1
CR-6 . 2
Date
4/22/71
4/22/71
Nitrogen
0.375
0.423
Water , ,
Depth, Type27 Odor27 Volatiles
Time Feet of bottom of bottom %
1350 15.0 Soft mud H2S 20
1700 Black muck Septic 19
Organic . .
Sediment Sediment Mercury—7
Index Type VR/R
3.4 III 2.0
3.1 III 1.7
Organic
Carbon
9.03
7.41
aj General appearance and odor at time of collection.
b_/ Results based on dry weight. Samples dried at 35°C for two days,
LO
-------
37
TABLE 13
SURVIVAL STUDIES OF WHITE SHRIMP IN THE
LOWER CALCASIEU RIVER, LOUISIANA
Station
a/
96-Hour Survival Study—
Exposure
Time
Number
Alive
Dead
Percent
Survival
CR-11.2
(Control)
CR-6.1
CR-1
(Control)
Initial
24-hour
48-hour
72-hour
96-hour
Initial
24-hour
Initial
24-hour
48-hour
72-hour
96-hour
10
9
8
8
5
10
0
10
8
8
8
5
1
2
2
5
0
10
0
2
2
2
5
100
90
80
80
50
100
0
100
80
80
80
50
a/ April 20-24, 1971
-------
CSC OIL REFINING
PLANT
Not To Scale
Figure 3. Effluent & Receiving Water Sampling Locations for Cities Service Oil Co. • Lube & Wa« Plant (CIT-CON) & Petrochemical Plant
-------
38
Sediment analyses from CR-6.1 indicated a 20 percent volatile material
and an organic sediment index (OSI) of 3.4 [Table 9]. This OSI value
indicates a highly organic bottom deposit that is undergoing decomposition
and stabilization. Upstream of the lube and wax plant discharge the sedi-
ment was composed of decaying material, vegetation, leaves, etc. At this
location the OSI was only slightly lower (3.1); likewise, the volatile
material (19 percent) was lower.
DATA REPORTED TO LOUISIANA STREAM CONTROL COMMISSION
The Louisiana Stream Control Commission approved (December 16, 1970)
the discharge levels of certain materials based on data submitted by the
Cities Service Oil Company for its lube and wax plant. A summary of the
information from the Commission files is as follows:
Quantity of Discharge: 5.1 cfs*
Temperature: 65-87°F
Turbidity: 36 JTU
True Color: 30
Organic Materials (BOD): 2870 Ibs/day - 104 ppm
Phenol 825 Ibs/day - 30 ppm
Organic Materials (oil): 5,520 Ibs/day - 200 ppm
Toxic Materials
Chromium 12 Ibs/day - 0.42 ppm
Zinc 4 Ibs/day - 0.16 ppm
* Approximately 87 percent of the 5.1 cfs is discharged to the
Cities Service refinery sewers and thence to the Lower Calcasieu
River; 0.7 cfs goes directly to Bayou d'Inde.
PROPOSED WASTE TREATMENT
A larger oxidation pond is being constructed for this plant. The cost
for new facilities was estimated at $1.5 million. (The plant was under con-
struction at the time of sampling.) They are scheduled to be in operation
by the latter part of 1971.
-------
39
CONCLUSIONS
1. The daily discharged loads of 410 pounds of carbonaceous material;
630 pounds of suspended solids; and 190 pounds of oil and grease are vio-
lations of Section 407, Rivers and Harbors Act of 1899 (33 USC: 401-413).
2. The Company is engaged in construction of new facilities for treat-
ment of the lube and wax plant liquid wastes.
3. Results of survival tests with shrimp were inconclusive because
effects of other nearby discharges could not be separated from those of the
lube and wax plant.
RECOMMENDATIONS
It is recommended that:
1. The Office of Enforcement, EPA, monitor progress toward completion
and operational status of the treatment facility, now under construction.
2. If suitable treatment is not operational by June 1, 1972, con-
sideration be given to initiating appropriate abatement actions against
the Company for the discharge of carbonaceous materials; nitrogenous mate-
rials; suspended solids; and oil and grease.
