Document OEEw3JoVLNbM0oMJwLdp9Jzb1

Charles L. Whautone, M. D. Assistant Madicjl Director July 7, 1977 (conoco) Continental Oil Company P. 0. Box 1267 Ponca City, Oklahoma 74601 (405) 762-3456 1/ Dr. Pierre Decoufle Environmental Epidemiology Branch National Cancer Institute Landow Building, A521 Bethesda, Maryland 20014 Dear Doctor Decoufle: After a number of unanticipated delays. Continental Medical Division has extracted the additional information you requested. At the time of your visit to Ponca City, Viola Smith, Conoco Personnel, supplied lists of present and past employees of the Baltimore plant. Medical Division has retained identical copies of the lists and it is from these that points of reference will be made. Shown below are the headings on each list so that the information can easily be correlated. 1. "Terminated Employees (have kardex)" - Out of a total of 111 names we were able to locate only eight (8) medical files. 2. ''1971-1976 Retirees" - Out of a total of 30 names, we have available thirteen (13) medical files. 3. "Still Employed" - Out of a possible 49 individuals we have all forty-nine (49) medical files available in our Medical Division. 4. "Terminated Employees (not having kardex)" - In searching our files, no medical records could be found on this group of employees. Altogether this makes a total of seventy (70) medical files available for your study through to 1960. These records are included. In order not to violate medical/legal ethics, a simple code system has been devised with each individual lab test and date shown, but the name is omitted. My knowledge of the stability and long service of employees at the Baltimore plant is consistent with the observations you made in your May 10, 1977, letter reporting your review of the employee history and mortality there. I agree that any study is best considered to be of petrochemical workers in general rather than benzene specifically. The potential for employee exposure to many other chemicals besides benzene has, as you know, always led me to believe that a simple cause and effect linkage between benzene in any abnormal VEU-221463 --2 health effect was scientifically unsound, unless great care to quantify the levels of benzene exposure and isolate them from other significant exposures, could be carefully accomplished. If we were to develop a simplistic benzene/health effect conclusion, it might divert our focus from real causes. Consequently, any future study should be approached objectively, with an open mind, so we can have fully as much effort di rected on analyzing cause as we do determining effect. This was the major point we were trying to make in the meeting we had with you prior to your initial efforts. At that meeting we presented a table of chemicals present in the plant over the years. We rated these according to their potential for hazardous expo sure based on a qualitative assessment of 5 criteria. (1) (2) (3) (4) (5) How the chemical is handled. The volume present in the plant. The physical properties of the chemical. The length of time it was present in the plant. The chemical's toxic properties. You will recall that it was on the basis of this table that you chose to limit the cohort of your initial study to between 1947 and 1960, because that tended to minimize the multiplicity of chemical exposure. Now you indicate you wish to include only those who were hired after 1947 and the present and future work force. This means that your cohort will include those who have had exposure to the many additional chemicals in the plant in recent years. To refresh your memory in this regard, here is the list of chemicals and the qualitative potential exposure we presented in our first meeting. POTENTIAL FOR HAZARDOUS EXPOSURE HIGH MEDIUM LOW Aluminum Chloride Toluene Nonene Hydrogen Chloride Xylene Naphthalene Benzene Eicosine Acetylene Chlorine Caustic Soda DiaIkylbenzene n-paraffins Dodecylbenzyl chloride Diphenylalkane Methyl cellosolve Dodecylbenzyltrimethyl ammonium chloride Calcium Carbide Formaldehyde Dodecylbenzene Thiourea Ammonia bis(chloromethyl) ether Tridecylbenzene n-chloroparaffins Sulfonated coker gas oi Sulphur dioxide/sulphur trioxide VEV-221464 --3 POTENTIAL FOR HAZARDOUS EXPOSURE (Continued) HIGH Isopropyl alcohol MEDIUM Dodecene LOW Mercury Trimethylamine Asphalt distillation product (Chevron) Carbon