ENVIRONMEimf PROTECTKn UEX~\
OF K\HHt«»1KM
REPORT ON
EVALUATION OF INDUSTRIAL WASTE DISCHARGES
CONTINENTAL OIL COMPANY
WESUAKE. LOUISIANA
Prepared By
DIVISION OF FIELD INVESTIGATIONS - DENVER CENTER
DENVER. COLORADO
AND
REGION VI DALLAS, TEXAS
LEAj
OCTOBER 1971
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ENVIRONMENTAL PROTECTION AGENCY
OFFICE OF ENFORCEMENT
Report on
Evaluation of Industrial Waste Discharges
at
Continental Oil Company Plants
Westlake, 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
Initial Contact A
CONTINENTAL CARBON COMPANY 6
BACKGROUND INFORMATION 6
Facility Description 6
Water Supply 6
Existing Waste Treatment 6
Chronology of Contacts 6
SAMPLING PROGRAM AND RESULTS 7
DATA REPORTED TO LOUISIANA STREAM CONTROL 7
COMMISSION
PROPOSED WASTE TREATMENT 7
CONCLUSION 7
RECOMMENDATIONS 7
CONTINENTAL OIL COMPANY - LAKE CHARLES 10
PETROCHEMICAL PLANT
BACKGROUND INFORMATION 10
Facility Description 10
Water Supply 10
Existing Waste Treatment 10
Chronology of Contacts 11
FIRST SAMPLING PROGRAM AND RESULTS 12
SECOND SAMPLING PROGRAM AND RESULTS 15
DATA REPORTED TO LOUISIANA STREAM CONTROL 15
COMMISSION
PROPOSED WASTE TREATMENT 17
CONCLUSIONS 17
RECOMMENDATIONS 18
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TABLE OF CONTENTS (continued)
Section Page
CONTINENTAL OIL COMPANY - LAKE CHARLES REFINERY
BACKGROUND INFORMATION 19
Facility Description 19
Water Supply 19
Existing Waste Treatment 19
Chronology of Contacts 19
SAMPLING PROGRAM AND RESULTS 21
DATA REPORTED TO LOUISIANA STREAM CONTROL 24
COMMISSION
PROPOSED WASTE TREATMENT 24
CONCLUSIONS 24
RECOMMENDATIONS 25
CONTINENTAL OIL COMPANY - LAKE CHARLES VCM PLANT 26
BACKGROUND INFORMATION 26
Facility Description 26
Water Supply 26
Existing Waste Treatment 26
Chronology of Contacts 27
FIRST SAMPLING PROGRAM AND RESULTS 27
SECOND SAMPLING PROGRAM AND RESULTS 27
DATA REPORTED TO LOUISIANA STREAM CONTROL 29
COMMISSION
PROPOSED WASTE TREATMENT 29
CONCLUSIONS 31
RECOMMENDATIONS 31
REFERENCES 33
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 Sampling Locations for 6
Continental Oil Co. VCM Plant,
Petrochemical Plant, & Carbon Plant
Effluent Sampling Locations for 12
Continental Oil Co. Conoco Refinery
iii
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LIST OF TABLES
Table No. Title Page
1 Summary of Analytical Results 8
and Field Measurements
2 Description of Effluent Sampling 13
Points
3 Results of Organic Analysis 13
4 Summary of Analytical Results and 14
Field Measurements
5 Summary of Analytical Results and 16
Field Measurements from
Second Sampling Program
6 Description of Effluent Sampling 22
Points
7 Results of Organic Analysis 22
8 Summary of Analytical Results and 23
Field Measurements
9 Summary of Analytical Results and 28
Field Measurements from First
Sampling Program
10 Summary of Analytical Results and 30
Field Measurements from Second
Sampling Program
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 Calcaselu River or
its tributaries - Bayou d'Inde, Bayou Verdine, Houston 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.
4. 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 four facilities of the
Continental Oil Company, Westlake, Louisiana, and recommends actions
necessary to protect the quality of the receiving waters. Complete
custodial 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) [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
Calcasieu River consists of the fresh water portion of the watershed
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Figure 1. Location Map • Calcasieu River Drainage
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extending upstream from the salt water barrier to the basin headwaters.
The River is navigable upstream to Moss Bluff, Louisiana (about
3/
ten miles upstream of 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 hi°h 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
water supplies, recreation, irrigation, and navigation.
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In conjunction with other chemical plants and petroleum refineries,
the Continental Oil Company plants are substantial contributors to the
economy in the Lower Calcasieu River area. These facilities are involved
primarily in the production of organic chemicals, carbon black, and oil
refinery products.
The Company operates four industrial facilities in the Lake Charles
area: (1) Continental Carbon Company; (2) Continental Oil Company -
Lake Charles Petrochemical; (3) Continental Oil Company - Lake Charles
Refinery; and (4) Continental Oil Company - Lake Charles VCM Plant.
Although these plants are in proximity to each other, all are under sep-
arate management.
Initial Contact
Representatives of EPA's DFI-DC staff visited these industries during
the period March 24-31, 1971, to obtain information for an industrial
waste inventory. The Company officials contacted at that time were very
cooperative, provided the information requested, and conducted tours of
their respective plants. Subsequent to these meetings, Refinery and VCM
plant officials were contacted, on April 15, to discuss sampling of plant
effluents. Officials of the carbon Company and Lake Charles Petrochemical
were contacted on April 16. They were informed that the industrial waste
source sampling was in conjunction with a survey of the Calcasieu River
Basin being conducted by EPA, and that the sampling was designed to pro-
vide the basis for:
(1) Evaluation of Corps of Engineers permits as required under the
Rivers and Harbors Act of 1899;
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(2) Determination of present water quality conditions In the
Calcasleu River and Its tributaries;
(3) Evaluation of the individual and collective impacts of waste-
water 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 the effluent discharges was granted. No re-
strictions were placed on the sampling of process wastes prior to treatment.