3. If the new treatment facilities are in operation by June 1, 1972,
the discharge from the lube and wax plant be reevaluated and, if the
quality does not meet applicable criteria, appropriate abatement actions
be initiated.
4. The Corps of Engineers permit, to be issued, limit concentrations
of BOD; COD; TOC; suspended solids; oil and grease; and complex organics, to
levels consistent with best available treatment and applicable water quality
standards.
-------
40
BACKGROUND INFORMATION
Facility Description
H
pi
70
n
PJ
a
w
r
w
The materials produced at the Cities Service Petrochemical and Ethy-
lene-Propylene plant are propylene; ethylene; butadiene; butane and dimer;
ethylene glycol; ethylene oxide; polyglycols; and ammonia.
The plant operates continuously. Of the 498 persons employed in
production, three - an engineer, a chemist, and an equipment operator -
are involved in water pollution control.
Rated annual capacities of the facility are 900 million Ibs of ethy-
lene; 500 million Ibs, propylene; 220 million Ibs, polyethylene; six
million Ibs, ethylene oxide; and 22 million gal. of ethylene glycol.
The raw materials employed include raw gas; ethane; by-products from
the Cities Service Oil Company refinery identified only as C_ stream and
C. mix; propane; butadiene; nitrogen; hydroformer gas; platformer gas;
caustic soda; and sulfuric acid.
Water Supply
Water Is obtained from seven wells, each of which is rated at 1,000 gpm
H
(1.44 mgd). This water Is used for cooling water makeup, boiler feed, and
process water. Approximately 223 mgd of cooling water is recirculated
through the cooling systems. The condensate from the cooling water is sold
to a neighboring industry.
Existing Waste Treatment
The wastewater discharge from this industry is approximately 3 mgd.
Treatment consists of neutralization; oil separation (gravity); and three
-------
41
aerated lagoons — totalling five acres, which are operated in series. The
effluent from the lagoons is discharged to Bayou d'Inde.
SAMPLING PROGRAM AND RESULTS
Aliquots (250 ml) of the treated waste were collected every four hours
and composited over a 24-hour period commencing at 8:40 a.m. on April 21.
A grab sample was collected for oil and grease analysis at 4:15 p.m. on
April 17. A grab sample for special organic analyses was collected at
11:45 a.m. on April 21. Sampling, made of the effluent from the petro-
chemical plants' third lagoon, was collected at the overflow structure
prior to discharge in Bayou d'Inde (CSC-5). [Its locations are shown in
Figure 3. Analytical results for station CSC-5 are tabulated in Table 14.]
The organic compounds [Table 15] represent the major constituents
in the effluent sample. Other compounds were observed in lesser concen-
trations, but were not positively identified. The results demonstrate
that a wide variety of aromatic chemicals are discharged by the Company's
petrochemical plant. The specific toxicity of these compounds has not been
determined. However, discharge of these compounds undoubtedly has a
detrimental effect on the receiving water.
Net loads discharged by the petrochemical plant during the 24-hour
sampling period included 59 Ibs of chromium; 20,200 Ibs, COD; 5,900 Ibs,
TOG; 180 Ibs, ammonia; 2,600 Ibs, suspended solids; and 165 Ibs of oil and
grease.
Shrimp survival tests and sediment analyses for the stations in Bayou
d'Inde are discussed under the section covering waste treatment and disposal
at Cities Service Oil Conpanv lube and wax plant.
-------
TABLE 14
SUMMARY OF ANALYTICAL RESULTS AND FIELD MEASUREMENTS2'
Conductivity Solida
pH ymhos/cm Temp °C TOG COD total SUSP NHi aa N
Sta Flow range range range nig/l lha/day mg/1 Ibs/day mg/1 Ibs/day _._mg/l Ibs/day ng/1 Ibs/dav
CSC--5 3.95 9.2-9.7 1,000-1,600 26-28 180 5,900 612 20.200 868 28,600 78 2,600 5.35 180
Oil & Crease Cadmium Chromium Mercury Lead Copper
Sta THR/I Ibs/day mg/1 mg/1 Ibs/day ue/1 Ibs/day mg/1 mg/1 Ibs/day
CSC-5 5 165 <0.05 1.8 59 0.8 ' 0.0264 <0.1 0.09 3
a/ Analytical procedures are outlined In Appendix D.