black Gasoline (Citco) Asbestos Tetraethyl lead (Citco) Sulfuric acid If we proceed with the study I believe we can help out by supplying the time intervals each of these chemicals were in the plant. Your letter implies a desire to extend the study beyond looking at mor tality, to include examination of our medical surveillance records to try to correlate these with benzene exposure. You note, for Instance, certain abnormalities that have not been previously associated with benzene. The more valuable approach of this work may be to tie those abnormalities to chemicals where they have been noticed before, as the measure of the effect of that chemical on the work force. In summary, I think the study should go forward provided: (1) (2) (3) The same care is used to analyze the causative chemical as is used to determine the health effect. That conclusions be drawn in the best spirit of scientific objectivity. That all information regarding the study be made available to Conoco Chemicals to help us manage the Baltimore plant consistent with ample regard for the health of our employees. Charles L. Whetstone, M.D. Assistant Medical Director Attachments cc: Mr. Dave Kuhn - Houston (attachments not included) bjc VEV-221465 *l/ National Cancer Institute Landow Building, A521 Bethesda, Maryland 20014 Dear Doctor Decoufla; Your letter of December 21, 1976, requesting Conoco undertake an epidemiology study at the Baltimore Chemical plant has bean reviewed by Management. Chemicals Division has responded favorably to your request and asked Medical Division to notify your office of this de cision. Even though Chemicals proposes a willingness to cooperate fully with the National Cancer Institute, we would be remiss in not pointing out certain potential problem areas which might dilute the anticipated impact you wish to derive from such an epidemiology study* You should be well briefed on the history of the plant; l.e. how it evolved at one time from a refinery to the present day petrochemical plant, and that older employees or retirees will have had exposures to bi or end product interim compounds* We are concerned that this plant will not provide as pure an exposure to benzene that you seek because of the presence of significant amounts of many other chemicals that have gone heretofore* Accordingly, I think it appropriate that designated key officials from Conoco and NCI at some suitable time have a session to evaluate these variables and conduct a briefing as to how you propose to undertake this study* + We look forward to meeting with you and your staff* Sincerely, Charles L Whetstone, M*D. Assistant Medical Director bje vv 4 VEY-221466 Conoco Ctomicats Company Conoco Inc. P.0 Box2^97 Houston. TX 77001 September 10, 1980 Dr. Pierre Decoufle School of Health Related Professions Health Sciences Center University of Arizona 1535 North Freemont Tuscon, Arizona 85719 Dear Dr. Decoufle: Enclosed is the plant process information we have discussed. I trust this is detailed enough to satisfy your needs. As you are aware, it was difficult to obtain information on the plant prior to 1947, when it was a refinery. I have also enclosed a history of the refinery with my summary description. It is our understanding that we will review the report in draft form before publication, to assure the accuracy of information as it relates to plant operations, as well as other aspects of the study. Please let us know when this can be done. If further information is needed at this time, please feel free to call. - Sincerely, Thomas 6. Grumbles Director, Industrial Hygiene cc: Dr. Whetstone Virginia Moore R.E. Lehmkuhl VEV-221467 CHRONOLOGICAL HISTORY OF BALTIMORE PLANT 1915 1929 1947 1949 1954 1955 1960 1961 1964 1964 1964 1965 196B 1971 1972 1973 Refinery built by Prudential Refining Co. Refinery purchased by Marl and Oil Cc^.