Allquots (125 ml) were collected of each of the industrial discharges and
composited over a 24-hour period. These composite samples were analyzed
for total organic carbon (IOC); chemical oxygen demand (COD); total and
suspended solids; and selected heavy metals. All of the industrial waste
effluents from Continental Oil Company discharge to Bayou Verdine.
Responsible Company officials contacted, information on plant oper-
ations, etc., and the results of each sampling program are discussed in
the following report.
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BACKGROUND INFORMATION
Facility Description
The plant is owned by the Continental Oil Company (80 percent) and
the Witco Chemical Corporation (20 percent). The plant's rated capacity
3
per day is 250,000 to 300,000 Ibs of carbon black. The raw materials §
used in the process include coke and gas oil. This plant operates con-
•a
tinuously and employs seventy-one persons .
Water Supply
Water is purchased from Continental Oil Company, which borders
Continental Carbon Company on two sides. Water is used for washdown
(quenching) , drinking, and pallatizing of the product.
s:
Existing Waste Treatment 5
A settling pond is employed to collect the small carbon fines. The
(0
pond effluent is discharged to Bayou Verdine [Figure 2] . Banks of Bayou
o
Verdine downstream of Continental Carbon have a flat gray-to-black color,
attributable to the discharge from the settling pond. According to the
a
Continental Carbon Company Manager, constant agitation of carbon fines by o
a*
Ox
the wind causes the material to be blown about the plant site. Some of
these fines find their way into the Bayou. The Manager stated that during
the period 1968 to 1971, the Company converted the air pollution control
system from wet scrubbers to bag houses. He indicated that this change
had reduced the water pollution problems caused by the carbon fines.
Chronology, _of_ Contacts
The Company Manager, Louis Herst, was contacted by M. R. Helton of the
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PETROCHEMICAL PLANT
TREATMENT FACIL.
Not To Scale
Figure 2. Effluent Sampling Locations fnr Continental Oil Co VCM Plant, Petrochemical Plant, & Carbon Plant
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DFI-DC staff, on March 31, 1971, to obtain inventory information. R. D. Harp
and J. L. Hathevay, also of DFI-DC, net with Mr. Herat, on April 16, to
plan the industrial sampling program.
SAMPLING PROGRAM AND RESULTS
Effluent sampling commenced at 9:00 a.m., April 20. Aliquots (125 ml)
were composited every two hours for 24 hours. Samples were collected from
the Continental Carbon plant settling pond effluent (Con-7) which is
discharged to Bayou Verdine. [Analytical results and recorded field mea-
surements are listed in Table 1.]
Loads discharged during the 24-hour sampling period included SO Ibs
of chemical oxygen demand (COD); 10 Ibs, total organic carbon (IOC); and
10 Ibs of suspended solids.
DATA REPORTED TO LOUISIANA STREAM CONTROL COMMISSION
The Louisiana Stream Control Commission had, in its files, no infor-
mation on the industrial discharge from the Continental Carbon Company.
PROPOSED WASTE TREATMENT
No new treatment facilities are proposed for the.next five years.
CONCLUSION
1. The pollutant loads discharged by Continental Carbon are of no
serious consequence to the receiving waters.
RECOMMENDATIONS
It is recommended that:
1. No abatement proceedings be initiated at this time;
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TABLE 1
SUMMARY OF ANALYTICAL RESULTS AND FIELD MEASUREMENTS5/
Flow
Sta mcd
CON-7 0.032
ranee
7.4-8.0
Conductivity
jj mhos/cm
Temp
°C TOC
ranr.e composite ranee me/1
500-825 570
Cadmium
Sta
CON-7
me/1
<0.05
22-30 A3
Chromium
niR/1
0.03
Ibs/dav
10
Ibs/day
0.01
Solids
COD total
me/1 Ibs/day me/1
180 50 440
UR/1
0.1
Ibs/dav
120
Mercury
SUSP
me/1 Ibs/day
36 10
Ibs/day
0.00003
a/ Analytical procedures are outlined In Appendix C.
oo
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2. The discharge permit, to be issued by the Corps of Engineers,
limit discharges of BOD; COD; TOG; heavy metals; complex organics; suspended
solids; and oil and grease, to levels consistent with best available treatment
and the water quality standards for the Lower Calcasieu River.
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10
BACKGROUND INFORMATION p
25
Facility Description
Headquarters for this plant (P. 0. Box 37, Westlake, Louisiana 70669) H
is the office of the Petrochemical Sales Division, Continental Oil Company, o
80 Park Plaza East, Saddlebrook, New Jersey 07662. This plant operates n
continuously and employs 320 persons in its production operation. Twelve
individuals (a superintendent; an engineer; a chemist; a foreman; four
equipment operators; and four maintenance men) are employed in the water
pollution control program.
The annual, rated capacities of this petrochemical facility are 150 w
C/5
million Ibs of industrial alcohol: 550 million Ibs, ethylene; 98 million n
»
Ibs, methyl chloride; 200 million Ibs, normal paraffins; and 50 million o
Ibs of ethoxylates. H
The raw materials used are: ethylene; aluminum; hydrogen; "raffinate";
sulfuric acid; ethylene oxide; acetic acid; caustic soda; phosphoric acid;
hydrochloric acid; kerosene; ethane; propane; and methanol.