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43
TABLE 15
RESULTS OF ORGANIC ANALYSIS
Concentration Load
Compound Identified (mg/1) Ib/day
2-Methylnaphthlene 0.030 1.1
1-Methylnaphthalene 0.025 0.9
2,6-Diraethylnaphthalene 0.015 0.5
Indan 0.007 0.3
Indene 0.026 0.9
m-Xylene 0.008 0.3
1-Methylindene 0.002 0.1
3-Methylindene 0.003 0.1
Naphthalene 0.053 1.9
o-Methylstyrene 0.001 0.05
m-Methylstyrene 0.02 0.8
p-Xylene 0.002 0.1
o-Xylene 0.006 0.2
Phenol 0.060 2.1
Styrene 0.031 1.1
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44
DATA REPORTED TO LOUISIANA STREAM CONTROL COMMISSION
The Louisiana Stream Control Commission had, in its files, no infor-
mation on the industrial waste discharge from the Cities Service Oil
Company petrochemical plant.
PROPOSED WASTE TREATMENT
The Cities Service Oil Company is presently constructing a new kind of
"extended aeration" facility in order to treat wastewaters from the petro-
chemical plant. This new facility, to cost approximately $3 million and
scheduled to be placed in operation during 1972, should reduce the loads of
COD, TOG, and suspended solids now being discharged to Bayou d'Inde.
CONCLUSIONS
1. Present discharges of chromium; carbonaceous materials; nitro-
genous materials; suspended solids; complex organics; and oil and grease
constitute violations of Section 407, Rivers and Harbors Act of 1899
(33 USC: 401-413).
2. Treatment facilities now under construction should reduce quantities
of carbonaceous and nitrogenous materials discharged to the Lower Calcasieu
River. The new facilities may also reduce quantities of complex organics
and suspended solids discharged. No evidence exists, nor has any claim been
made, to the effect that the new treatment will eliminate discharges of
heavy metals and oil and grease.
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45
RECOMMENDATIONS
It is recommended that:
1. The Office of Enforcement, EPA, monitor progress toward comple-
tion of new facilities for treatment of the liquid wastes generated by the
plant, and that it further conduct follow-up monitoring of actions taken
to reduce discharges of chromium and oil and grease.
2. If the new treatment facilities now under construction are not
operational by June 20, 1973, consideration be given to initiating appro-
priate abatement actions against the Company for discharges of carbonaceous
and nitrogenous materials, suspended solids, and complex organlcs.
.3. If the new treatment facilities are on-line by June 30, 1973,
the treatment provided be reevaluated, and abatement measures, as needed,
be initiated.
4. The Corps of Engineers permit, to be issued this industry, limit
discharges of BOD; COD; TOC; heavy metals; suspended solids; complex
organics; and oil and grease to levels consistent with best available treat-
ment and water quality standards for the Lower Calcasieu River.
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46
REFERENCES
I/ Rivers and Harbors Act of 1899, 33 U.S.C. 401-413, Section 407
referred to as Refuse Act of 1899.
2/ Federal Water Pollution Control Act, 33 U.S.C. 466 et seq, as
amended by the Federal Water Pollution Control Act Amendments of
1961-CPL 87-88), the Water Quality Act of 1965-(PL 89-234), the
Clean Water Restoration Act of 1966-(PL 89-753), and the Water
Quality Improvement Act of 1970-(PL 91-224).
$/' U. S. Department of Commerce, Environmental Science Service
Administration Coast and Geodectic Survey, Atlantic Coast Sixth
(1967) Edition 163-165.
