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 ------- 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 ------- 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 ------- 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 ------- 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 ------- 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 ------- 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 ------- 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 ------- Figure 1. Location Map • Calcasieu River Drainage ------- 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. ------- 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; ------- (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. ------- 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 ------- PETROCHEMICAL PLANT TREATMENT FACIL. Not To Scale Figure 2. Effluent Sampling Locations fnr Continental Oil Co VCM Plant, Petrochemical Plant, & Carbon Plant ------- 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; ------- 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 ------- 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. ------- 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. ------- 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. ------- 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 ?. ------- 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 ------- 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. ------- 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 ------- 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) ------- 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. ------- 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. ------- 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. ------- 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 ------- 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. ------- 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. ------- 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. ------- 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. ------- 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. ------- 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. ------- APPENDIX D ANALYTICAL PROCEDURES ------- 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. ------- 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. ------- 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 ------- 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. ------- 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). ------- |