Water Supply
Water is obtained from five wells (700 ft deep), each rated at 1,500
gpm (2.16 mgd). It is used for process, boiler feed, and non-contact cool-
ing.
Existing Waste Treatment
There are three wastewater discharges from this industry. These
originate in the alcohol plant, paraffin plant, and the ethylene plant
[Figure 21.
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11
Effluents from the alcohol and paraffin plants discharge to a drainage
ditch that subsequently enters Bayou Verdlne. The ethylene plant effluent
(cooling water) discharges to a second drainage ditch that also collects
the VCM plant discharge before entering Bayou Verdine.
Present treatment of the waste discharges consists of the following:
1. Vastewater passes through an API separator, at the paraffin plant;
2. Caustic wastes are treated in a neutralization basin and oily
wastes pass through an API separator — both waste streams passing
through a settling basin prior to discharge, at the alcohol plant;
(The Company representative stated that total chromate removal
is obtained in the system.)
3. Cooling water receives no treatment prior to discharge, at the
ethylene plant.
Chronology of Contacts
On March 29, J. L. Hatheway of the Division of Field Investigations-
Denver Center, EPA, met with Gary D. Johnson, environmental engineer at
the Lake Charles Petrochemical plant, to obtain inventory information.
R. D. Harp and Mr. Hatheway, DPI-DC, contacted Mr. Johnson, on April 16,
to plan the first industrial sampling program. J. V. Rouse, DFI-DC, con-
tacted J. D. Mlnott, a senior process engineer at Continental's Lake Charles
VCM plant — in the absense of Mr. Johnson, at the beginning (November 1)
of the second industrial sampling program. Mr. Minott was cooperative,
consented to the resampling of the Petrochemical Plant effluent, and re-
quested samples, duplicate to those collected by EPA, for the Company.
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12
FIRST SAMPLING PROGRAM AND RESULTS
Aliquots (125 nl) were collected at two-hour intervals, beginning at
6:45 a.m., April 20, and continued for 24 hours. Grab samples for oil and
grease analysis were collected at Station CON-2 at 2:30 p.m., April 17,
and at 6:45 a.m., April 20. One grab sample for oil and grease analysis
was collected at CON-8, at 9:30 a.m., April 29. A grab sample for specific
organic analyses was taken at station CON-8 at 9:30 a.m. on April 29. [See
Table 3. In Table 2 is a description of the sampling stations for the
petrochemical plant. In Table 4 is a summary of analytical results and
field measurements.]
Four alcohols [Table 3] comprise the major extractable organics in
this effluent. However, numerous other materials were observed in lower
concentration, but were not identified. Although these alcohols probably
have little toxic effect on the receiving environment, they do exert a
considerable oxygen demand, and in the concentrations observed, may repre-
sent an economic loss to the Company.
At the request of Ilr. Johnson, an additional 24-hour composite sample
*/
of the ethylene plant effluent was collected at CON-2A.— A TOC value
of 620 mg/1 was measured at Station CON-2, but at CON-2A the TOC value
was only 8 mg/1. The Company official contended that both tidal action
and the discharge from the vinyl chloride monomer (VCM) plant interfered
with the sample obtained at CON-2. This contention was not borne out
by the pH, TOC, and total solids values observed at CON-2. No waste
Ttiis station is located within the Company property at the point of
discharge to the drainage ditch. Access to the ethylene plant DOS
initially denied to the investigators because of the latent dangers
associated with not being familiar vith the processing and production
of r:etrc?i'.er~:.cc.1 ?.
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13
TABLE 2
DESCRIPTION OF EFFLUENT SAMPLING POINTS
Station
Number Description and Remarks
CON-2 The cooling water effluent from the ethylene plant; samples col-
lected from a ditch to Bayou Verdine at a point 500 ft outside
the south property fence. (This is 100 ft upstream of Station
No. CON-1.)
CON-2A The cooling water effluent from the ethylene plant; samples col-
lected at the point of discharge from a 42-in reinforced concrete
pipe to a drainage ditch to Bayou Verdine. Sampled April 23-24,
1971.
CON-8 Samples collected from a drainage ditch crossing the plant pro-
perty at the weir. The flow is primarily made up of wastewatcr
from the API separator at the paraffin plane, wastewater from
the alcohol plant, and discharges from the oily water sewers of
the ethylene plant.
TABLE 3
RESULTS OF ORGAiJIC ANALYSIS
Concentrations Load
Compounds Indentified (nig/1) Ibs/day
n-Butanol 16 90
n-Decanol 2.3" 15
n-Hexanol 65 375
n-Octanol 19 110
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TABLE 4
SUMMARY OF ANALYTICAL RESULTS AND FIELD MEASUREMENTS-
Sea
co:i-2
CON-2A
CON-8
Sta
CON -2
COIJ-2A
CON-8
Flow pll
mad ranc>e
1.33 5.f>-7.2
1.30 7.1-7.9
0.72 '..1-6.7
Cndmi (in
niR/1
<0.05
<0.05
<0.05
Conductivity
unhos/cm
ranf»e composite
560-1,150 750
900-1,600 1,140
2,500-5,000 4,000
Chromiun
mg/1 Ibs/day
<0.01
<0.1
0.30 2
Temp
°C TOC
range mt»/l Ibs/day
30-34 620 6,890
24-36 8 90
30-36 130 780
Mercury
PR/1 Ibs/day
<0.1
0.2 0.0022
0.2 0.0018
Solids
total SUSP
TOR /I Ibs/day me/1 Ibs/day
570 6,330 32 355
827 8,980 36 390
2,650 15,900 34 200
Copper Lead
mp/1 mjs/l
<0.02 <0.1
<0.02 <0.1
<0.02 0.2^
Oil & Grease
me /I Ibs/day
2-5^X 22-56
7 40
Ibs/day
1.2
n/ Analytical procedures are outlined in Appendix C.
b/ Two separate grab samples.
c/ !!u interference from calcium detected.