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APPENDIX A
APPLICABLE WATER QUALITY REGULATIONS
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A-l
APPENDIX A
APPLICABLE WATER QUALITY REGULATIONS
General
The Calcasieu River is a navigable waterway in law and in fact.—
Large ocean-going vessels travel up the Calcasieu River to Westlake,
Louisiana. The remainder of the Calcasieu River upstream of Westlake is
also used for navigation. Similarly, the lower portion of the Calcasieu
River complex can be classified as a coastal water in that tidal influ-
ences are felt for significant distances upstream of the point where the
Calcasieu joins the Gulf of Mexico. In compliance with the Federal Water
Pollution Control Act, as amended, the State of Louisiana established water
quality standards for interstate streams, coastal waters, and streams dis-
charging into coastal waters. These standards were approved by the
Secretary of the Interior. The Calcasieu River is also subject to the pro-
visions of Section 407 of the 1899 Rivers and Harbors Act (the Refuse Act),
and the oil discharge regulations established pursuant to the Water Quality
Improvement Act of 1970.
Water Quality Standards^
The State of Louisiana divided the Calcasieu River from the Gulf of
Mexico to its origin into three distinct zones for the purpose of establish-
ing water quality standards: (1) Zone 1, the Calcasieu River fron its
origin to the Salt Water Barrier; (2) Zone 2, the Calcasieu River fron the
Salt Water Barrier to the upper end of Moss Lake; and (3) Zone 3, that
portion of the Calcasieu River fror. the upper end of Moss Lake to the Gulf
of Mexico. Louisiana State Water OuaiiLv Standards for the Calcasieu River
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A-2
describe a series of present uses of that river. They are industrial
supply, primarily cooling water in the Lake Charles area; propagation of
aquatic life for commercial fishing, including shellfish; irrigation water
for considerable acreage of river; recreational use, including water contact
sports; navigational use from the Lake Charles area to the Gulf of Mexico;
and finally, carriage of municipal and industrial wastes.
Conditionally, the State indicated that they expected changes in the
usage of this water with the progression of time. Primarily, these changes
will take the form of municipal water supply in the upper reaches, carriage
of treated municipal and industrial wastes in the lower area, and increased
use for industrial supply.
No water quality standards have been established for the following
tributaries: Bayou d'Inde, Bayou Verdine, Contraband Bayou, English Bayou,
Houston River, Mill Creek and Palmetto Creek, all intrastate waters. The
Standards established for the Calcasieu River follow.
Zone 1 - The River from Its Origin to the Salt Water Barrier
General criteria were established in Zone 1 by the Louisiana State
Stream Control Commission in 1968. These criteria state that no discharge
to Zone 1 shall result in conditions in the stream that will adversely
affect the public health or use of the water (i.e. municipal and industrial
supplies, recreation, propagation of aquatic life, etc.).
Specific criteria are as follows:
pH From 6.0 to 8.5
Dissolved Oxygen Not less than 50 percent saturation at
existing water temperature.
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A-3
Temperature
Oil and Grease
Toxic Materials
Not to be raised more than 3°C above
nornal ambient water temperature nor
to exceed an absolute maximum of 36°C.
No oil slicks of free or floating oil
are present in sufficient quantities
to interfere with the designated uses
nor shall emulsified oils be present
in the same quantity.
None present in quantities that alone
or in combination will be toxic to
animals or plant life, but in all
cases the level shall not exceed a
TLM
48/10'
No foaming or frothing
materials
Coliform Density 1600/100 ml, calculated as the most
probable number, as a monthly mean.
However, 10 percent of the samples may
exceed the previous number up to
5420/100 ml in any one month.
Other Materials Limits on other substances not hereto-
fore specified shall be in accordance
with recommendations set by the
Louisiana Stream Control Commission
and/or by the Louisiana State Board of
Health for municipal raw water sources.
Zone 2 - The Calcasieu River from the Salt Water Barrier
to the Upper End of Moss Lake
General criteria for this zone indicate that, at present, the water is
suitable for propagation of aquatic life, recreation, navigation, and low
grade industrial supply when necessary adaptations are made by industry.
No discharge is to be permitted that will result in stream conditions that
will adversely affect public health, propagation and harvesting of aquatic
life, recreation and navigation, or impose additional burdens of adaptation
on industrial use.
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A-4
Specific criteria for Zone 2 are shown in the following table:
pH
Dissolved Oxygen
Temperature
Oil and Grease
Toxic Materials
6.0 to 8.5
Not less than 50 percent saturation at
the existing temperature.
