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.

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                                                                  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

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                                                                 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

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                                                                  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

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                                                        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

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                                                                  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

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                                                               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

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                                                                 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

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                                                                  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.

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                                                                 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

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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 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

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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.

-------
                                                                    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

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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 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.

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    APPENDIX B
CUSTODY OF SAMPLES

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                                                                    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

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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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         APPENDIX C
  BIOLOGICAL STUDY METHODS
FOR PALATAEILITY AND SURVIVAL
           STUDIES

    Lower Calcasieu River
          Louisiana
     (April 20-24, 1971)

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                                                                  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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