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N
/ PETRO- CHEM
PLANT
CONTINENTAL
CARBON
API CPI ACTIVATED SLUDGE.
CLARIFIER AERATED LAGOON
Not To Scale
Figure 3, Effluent Sampling locations for Continental Oil Co Conoco Refinery
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15
streams enter the drainage ditch between CON-2 and CON-2A.
Calculations, based upon analytical data obtained from CON-2 and
CON-8, indicate net discharge loads during the 24-hour sampling period,
of 7,670 Ibs of TOC; 560 Ibs, suspended solids; and 60 to 95 Ibs of oil
and grease.
SECOND SAMPLING PROGRAM AND RESULTS
In order to resolve the disparities noted earlier between results for
CON-2 and CON-2A a second survey was conducted on November 1, 2, and 3,
1971.
Effluent sampling commenced at 6:30 a.m., November 1. Aliquots (125 ml)
were composited every two hours for 24 hours and continued for 48 hours,
yielding two separate-daily-composited samples. Each of the daily composite
samples was thoroughly mixed in Its container and divided, with a portion
given to the Company and the remainder forwarded to EPA laboratories for
analysis. [Analytical results and field measurements of the second sampling
program are listed in Table 5.J Results of the second sampling program
indicate little difference between the waste loads measured at CON-2
and CON-2A.
Waste loads discharged from the Lake Charles Petrochemical Plant were
calculated by summing the discharge loads from either CON-2 or CON-2A
with those from CON-8. These calculations indicated daily discharge
levels of 780 Ibs of TOC, 310 to 590 Ibs of suspended solids, and 40-95 Ibs
of oil and grease.
DATA REPORTED TO LOUISIANA STREAM CONTROL COMMISSION
The Louisiana Scream Control Commission approved (December 16, 1970)
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TABLE 5
SWMARY OF ANALYTIC/ L RESf L*S AND FIfiXD
SEC OND Si MILLING PROCRA
ISUTEMENTS PROM
Sta
CON-25/
co:i-2^
COH-2A-'
CON--2A-'
Flow
1.33
1.33
1.30
1.30
nil
7.7-8.1
7.6-8.8
7.3-7.9
7.5-8.8
Conductivity
pmlios/cn
850-1,750
850-2,100
850-900
800-1,700
Temp
°C
ranp.e
31-35
30-36
33-37
33-37
Solids
TOC
me, /I
<5
<5
<5
<5
COD
mr,/l
16
20
22
20
Ibs/day
180
220
240
220
total
mp./l
640
700
620
690
Ibs/dny
7,100
7,800
6,700
7,500
SUSP
mc/1
10
15
20
20
Ibs/day
110
170
220
220
&J Analytical procedures are outlined In Appendix C.
b_/ Composite sample collected November 1 and 2.
c_l Composite sample collected November 2 and 3.
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17
the discharge levels of certain materials based on data submitted by
Continental Oil Company's Lake Charles Petrochemical Plant. A summary of
the information from the Commission files is as follows:
Date of Application: August 28, 1970
Quantity of Discharge: 1.7 cfs
Temperature: 80*F
Turbidity: 100 BTU's
True Color: 15
Organic Material: 15,150 Ibs/day equivalent to 1,652 ppm COD
Inorganic Material: Equivalent to 23,900 Ibs/day equivalent
to 26,007 ppm total dissolved solids
Toxic Materials:
Phenols 4.8 Ibs/day, equivalent to 0.5 ppm
Sulfide 7.5 Ibs/day, equivalent to 0.8 ppm
Chromate 2.9 Ibs/day, equivalent to 0.3 ppm
PROPOSED WASTE TREATMENT
In order to provide additional treatment to the wastes from the petro-
chemical plant a new aerated lagoon is under construction. The new system
is expected to provide satisfactory removal of the TOC, GOD, and suspended
solids. The new treatment facility may bring about further reduction of
oil and grease.
CONCLUSIONS
1. From the results of two surveys there appears to be no significant
difference between the waste loads measured at Station CON-2 or CON-2A.
The data collected at Station CON-2 during the first survey may have
reflected an inplant "spill", but is generally not representative of the
waste loads discharged.
.2. Of the measured waste loads that are discharged by petrochemical
plant operations, the major portion originates at the paraffin and alcohol
plants (CON-8), for which treatment measures are proposed.
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18
3. Still, discharges of carbonaceous materials, suspended solids, and
grease and oil from the entire petrochemical plant operations constitute
violations of Section 407, Rivers and Harbors Act of 1899 (33 USC: 401-413).
4. New facilities for the treatment of these wastes are under con-
struction and can be expected to reduce present pollutant loads to accept-
able levels.
RECOMMENDATIONS
It is recommended that:
1. The Office of Enforcement, EPA, monitor progress toward completion
of the facilities now under construction.
2. If the facilities now under construction are net operative by
March 1, 1972, consideration be given to initiating appropriate abatement
proceedings against the Company for discharging carbonaceous materials,
suspended solids, and oil and grease to Bayou Verdinc, a tributary to a
navigable stream.