Not to be raised more than 3°C above
normal ambient water temperature nor
to exceed an absolute maximum of 36°C.
There shall be no slicks of free or
floating oil present in sufficient
quantities to interfere with the
designated uses nor shall emulsified
oils be present in the same quantity.
None present in quantities that alone
or in combination will be toxic to
animals or plant life, but in all cases
the level shall not exceed a TLM/0/1..
Ao/10
No foaming or frothing
materials
Coliforms The monthly median for coliform density
shall not exceed 542/100 ml (MPH) nor
shall this count exceed 1750/100 ml in
more than 10 percent of the samples in
any one month.
Zone 3 - The Calcasieu River from the Upper End of Moss Lake
to the Gulf of Mexico
The general criteria for this zone indicate that during periods of
low flow the high mineral content of the water approaches that of the
marine water itself. This mineral content is caused by tidal intrusion.
Therefore, no discharge shall produce conditions in the stream adversely
affecting public health or the use of waters for propagation and harvesting
of aquatic life, recreation, or navigation.
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A-5
Specific criteria for this zone are as follows:
pU
Dissolved Oxygen
Temperature
Oil and Grease
Toxic Materials
Prom 6.0 to 8.5
Not less than 60 percent saturation at
existing water temperature.
Not to be raised more than 3°C above
normal anbient water temperature nor
to exceed an absolute maximum of 36°C.
No oil slicks of free or floating oil
are present in sufficient Quantities
to interfere with the designated uses
nor shall emulsified oils be present
in the same quantity.
None present in quantities that alone
or in combination will be toxic to
animals or plant life, but in all cases
a level shall not exceed a TLM,g . _.
No foaming or frothing
materials
Coliforms The monthly median shall not exceed
70/100 ml nor shall this count exceed
230/100 ml in more than 10 percent of
the samples in any one month.
The Rivers and Harbors Act of 1899 (Refuse Act)
The Rivers and Harbors Act of 1899 prohibits the discharge of indus-
trial wastes to navigable waters without a permit from the U. S. Army
Corps of Engineers. Section 407 of the Act (referred to as the Refuse Act)
makes it unlawful to discharge from any "... manufacturing establishment,
or mill or any kind, any refuse matter of any kind or description whatever,
other than that flowing from streets and sewers and passing therefrom in a
liquid state, into any navigable water of the United States, or into any
tributary of any navigable water from which the same shall float or be
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A-6
washed into such navigable water ..." provided that a discharge may be
permitted under certain conditions specified by the Corps of Engineers.
Executive Order No. 11574, Administration of the Refuse Act Permit
Program, signed by President Nixon on December 23, 1970, tightens enforce-
ment of the Refuse Act of 1899 by requiring that all sources of industrial
wastes discharging to navigable waters or their tributaries must apply to
the Corps of Engineers for permits to continue such discharges. All
sources of industrial wastes investigated during this study will thus need
to apply for such permits.
Water Quality Improvement Act of 1970
On September 11, 1970, Federal regulations regarding the discharge of
oil to navigable waters were established pursuant to the provisions of
Section ll(b)(3) of the Federal Water Pollution Control Act, as amended by
the Water Quality Improvement Act of 1970. This legislation required the
President to publish, in the Federal Register, rules regarding the allow-
able discharge of oil to navigable water from any source. Subsequently,
the President published rules which specifically stated:
(1) That discharges of oil shall not occur in amounts which violate
applicable water quality standards, or;
(2) That discharges of oil shall not occur in amounts to cause a
film or sheen upon or discoloration of the surface of the water
or adjoining shorelines or cause a sludge or emulsion to be
deposited beneath the surface of the water or upon adjoining
shorelines.
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APPENDIX B
CUSTODY OF SAMPLES
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B-l
APPENDIX
CUSTODY OF SAMPLES
Special procedures were employed during the field investigations of
waste sources in the Calcasieu River Basin to insure that a chain of
custody was documented for water quality samples potentially useful as
evidence for enforcement actions. This documentation was designed to
maintain a record of the collection and source of each sample, as well as
of the personnel involved in the handling, preparation, and disposition of
each.