* Refinery converted to Chemical Plant to make detergent alkylene. Began producing "Neolene". Hydrotrope (STXS) unit start-up. DoDecyl Benzyl Chloride (DBCL) unit start-up. "ADOQUAT" production started. Calcium Intermediate Unit start-up. Main product switched from Neolene to Nalkylene. Trainer Feed Stock production started. Bollestra Unit start-up. A-390 production started. Adoquat production stopped. DBCL production stopped. Calcium Intermediate plant shut-down. Baltimore Base Oil (BBO) production started. * Marland Oil Co. merged with Continental Oil in Tate 1929. Exposure Potential - Chemical Plant NEOLENE/NALKYLANE PRODUCTION (1950 - PRESENT) The major process at the Baltimore plant has been the production of / detergent Alkylates. This is a continuous process utilizing benzene, paraffins and chlorine. Muriatic Acid and aqueous aluminum chloride are produced as by-products. Basically, paraffins are received and fractionated into specified cuts. Chlorine is vaporized with steam and reacted with the paraffin cuts. The chloroparaffin is then sent to an alkylation reactor where it is reacted with benzene. This is a conventional aluminum chloride Friedel-Krafts Reaction. HYDROTROPE (STXS) UNIT (1954 - PRESENT) This unit consists of a small batch reactor that produces sodium toluene, sylene sulfonates and anmonium sylene sulfonate. These materials are hydrotropes, used as detergent additives. The process involves reacting xylene or toluene with 99% H2SO4 in the presence of heat to produce sulfonic acid. This product is then neutralized with caustic solution and dilute aqueous ammonia. *v DODECYL BENZYL CHLORIDE (DBLC) UNIT (1955 - 1971) This is a batch operation involving two reaction steps in a stirred pot reactor. The initial step involves the reaction of paraformaldehyde, methanol and phosphorus tirchloride to form methyl chloromethyl ether (MCME). MCME was then reacted with Neolene/Nalkylene (alkylate) in the presence of concentrated sulfuric acid to produce DBCL. Bis-chloromethyl ether (BCME) is an intermediate reaction product in this process. "ADOQUAT" was produced in the same vessel as DBCL. "ADOQUAT" is manu factured by reacting DBCL with an aqueous solution of trimethylamine in the presence of aqueous 2-propanol and heat. The product is used as an inhibitor of bacterial growth and corrosion in secondary oil recovery and water injection systems. VEM-221469 CALCIUM INTERMEDIATE UNIT (1961 - 1972) This is a continuous process utilizing calcium carbide, methyl cellosolve ( (2-methoxyethanol) and carbon dioxide in a two step reaction to produce calcium % intermediate (calcium ethylene glycol monomethyl ether mono carbonate). Calcium / Intermediate is the neutralizing and overbasing agent used in producing calcium sulfonate from heavy alkylbenzene sulfonic acid. Calcium carbide and methyl cellosolve are reacted and Acetylene is formed as by-product. This reaction product is mixed with carbon dioxide to form the Calcium Intermediate product. TRAINER FEED STOCK UNIT (1964 - 1978) This unit produced several different products including A-390 Baltimore Base Oil (BBO), and H-380 (trainer feedstock). This unit produced high molecular weight defergent alkylates from Olefins and Benzene for conversion into oil. T soluble sulfonates. The process involves the dimerization of dodecene, a Friedel-Crafts alkylation of benzene using powdered Aluminum Chloride and a distillation of the reaction products. BOLLESTRA PLANT (1954. - 1966) This was basically a sulfonation unit. Bulfur-was burned to produce SO2 which was then converted to SO3 in a catalytic reactor. The SO3 gas is then reacted with alkylate (Neolene) to form sulfonic acids. The sulfonic acid is then neutralized with caustic. C VEU-221470 Refinery Process Information Enclosed is a history of the Baltimore Plant from 197*5 until it's conversion to a chemical plant in 1947. This history puts emphasis only on the type and capacity of equipment or processring units at the Refinery. However, in knowing this and the products produced, some estimates of exposure potential can be made. The Plant produced a full line of refinery products that included light oils, bunker, lube oils and wax. It appears no petrochemical, operations (aromatic extraction, ethylene production, etc.) were done. Knowing this, exposures of concern would be those encountered in any refinery producing similar products. Acid gases (H2S, SO2), aromatics (benzene, toluene, xylene), gasoline additives (TEL, dyes, etc.) and PNA's associated with asphalt production were present. The degree of exposure to these chemicals is difficult to estimate without knowledge of the refinery operations. The aromatics were present only as stream constituents and exposure to them could be estimated as low to moderate on an 8-hour basis. Without knowing more about what crude the plant processed the exposures