3. If the facilities are in operation by March 1, 1972, the nature
of the discharge from the plant be reevaluated.
4. The Corps of Engineers permit, to be issued to Continental Oil
Company Lake Charles Petrochemical Plant, limit discharges of BOD; COD:
TOG; complex organics; heavy metals; suspended solids; and oil and grease
to levels consistent with best available treatment and applicable water
quality standards.
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19
BACKGROUND INFORMATION
Facility Description
The refinery (P. 0. Box 37, Westlake, Louisiana 70669) is a subdivision
of the Continental Oil Company, Refinery Headquarters, Houston, Texas. It
operates continuously and employs 475 persons. Eight employees (six full-
time and two part-time) are involved in pollution control efforts.
Finished products from this plant are propane; butane; LPG; gasoline;
kerosene; diesel fuel; heating oil; No. 6 fuel oil; and coke.
The rated plant capacity is 71,000 barrels per day. The production
rate is to be increased to 81,000 barrels per day by January 1972.
The primary raw material is crude oil. Other materials added in the
various processes include isobutane and polyvinylchlorlde. Also, the opera-
tion uses various metals that are of concern from the standpoint of water
pollution. These include chromates, zinc, copper, and tetraethyl and
tetrasethy1 lead.
Water Supply
The plant obtains water from six wells, each of which Is rated at a
capacity of 2,000 gpm (2.88 mgd). These wells pump from the 200, 500, and
700-ft strata. Two reserve wells are not used routinely.
Existing Waste Treatment
Original wastewater treatment and disposal facilities included an API
trap, a settling pond, and separate wastewater collection system. The
Company began a water pollution abatement program In 1967. A corrugated
plate interceptor (CPI) that Is reputed to give higher oil recoveries than
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20
the API separators has been installed. An activated sludge and an aerated
lagoon follow the CPI.
Discharges to Bayou Verdine which results from the refinery are:
(1) Effluent from the aerated lagoon;
(2)- The effluent from a "firewater pond" that receives cooling water
blowdown;
(3) Effluent from the coker area;
(4) The cooling water discharge;
(5) At least two intermittent discharges of small amounts of
unidentified liquid wastes.
At the time of the survey, the activated sludge unit was operating.
However, difficulties in maintaining an activated sludge were evident. The
activated sludge unit is designed with a retention time of 24 hours, but
owing to leaks in the aeration basin, it had been necessary to shut down the
unit and drain the basin several times in order to repair the leaks. Con-
sequently, the system had not stabilized and was not, according to Company
officials, providing effective treatment.
At the present time the activated sludge-aerated lagoon system does
not treat the effluents either from the "firewater pond", the coker area, or
the cooling water. The receiving water at the point where discharges enter
the Bayou appeared gray-black in color. According to Company officials,
this color is caused by carbon fines from the Continental Carbon Company
[Figure 2]. The banks of the channel were caked with what appeared to be
carbon fines. The DFI-DC investigating team observed black'fines from the
coker blowing about the area and into Bayou Verdine.
-------
21
Chronology of Contacts
On March 24, 1971, Company representatives Steve Carson and Bill Cayan
were contacted by J. L. Bathevay and M. R. Helton, Division of Field Investi-
tations-Denver Center, EPA, for inventory information. R. D. Harp and
Mr. Hathevay, DFI-DC, met with these officials, on April 15, to plan the
industrial sampling program.
SAMPLING PROGRAM AND RESULTS
Sampling of the refinery discharges commenced at 7:30 a.m., April 20.
[In Figure 3 sampling locations are shown; their description is found in
Table 6.] Grab samples for oil and grease analysis were collected at
CON-6A and CON-7A, on April 17 at 11:25 a.m. and 1:50 p.m., respectively,
and at all other locations starting at 7:50 a.m., April 20. A grab sample
for organic analysis was also collected at Station CON-3 at 8:15 a.m.,
April 20. [See Table 7.]
Samples at CON-6A and CON-7A contained high concentrations of oil and
grease. On April 20, it was observed that at CON-6A there was no flow and
at CON-7A the flow contained no visible oil and grease. [Analytical results
and field measurements are summarized in Table 8.]
All the organic compounds identified [Table 7] in the refinery effluent
are normal aliphatic hydrocarbons that represent a portion of the oil and
grease discharged by the refinery.
During the 24-hour sampling period, the refinery discharged 48 Ibs of
chromium; 2,400 Ibs, TOC; 490 Ibs, ammonia as nitrogen; 8,600 Ibs, suspended
solids; and 1,400 Ibs of oil and grease to Bayou Verdine.
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22
TABLE 6
DESCRIPTION OF EFFLUENT SAMPLING POINTS
Station
Number Description and Remarks
CON-3 Effluent from the refinery's aerated lagoon that receives the
majority of process wastes of the refinery. Effluent is dis-
charged directly into Bayou Verdine.
CON-4 Effluent, from the "fire-pond", discharged directly into Bayou
Verdine.
CON-5 Effluent is from the triangular pond that receives the cooling
water from the calcined coke shaker plus miscellaneous streams
from the coking area. Effluent is discharged directly into
Bayou Verdine.
COH-6 Cooling water effluent from the refinery to Bayou Verdine.
CON-6A Discharge from the coker area sampled for oil and grease on April
17, 1971. No flow on April 20-21. Discharge goes to Bayou Verdine.
CON-7A Sample collected, April 17, 1971, for oil and grease analysis,
from a drainage ditch that commences at the refinery, flows across
Continental Carbon property and discharges into Bayou Verdine.
No samples was collected on April 20, 1971.