A unique "custody" number was assigned to each of the Company's waste
effluent samples collected. This number was recorded on the sample tag,
the corresponding "custody" information sheet, and on the laboratory receipt
log.
As each sample was collected, a labeled tag was attached to each
bottle or container. The tray information recorded on the tag included
the "custody" number; the sampling station number and description; the time
and date of collection; the types of analyses to be performed on the sample
by the laboratory; the types of preservatives added [see Appendix D
Analytical Procedures]; and the personnel collecting the sample and per-
forming the sample preservation. Sample containers were placed in plastic
bags and the bags sealed with paper tape bearing the initials of the Indi-
vidual packaging the sample. The intact seal and bag guaranteed the
integrity of the sample during shipment.
A special "custody" information sheet was prepared for each "custody"
number assigned. In addition to information being recorded on the sar.nlc
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B-2
tag, the information sheet recorded the laboratory to which the sample
was sent, the time and method of shipment, and the carrier. Federal
Government bills-of-lading provided additional records of the shipments
made.
Upon arrival of each shipment at its destination, laboratory personnel
recorded the time and date of receipt; the number and type of samples
received; and the analyses to be performed. This documentation procedure
maintained a "custody" record for the field-to-the-laboratory transit.
Each analytical laboratory involved (Division of Field Investigations-
Denver Center; Division of Field Investigations-Cincinnati Center; Analytical
Quality Control Laboratory, Cincinnati, Ohio; and the Southeast Water
Laboratory, Athens, Georgia) then maintained custody of each sample, using
procedures and records standard for the specific laboratory.
This special "custody" documentation was employed for industrial
waste effluent samples only. No "custody" numbers were assigned for water
and sediment samples collected from streams. Normal documentation pro-
cedures including tagging of samples, as discussed above, and logging of
field measurements were followed.
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APEENDIX C
BIOLOGICAL STUDY ^ETHODS
FOR PALATABILITY AND SURVIVAL
STUDIES
Lower Calcasicu River
Louisiana
(April "20-24, 1971)
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C-l
APPENDIX C
"STUDY METHODS
Common white, or lake, shrimp (Penaeuc setiferus), sized from 90-110 mm,*
were used for survival and palatability studies in the Lower Calcasieu River.
Shrimp were captured by bottom seining at 5-minute intervals in Lake
Calcasieu near Turner's Bay. The catch was released from the seining net
into a holding tub. These test shrimp were transferred, with extreme care,
employing a nylon dipnet, or by hand, from the tub to an aerated acclimation
tank filled with clean water from Lake Prein. Shrimp exposure out of the
water was kept to a minimum.
After a 24-hour acclimation period in the tank, less than ten percent
of the shrimp were found in distress or dead because of the previous day's
netting and handling. These were culled from the tank. Live, healthy
shrimp were taken from the holding tank, decapitated, wrapped in foil, and
frozen with dry ice for use as a taste and odor reference sample. The re-
maining live, healthy shrimp were used for survival and palatability tests.
At selected stations, wire, minnow baskets were attached to floats
and suspended at 1-foot depths in the River. Cloth net bags, measuring
12 by 24 inches and having a mesh opening of one-quarter inch, were placed
inside the baskets. Live shrimp were carefully transferred from the hold-
ing tank to cloth net bags inside the wire baskets. This basket apparatus
permitted free circulation of River water through the cages, retained the
test shrimp, and reduced predation by crabs.
* Determined by measuring from the tip of the rostrum to the end of the
telson.
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C-2
Flavor and Odor Evaluation (Field and Laboratory Procedures)
Baskets, each containing six shrimp, were placed at control stations
and near the Company's effluents in the Lower Calcasieu River and its tri-
butaries. After a 6-hour River exposure near the Company's discharge, the
shrimp were retrieved and examined. Survivors were decapitated, wrapped,
in foil, and frozen with dry ice. These frozen shrimp were shipped to the
Department of Food Science and Technology at Oregon State University,
Corvallis, Oregon, for flavor and odor evaluations by a panel of experi-
enced judges.