to SO2 and H2S are hard to estimate also. However, they would probably be in the.same range of low to moderate. Exposures to the gasoline additives were intermittent, and the PNA exposures were most likely very low. VEV-221471 The Baltimore Plant The Baltimore Plant ves born In 1915 when the Prudential Oil Company began construction of an 11,000 barrel refinery; addi / tional equipment was added in 1920 and 1921 to increase the capa city of the plant by 501 when running light Mexican crude to coke. The original plot consisted of 150 acres with over twelve hundred feet of vater front property. The dock is connected by an eighteen hundred foot channel, 35 feet deep, with the42 foot deep Port McHenry channel which connects the Chesapeake Hay with the Port of Baltimore. In 1921 five additional 55,000 barrel tanks were added. In 1922 three 80,000 barrel tanks, and In 1923 four Dubbs'cracking units with necessary equipment including ten, 30,000 barrel tanks, and six additional 80,000 barrel tanks were added. Hot oil pumps and recirculating flue gas systems were added In 1925 to two of the Dubbs cracking stills. During this period we produced a full line of refinery products that included light oils, bunker, lube oils, and vex. YEV-221472 The plane had three distinct vaeer systems, one supplying river water for plant operations, the second supplying well water for plant operations, and the third wee river water for fire protection. These river water systems were effective enough normally, hut occ asionally we had to shut down to remove the fiah and crabs that had elipped through the strainers. In addition to the water and truck facilities, Prudential Oil Company maintained a fleet of 400 tank cars with a, combined capa city of 77,000 barrala. The Major share of crude oil was shipped by tanker from Mexico and California. Ve also had four asphalt converters (12% x 35% feme each), end all were connected to one nnmon 80 foot radial brick stack. v m The converters were elevated so that the contents eould gravitate into tank cars or druse. The converters were fired by gas from the main gas system. The main distillation unit consisted of four (14* x 40 foot) end-fired reducing stills. YEV-221473 Eighteen (14 x 40 foot) side-fired coke stills built in pairs, each pair equipped with one 60 foot stack., Each still was equipped with one tower, 4 ye also bad two (14 x 40 foot) side-fired lube stills. These twenty-four stills and two topping plants were served by two receiving bouses that were equipped with look boxes and manifolds so that complete frsetioas could be cut to any one of the seventeen (35 x 12 foot) run-down tanks. , We bed four (six cubic foot) Connersville Gas Exhausters that pulled gas from the stills thru two cast iron scrubbers and discharged to burners throughout the refinery. The lines also connected to one 250,000 cubtc foot and one 500,000 cubic foot gas holders for storage of surplus ga\s and holding ranks for trans- .* fert to the Baltimore Gas and Zleetric Company who distributed it to hones and industry throughout the City. Interest in an East Coast outlet prompted Mar land Oil Company to purchase Prudential in 1929. Baltimore employee# became members of the Conoco family later that year when the merger between Continental and Marland was completed. VEV-221474 Since Chat else we, along with the other Conocoaxu have sees secy, stay changes* One of Che biggest in Che eyes of the Baltimore employees was the conversion from the refinery to a petrochemical plant* In 1946 tha refinery vat shut down and converted into Continental Oil Company's first petrochemical plant. UEV-221475 laitital work on the production of dodeeylbexasene vsa begun early in June 1949 in the Baltimore Sale* Service Laboratory, The object we* to determine if * product eould be produced that y would be comparable to Orcm.ite Chemical Company's "AITrine" using benzene and Continental Oil Company* * dodecene. This alkylation was to be catalyzed by anhydrous aluminum chloride. Toe initial laboratory work proved that a dodecylbeasene alkylate comparable to Alkane could be produced by using aluminum chloride as the catalyst (AD-LIB reasons for Alkane! i,e. H? catalyst, bottoms no good for Trainer and Oronlte'* patents, etc.). The procedure v&s very similar to the procedure used to produce dodecyltoluene in the plant. VEV-221476