TABLE 7
RESULTS OF ORGANIC ANALYSIS
Concentrations Load
Compounds Identified (mg/1) Ibs/day.
Dodecane 0.22 2.2
Eicosane 0.30 2.9
Heneicosane 0.19 1.8
Heptadecane 0.34 3.3
Hexadecane 0.43 4.0
Nonadecane 0.31 3.0
Octadecane 0.33 3.2
Pentadecane 0.49 4.8
Tetradecane 0.58 5,6
Tridecane 0.39 3.8
Undecane 0.05 0.4
-------
TABLE 8
SUMMARY 07 ANALYTICAL RESULTS AND FIELD MEASUREMENTS2/
Sta
COH-3
CON-4
CON-5
CON-6
CON-6A
CON-7A
Sta
CON-3
cot;-4
CON-5
COH-6
.-ii-.d ranee
1.12 7.4-8.
5.43 6.9-8.
1.74 6.8-8.
0.984 3.3-8.
Cadmium
m(«/l
<0.05
<0.05
<0.05
<0.05
Conductivity
umhos/cm
range
6 3,400-
5,000
5 400-650
2 540-750
9 1,150-
4,000
Chromium
me/1 Ibs/day
0.17 1.6
0.16 7
0.41 6
4.0 33
composite
3,900
450
600
1,700
Temp ,. _.Solids
°C TOC COD-' total SUSP
ranee mR/1 Ibs/dav ms?/! Ibs/dav mp./l Ibs/day mR/1 Ibs/day
23-23 210 1,960 676 6,320 2,340 21,900 182 1,700
40-45 5 230 315 14,300 132 5,990
32-40 10 145 460 6,680 49- 710
34-42 7 60 1,130 9,290 30 250
Oil & Grease NHi as N
mR/1 Ibs/day mR/1 Ibs/day
130 1,215 52.1 490
4 180
1 15
3 25
190
100
Mercurv Copper Lead
UR/1
0.9
0.1
0.3
0.1
Ibs/dav mR/1 Ibs/day mR/1 Ibs/dav
0.0084 0.03 0.3 <0.1
0.0045 <0.02 <0.1
0.0044 <0.02 <0.1
0.0008 0.08 0.7 0.1^ 1
co
a/ Analytical procedures are outlined in Appendix C
b_/ COD analyses were performed when TOC values exceeded 20 mg/1.
~c.l No Inii-rftrcnce from calcium detected.
-------
It should be noted that the new activated sludge facility had not been
la operation for a sufficient period of time to achieve effective treatment.
When fully operational, the system in combination with the aerated lagoon
•ay reduce the TOG and suspended solids to satisfactory levels. It is doubt-
ful that the oil and grease will be reduced to a satisfactory level.
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
Continental Oil Company - Lake Charles Refinery. A summary of the informa-
tion from the Commission files is as follows:
Date of Application: August 19, 1970
Quantity of Discharge: 18 cfs
Temperature: 110°F Maximum
Turbidity: 160 ppm
True Color: Clear to slightly yellow or slightly gray
Organic Material: 1850 Ibs/day, equivalent to 19 ppm
Inorganic Material: 53,400 Ibs/day, equivalent to 350 ppm
suspended solids or dissolved solids
Toxic Material:
Phenols 4 ppm maximum - 390 Ibs/day maximum
Hydrogen Sulfide (H.S) 6 ppm maximum equivalent to 585 Ibs/day
maximum
PROPOSED WASTE TREATMENT
Hew waste treatment facilities have been constructed and placed in
operation. All discharge points still must be connected to these facilities,
Fo plans presently exist for treatment of oil and grease or heavy metals.
CONCLUSIONS
1. Present discharges of chromium; carbonaceous materials; nitrogenous
materials; suspended solids; complex organics; and oil and grease constitute
-------
25
violations of Section 407, Rivers and Harbors Act of 1899 (33 USC: 401-413).
2. New treatment facilities have recently been placed in operation.
These facilities may reduce the discharges of carbonaceous and nitrogenous
materials, suspended solids, and complex organics. There is no evidence at
hand and no claim by the Company that the treatment will reduce either
present discharges of heavy metals or of oil and grease.
3. Effluents from the "firewater pond" and the coker, as well as the
cooling water discharge, that carry substantial loads of suspended solids,
heavy metals, and oil and grease continue to be discharged to Bayou Verdine
without adequate treatment. At least two small intermittent discharges of
unidentified liquid wastes also flow directly to Bayou Verdine.
RECOMMENDATIONS
It is recommended that:
1. Consideration be given to initiating appropriate proceedings
against the Continental Oil Company - Lake Charles Refinery (Uestlake,
Louisiana) for the daily discharge of 48 pounds of chromium; 2,400 pounds
of carbonaceous materials; 490 pounds of nitrogenous materials; 8,600
pounds of suspended solids; 1,400 pounds of oil and grease; and a variety
of aromatic hydrocarbons to Bayou Verdine, a tributary to a navigable
stream.
2. The Corps of Engineers permits, to be issued, limit concentra-
tions of BOD; COD; TOC; complex organics; heavy metals; suspended solids;
and oil and grease to levels consistent with best available treatment and
applicable water quality standards.
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26
BACKGROUND INFORMATION g
Pacilitv Description
The VCM Plant (P. 0. Box 605, Uestlake, Louisiana 70669) operates g
t*
under the direction of the Petrochemical Sales Division, Continental Oil
Company, 80 Park Plaza East, Saddlebrook, New Jersey 07662. This facility
operates continuously and employs 80 production workers. The plant assigns
four persons (a senior engineer; a lab technician; an equipment operator;
and an unskilled laborer) to service on the water pollution control program.