Odor Test — At the Oregon State University facility, the wrapped,
frozen shrimp were transferred from the shipping container to a -10°F
freezer. Later, the shrimp were removed from the freezer and placed at
40°F. until defrosted, then cooked in eight ounces of unsalted boiling
water for five minutes. The cooked shrimp were quickly peeled and then
tightly wrapped with plastic film. The cooking water was poured into
100 ml beakers and the beaker then tightly covered with aluminum foil.
Each respective sample of shrimp and cooking water was placed on a plate
coded with a 3-digit random number.
The reference sample* was divided into four portions, two of which
were placed on coded plates and the other two on plates marked "Ref."
These shrimp were then alloted to two groups and placed on opposite counters
for odor testing, with the first sample in each group being a "Ref" sample.
Half of the judges smelled one group first and then smelled the other.
* Shrimp that were kept in aerated Lake Prien water and not exposed to
River water near industrial discharp,es.
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C-3
with a 3- to 5-minute wait between groups. The judges were asked to sniff
both the shrimp and the cooking water and score the intensity of "off-odor"
as related to the reference sample. Re-sniffing the reference sample was
allowed. Thirty minutes after the first odor test was completed, the
plates were receded with new 3-digit random numbers, the order changed,
and a second test conducted by the same ten judges.
Flavor Test — Each shrimp was cut into four pieces and each respec-
tive sample mixed, then served in paper cups coded with 3-digit random
numbers. The coded cups were randomly placed on two serving trays, each
of which contained a labeled and a coded "Ref" sample. The trays were
served in balanced order to the judges seated in individual testing booths
lighted with yellow-orange light. The judges were asked to score the
degree of "off-flavor" and the overall desirability of the samples on a
7-point scale. (0=extreme "off-flavor" and 7=no "off-flavor.") Because
the sample size varied from one to six shrimp, only five judges were served
on the flavor panel. Because there was only one shrimp in four of the
96-hour exposure samples, only two judges received these samples.
Survival Tests
Baskets, each containing ten shrimp, were placed at "flavor evaluation
test" stations and elsewhere. These shrimp were used as test animals for
96-hour survival studies. At the termination of each 24-hour exposure
—period, mortalities were recorded and the surface water near each basket
was tested for pH, temperature, and salinity.
Shrimp that survived the 96-hour exposure were tested for flavor in
the nanncr described above.
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APPENDIX D
ANALYTICAL PROCEDURES
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D-l
APPENDIX D
ANALYTICAL PROCEDURES
Grab, or 24-hour composite, samples of water, industrial waste, and
•
bottom sediments were collected in the Lake Charles area by DFI-DC person-
nel. Samples were preserved when collected as outlined in the Federal Water
Quality Administration's Manual for the Chemical Analysis of Water and
Wastes.—
One-liter grab samples were collected in glass containers from each
Company's effluent suspected of containing oil and grease. The samples
were preserved with 2 ml concentrated H.SO./l and shipped on ice to the
Division of Field Investigation-Denver Center. Within 24 hours after col-
lection, the samples were tested for oil and grease, according to the pro-
cedure outlined in Standard Methods for the Examination of Water and Waste
Water— - with tlie exception that n-hexane uas used as the extraction
solvent instead of petroleum ether. Because only single grab samples were
taken from each effluent, the results may not be representative of the
composite daily discharge.
Twenty-four-hour composite samples were collected at each of the
Company's effluents. One liter of the sample was preserved with 2 ml con-
centrated II SO, for total organic carbon (TOC), chemical oxygen demand
(COD), ammonia nitrogen (NH_-N), and organic nitrogen (org.-N) analyses.
One liter was preserved with 5 ml concentrated UNO. for metals analyses
and one liter was left untreated for total and suspended solids analyses.
Water and effluent sanples specified for metals analyses were shipped,
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D-2
air-freight, to the Division of Field Investigations-Cincinnati Center.
These samples were analyzed for cadmium (Cd), copper (Cu), Lead (Pb) ,
chromium (Cr), zinc (Zn), aluminum (Al), and nickel (Ni) by atomic absorp-
tion spectrophotometry. All samples were analyzed for total mercury (Hg)
•> I
according to the flameless AA procedure of Hatch and Ott.—
Other samples were shipped, air-freight, to the Analytical Quality
Control (AQC) Laboratory in Cincinnati where they were analyzed, by DFI-DC
personnel, according to procedures described in the FWQA Manual.-^
These samples were tested for TOC by injection of homogenized 100 ul
aliquots into a Beckman Model 915 Carbon Analyzer after having been purged
with nitrogen gas for five to ten minutes. Injections were made in dupli-
cate and triplicate; the average peak height was taken for comparison to
a standard curve. In general, reproducibility was within five percent.
Industrial waste samples with more than 20 mg/1 TOC were also analyzed
for COD. These determinations were made according to the procedure for
"high level COD", (i.e., digestion with 0.25N KjC^O ) . For this analysis
sufficient mercuric sulfate was added to each sample to tie up the chloride
ions — as determined by titration with mercuric nitrate. In general, each
sample was tested only once, although one duplicate analysis was reproduc-
ible within eight percent. Both NH.-N and org.-N were determined using
the micro-Kjeldahl apparatus. Consequently, all reagent concentrations
were scaled down to one-tenth of the level of the regular Kjeldahl proce-
dure. Several duplicate analyses were performed with reproducibilities of
four and six percent.
Total and suspended solids were determined on the unpreserved samples.
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D-3
The residues were dried at 105°C.
Bottom sediment samples were collected with an Eckman Grab Sampler at
selected sites along the Calcasieu River and in the vicinity of waste dis-
charges. The muds were packed in Whirlpack bags, frozen, and shipped air-
freight to the AQC Laboratory in Cincinnati.
Samples, when thawed, were air-dried at 35°C for two days under a
stream of clean, dry air. The percent volatile- were calculated from the
weight loss after heating the dried sample at 600°C for one hour. The
percent carbon and organic nitrogen were determined by the procedures out-
4/
lined by Ballinger and McKee.— The organic sediment index (OSI) was
calculated as the product of the percent carbon and percent organic nitrogen.
Mercury in the dried sediments was determined by an adaptation of the
"wet digestion/flameless AA procedure" for mercury in fish developed by
Uthe, et al.— Standard additions using mercuric chloride or methyl
mercuric chloride were made on each sample; recoveries ranged from 87 to
122 percent throughout the 20 samples.
One-liter grab samples were collected from the Company's effluents
for organic characterization. Immediately after collection, the samples
were frozen and shipped, air mail-special delivery, to the Southeast Water
Laboratory, Athens, Georgia. The samples were thawed, then extracted with
•chloroform. Chloroform extracts were concentrated to one ml or less and
injected into a Perkin Elrcer Model 900 gas chromatograph. Conditions were
adjusted to obtain the best resolved chronatogram by usin? open tabular
columns of Carbowax 20 M or SE-30. Once the conditions were selected, the
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D-4
column effluent was directed into a Perkin Elmer-Hitachi Mass Spectrometer,
Model KMLJ-7. Mass scans were made of all major peaks. Identity of the
extract components was confirmed by injecting known compounds under the
same conditions and comparing both the retention time and the mass spectrum.
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D-5
REFERENCES
1. U. S. Department of the Interior, Federal Water Pollution Control
Administration Hanual for tlic Gicrrical Ar&lysis of Mater and Wastes.
Washington, D.C. November 1969.
2. M. J. Taras, A. E. Greenberg, R. D. Hoak, and M. C. Rand, Standard
Methods for the Examination of Hater and Wastewater3 12th Ed., Amer.
Public Health Assn. Hew York, N.Y. 1965.
3. W. R. Hatch and W. L. Ott, Anal. Cnen.\ 40. 2085 (1965).
4. D. G. Ballinger and G. D. McKee, J. Hater Poll. Con. Fed., .43 (2)
216 (1971).
5. J. R. Uthe, F. A. J. Armstrong and M. P. Stainton, J. Fisheries Res.
Board of Canada, 27., No. 4, 805 (1970).
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