The primary product is vinylchloride monomer (Stauffer Process).
By-products of this process are 1, 2-dichlorethane and ethylene dichloride. gj
The plant is rated at 600 million pounds of vinylchloride and 960 million g
pounds of ethylene dichloride per year.
The principal raw materials used are ethylene and chlorine - the latter
purchased locally. Process additives include chromates, phosphates, com-
mercial dispersants, sulphuric acid, and zinc.
Water Supply
Hater is obtained from wells that supply about 600 gpm, of which about
100 gpm is used as process water and 400 gpm for non-contact cooling.
Easting Waste Treatment
The treatment provided consists of steam distillation, clam shell
neutralization and settling pits for light and heavy oil separation. The
effluent is discharged by a single outfall to a drainage ditch [Figure 2]
that subsequently enters Bayou Verdine.
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27
Chronology of Contacts
On March 29. J. L. Hathevay, of EPA'a DPI-DC staff, met with
R. H. Gerlock, chief process engineer, J. D. Minott, a senior process
engineer, and Plant Manager L. N. Vernon, for the purpose of obtaining
inventory information. R. D. Harp, also of the DPI-DC, and Mr. Hathevay
met with these officials, on April 15, to plan the industrial waste sampling
program. J. V. Rouse, DPI-DC, contacted John D. Minott at the beginning
(November 1) of the second Industrial sampling program. He was cooperative,
consented to the resampling of the VCM plant effluent, and requested, on
behalf of the Company, samples duplicate to those collected by EPA.
FIRST SAMPLING PROGRAM AND RESULTS
Aliquots (125 ml) of the effluent were taken at 2-hour intervals, for
24 hours, beginning at 6:05 a.m., April 20. The effluent from the VCM
Plant (CON-1) was sampled at the single oufall leaving the weir box
(Figure 2) and flowing into the drainage ditch coming from the ethylene
plant and subsequently entering Bayou Verdlne. A grab sample was taken
at the time composite sampling was initiated, and analyzed for oil and
grease. [Analyses of the samples are shown in Table 9.]
During the 24-hour sampling period, this industry discharged 12 Ibs
of chromium; 55 Ibs, TOG; 320 Ibs, suspended solids; and 9 Ibs of oil and
grease.
SECOND SAMPLING PROGRAM AND RESULTS
As noted in a previous section - one that describes waste discharges
from the Lake Charles Petrochemical plant, a second survey was initiated
-------
TABLE 9
SUMMARY OF ANALYTICAL RESULTS AND FIELD MEASUREMENTS FROM
FIRST SAMPLING PROGRAM^
Sta
COH-1
Sta
CON-1
Floy
mad
0.547
013.
tnR/J.
2
ran p;e
3.5
& Grease
Ibs/day
9
Conductivity
V mhos /cm
range
11,000-
17,000
Cadmium
me /I
<0.05
comnosite
13,000
Chromium
mg/1 Ibs/day
2.6 12
Temp
Solids
"C TOC total
ran-^e mtj/1
28-30 12
Mercury
"ycTI
<0.l
Iba/dav me /I
55 8,930
Leadk/
me/1 Ibs/day
0.2 0.9
Ibs/dav
40,800
susp
me/1
71
Ibs/day
320
Copper
aifi/1
0.09
Ibs/day
0.4
a/ Analytical procedures are outlined In Appendix G.
b/ No Intcrferi-.nce from calcium detected.
CO
-------
29
November 1, 2t and 3t 1971, in order to resolve differences In vaate load a
that were measured between stations which should have given comparable
values. Of the possible reasons given for these differences in waste
loads, one was the contention by Company officials, that the discharge
from the VCM plant interfered with samples collected at GON-2. Hence,
during the second survey the effluent from the VCM plant (CON-1) was also
resanpled.
Effluent sampling commenced at 6:30 a.m., November 1. Aliquots
(125 ml) were composited every two hours for 24 hours, and continued for
48 hours, yielding two aeparate-daily-composited samples. Each of the
daily composite samples was mixed and then divided, with a portion given
to the Company and the remainder forwarded to EPA laboratories for analysis.
[Analytical results and field measurements of the second sampling program
are listed in Table 10.]
Waste loads discharged from the VCM plant indicated daily levels of
at least 1,350 Ibs TOC; 5,200 Ibs, COD; 140 Ibs, suspended solids; and
17 Ibs of oil and grease. The discharge level of carbonaceous material
is appreciably higher than levels measured during the first survey [Table 9],
DATA REPORTED TO LOUISIANA STREAM CONTROL COMMISSION
The Louisiana Stream Control Commission had no information on the
industrial discharge from the VCM plant.
PROPOSED WASTE TREATMENT
An extended aeration treatment facility is under construction and is
scheduled to be completed in November 1971. This new system will have 12
-------
TABLE 10
SUMMARY OF ANALYTICAL RESULTS AND FIELD MEASUREMENTS FROM
SECOND SAMPLING PROGRAM5'
Sea
COK-1^
CON-J-'
Flow
mc.d
0.19
0.25
PH
rani-.e
1.4-4.0
2.2-3.2
Conduct ivi ty
p mhos/cm
26,500-55,000
22,000-26,000
Temp
•c
rant>e
31-34
30-35
Solids
TOC
nm/l
850
740
Ibs/day
1,350
1,550
COD
me/1
3,300
2,800
Ibs/day
5,200
5,800
total
TOR/1 Ibs/dav
21,700 34,400
17.500 36,400
SUSP
mjj/1
90
80
Ibs/dav
140
170
Oil & Crease
ms/1
11
Ibs/dav
17
aj Analytical procedures are outlined in Appendix C.
b/ Composite sanple collected November 1 and 2.
cf Composite sample collected November 2 and 3.
U)
O
-------
31
days' retention at the present vastewater production rate. At the time of
the second sampling program during the first part of November, construction
of this facility had not been completed. Sludge handling facilities are
scheduled to be constructed in 1972.
A caustic recovery system, also under construction, was scheduled to
be in operation in August 1971. Chromate recovery is being considered and
will be constructed in 1973 if required by the Ctate.
Currently, sums of from $100,000 to $250,000 are programmed for an
activated carbon filter for tertiary treatment as part of this water pol-
lution control program.
The proposed new vastevater treatment facilities should provide
adequate reduction of the pollutant loads now being discharged except
for chromate.
CONCLUSIONS
1. Present discharge levels of carbonaceous materials and chromium,
by the Continental Oil Company's Lake Charles VCM plant, constitute a vio-
lation of Section 407, Rivers and Harbors Act of 1899 (33 USC: 401-413).
2. Additional treatment facilities are under construction. These
facilities should bring about further reduction of all pollutant loads
except chromium.
RECOMMENDATIONS
It is recommended that:
1. The Company be informed of the discharge of heavy metals (chromium)
to Bayou Verdlne, a tributary of a navigable stream, and that appropriate
-------
32
measures be taken to eliminate this discharge.
2. The Office of Enforcement, EPA, monitor progress toward comple-
tion of the facilities now under construction.
3. If the facilities now under construction are not operative by
December 31, 1971, appropriate abatement actions be initiated against
the Company.
4. If the facilities are in operation by December 31, 1971, the
nature of the discharge from the plant be reevaluated.
-------
33
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-(PL 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).
Zj U. S. Department of Commerce, Environmental Science Service
Administration Coast and Geodectic Survey, Atlantic Coast Sixth
(1967) Edition 163-165.
-------
APPENDIX A
APPLICABLE WATER QUALITY REGULATIONS
-------
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 from its
origin to the Salt Water Barrier; (2) Zone 2, the Calcasieu River from the
Salt Water Barrier to the upper end of Moss Lake; and (3) Zone 3, that
portion of the Calcasieu River from the upper end of Moss Lake to the Culf
of Mexico. Louisiana State Water Oualitv Standards for the Calces leu r.t"-r
-------
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.
-------
A-3
Temperature
Oil and Grease
Toxic Materials
Not to be raised more than 3°C above
normal 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
W10*
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 Co
5420/100 ml in any one month.
Other Materials Limits on other substances not hereto-
fore specified shall be in accordance
with recommendations sec 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 fron 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.
-------
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
No foaming or frothing
materials
Coliforms The monthly median for col i form density
shall not exceed 542/100 ml (MPN) 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.
-------
A-5
Specific criteria for this zone are as follows:
pH From 6.0 to 8.5
Dissolved Oxygen
Temperature
Oil and Grease
Toxic Materials
Not less than 60 percent saturation at
existing water temperature.
Not to be raised more than 3°C above
normal 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
a level shall not exceed a TLM
No foaming or frothing
materials
Coliforms
W10'
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 1399 (Refuse Act)
The Rivers and Harbors Act of 1699 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
-------
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 Ho. 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 enulsion to be
deposited beneath the surface of the water or upon adjoining
shorelines.
-------
APPENDIX B
CUSTODY OF SAMPLES
-------
B-l
APPENDIX B
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 C,
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 beine recorded on t'-o «??.-r!e
-------
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.
-------
APPENDIX C
BIOLOGICAL STUDY METHODS
FOR PALATAEILITY AND SURVIVAL
STUDIES
Lower Calcasieu River
Louisiana
(April 20-24, 1971)
-------
C-l
APPENDIX
STUDY METHODS
Common white, or lake, shrimp (Penaeus 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 Ik 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 cases, 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
AO°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 discharges.
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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 recoded 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=extrene "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 bosket
was tested for pll, temperature, and salinity.
Shrimp that survived the 96-hour exposure were tested for flavor in
the manner 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 jEor_ the Chemical Analysis of Water and
I/*
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 the exception that n-hexane was 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 Hn,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 HNO_ for metals analyses
and one liter was left untreated for total and suspended solids analyses.
Water and effluent samples specified for metals analyses were shipped,
* Numbers in _/ refer to listing in References.
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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)
3/
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 DPI-DC
personnel, according to procedures described in the FWQA Manual.—
These samples were tested for TOG 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 TOG were also analyzed
for COD. These determinations were made according to the procedure for
"high level COD," (i.e., digestion with 0.25N K^r^) . 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 volatiles 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-
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 development 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 Elmer Model 900 gas chromatograph. Conditions were
adjusted to obtain the best resolved chromatogram by using 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 RMU-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 Maker Pollution Control
Administration Manual for the Chemical Analysis of Water 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 Water and Wasteuater, 12th Ed., Amer.
Public Health Assn. New York, N.Y. 1965.
3. W. R. Hatch and W. L. Ott, Anal. Chem., 40. 2085 (1965).
4. D. G. Ballinger and G. D. McKee, J. Water Poll. Con. Fed. . 43 (2)
216 (1971).
5. J. R. Uthe, F. A. J. Armstrong and M. P. Stainton, J. Fisheries Pes.
Board of Canada, 2T_, No. 4, 805 (1970).
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