Document b6jNEo4QKrxM3M9NdR6Eg1v3

FILE NAME: Exxon (EXX) DATE: 1949 DOC#: EXX006 DOCUMENT DESCRIPTION: Internal Report - Industrial Hygiene Survey Baton Rouge Refinery CONFIDENTIAL - CSS-U INDUSTRIAL HYGIENE FOUNDATION OF AMERICA, In c . 4400 FIFTH AVENUE PITTSBURGH. PA INDUSTRIAL HYGIENE SURVEY of the Baton Rouge Refinery LOUISIANA DIVISION ESSO STANDARD OIL COMPANY Baton Rouge, La. February - April. 1949 E MO 0160 5 tw tv k t o t t. JHTCTErcg FOOSDSZQE CP AMEBICA, JSC. 42(00 Firth Avenue Pittsburgh. 13, Pa TNniK TOTAL ffTHTENE SIEVE! QF TOT BATCH BOUGE BZnJEBI LOUIBIAIIA DIVISICJI ESSO STAHDABD O U COMPAS! FZSRUABX, MABCS, AHD APSIL, 194-9 by Janea F. Morgan W. C. L. Henean Industrial Hygiene Foundation of Aoeerioa, In By Date Submitted :M A R # !3 IQXn ~r~ / John F. McMahon Managing Director EHO 01606 TABLE OF c o n t e n t s IE THODDCTIOS .................................... s U KMART ......................................... PROCESS W O R K E R S ...................................... 1 CHEMICAL PRODUCTS DIVISION .................................. CRACKING DEPARTMENT ...................................... Peraeril Plant............................................. Steam Cracfcing Plants, No.1 and No. 2 ................ Butadiene Extraction Plants ........................... ' Isobutylene Extraction Units Nos. 1, 2, and 3 ......... Diolefin Extraction Unit .............................. BUTTL RUBBER UNITS ....................................... Materials and Process ................................. , Exposures ............................................. ALCOHOL PLANTS ............................................... Accident Hazard............................................ Blending Agents................. .......................... Carcinogenic Problem....................................... CATALTST PLANT ........................................... Toxicity of Some Chemicals Used in the Catalyst Plant .. ' PETROLEUM PRODUCTS DIVISION ................................. REFINING AND OIL MOVEMENT ................................ Distillation .......................................... No. 2 D. & S. and Hydrogen Sulfide Recovery Unit ...... Oil Movement .......................................... LUBRICATING AND PARAFFIN DEPARTMENT ..................... Wax Presses ........................................... ! Plate Shop ............................................. : Refrigeration Unit .................................... Crude Scale Wax Sweaters .............................. Refined Wax Sweating .................................. Propane De-waxing, Propane De-oiling, and Propane De-asphalting .................... . MEE Plant ............................................. Wax Filtering ......................................... . Lube Filter Plant ..................................... I Phenol Plant .......................................... l Lube Oil Treating ..................................... [ Lube Oil Blending ..................................... / Grease Manufacture ..................................... f Inhalation of Mists ................................... | Inhalation of Bust ..................................... f Shin Contact .......................................... . CRACKING DEPARTMENT ...................................... t Thermal CradH^g ......................................... | 1,000-pound Coils: No. 21 and No. 22Units ...... ....... | 750-pound Coils: No. 19 and No. 20Units ............... i Conclusions RegardingExposures ofMen .................. " Steam Craefe^wg ........................................... Process ............................................... Catalytic Cracking ....................................... " Materials and Process .................................. Significant Exposures .................................. EPO 01607 Pases i . ii-xiv 1-50 1-18 1-5 1-3 3-1* L-5 5 5 6-7 6 7-11 11-12 11 11 12-15 15-18 15-18 19-50 19-21 19-20 20-21 21-23 2^38 2^-27 27-28 28 28 28 29 29-52 32 ^3 3i*-35 36 36-37 37 37 38 58-39 UO-^7 hO--L-3 1*0-1*2 1*2-1*3 1*3 1*1* 1*1*-1*5 1*5-^7 1*5 1*5-L" TA'BT,? CF COM'iaSMTS (Continued) UTILITIES AHD LIGHT ENDS ................................. Light Ends ......... Petroleum Vapor ....................................... Hydrogen Sulfide ...................................... Acid Recovery Plants .................................. Boiler Houses and Power Houses ........................ MAINTEHAHCE AHD COBSTRUCTION ...... PIPE DIVISION .................................................. Catalytic Cracking Units .............................. Alkylation Units .... ................... ............. War Manufacture ....................................... Phenol Plants ............................ ............ Barisol Plant ......................................... Lube Treating Area .............. ..................... Alcohol Plants ........................................ M. & C. Machinists ....................................... Outside Machinists .................................... MEK Plant ................. ........................... Phenol Treating Units ............ .................... Paraffin War Presses .................................. Butyl Rubber Reactors *nd Finishing Building .......... Paraeril Plant ........ ........................ ....... Gas Compressors ..................................... .. Contact with Heavy Catalytic Cycle Gas Oil and OLA Tars .. Machine Shoo ............................................. Main Shop .......... .................................. Disassembly and Reassembly Shop . ...................... Metal Spraying ........................................ BOILERMAKER DIVISION ........................................ Riggers ............................................... Welders and Burners .................................... Pipe Shop, Chemical ProductsDivision .................. Boilermaker Shoo. "Old BoilerShop." .................. Welders at Catalytic CrackingUnitTurnaround ........... Lead Burners ....... Lead Burner Shop at Ho. 3 Acid Plant .................. Lead Burning Shop in Crafts Building in Chemical Products Area ........... Outside Lead Burning and Bonding ...................... Medical Control Measures ....... ...................... Utility of Lead Urinalysis ............................ MEIER AHD INSTRUMENT DIVISION ....... ....................... Shops ..... Outside Men ........................................... Shift Men ............................................. ELECTRICAL DIVISION ......................................... Line Gang .................. .......................... Electricians Assigned to Process Units, Laboratories,and Offices ......... Main Electrical Shop ............ Pages W-50 W-50 U8-&9 1*9 1*9 50 51-85 51-59 52-53 53 53 53 51* 51* 51* 55-58 55 55-56 56 56-57 57 57 57-58 58 58-59 58 58-59 59 60-67 60 60-63 63-61* 61*-65 65-66 56-65 66 66 66 67 67-69 70-72 70-71 71-72 72 75-75 73 73 7^-75 EMO 0160 8 TABLE or contents (Coat limed) Skin Contact with Suspected Carcinogens ............... Underground Lead Work ................................. Occurrence of nitrogen Oxides ......... ............... MASON DIVISION .............................................. Masons ............................................... Concrete and Sandblast ......... Brick and Asbestos Grinding .......................... Insulators ............................................ GENERAL LABOR .............................................. Refinery Disposal Dump ............................... Ethyl Lead Tanks Cleaning ............................ Exposure to Powder Catalyst Dust. , Cleaning Reactor Chamber (PCLA) ... Cleaning Bubble Towers ............................... Cleaning Reactors, Light Ends Plant ................... Tank Cleaning ......................................... Tube and Soaker Cleaning ............................. Cleaning Soaking Drums at Thermal Cracking Units ...... Dismantling Condenser Boxes ........................... Exposures to Heayy Aromatics .......................... CARPENTER AND PAINTER DIVISION .............................. Paint Shop ............................................ Painters .............................................. M I S C E L L A N E OUS ...................................... LABORATORIES ................................................ Refinery Laboratory ...................................... Aniline ............................................... Mercury Vapor ......................................... PRINTING STANDARDS .......................................... Materials Handled ..................................... Ventilation ........................................... ASPHALT PLANT ............................................... A P PEND I Z ................................................ PREVENTION OF EZPOSUEE TO HIGE BOILING AROMATICS ............ BENZOL EXPOSURES ............................................ Pages 75 75 75 76-79 76-77 77-78 79 79 80-3L 80 80 80-8l 81 8l-82 82 82 83 3-8^ 81 85 65 85 86-91 86*88 86-88 86 86-88 89-90 89 89-90 91 92-95 92-9^ 95 i TTgm nv v&Trrrs Table I. Table H . Table m . Table IV. Table V. Table 1. Table 2. Table 3* Table 4. Table 5 Table 6. Table 7. Table 8. Table 9 Table 10. Table 11. Table 12. Table 13. Table 14. Poses Hazardous Exposures to Materials of Known Toxicity . Exposures to Hazardous Materials Judged to be Within Safe H a l t s ........................ Exposures Classified as Suspicious But About Which Exposure "and/or Toxicity Data ere Incomplete .. Exposures of Lo* Intensity to Materials of a Lov ' Order of Toxicity ......................... Secoggnendations far Mechanical Improvement of Conditions ................................ iv v-vi vii-x xi-xii xiil-xiT Dust Concentration-- Talc Dust in Butyl Buhber Pinishlng Building ........................ Chemicals and Other Eav Materials Used at Catalyst Plant During last Fire Tears ..... Petroleum Vapor Measurements in Ho. 16 and Ho. 17 Battery Still Houses ............... Oil Droplet Counts-- Peraffin Press Building ...... Measurement of Solvent Vapor in MEK Plant ...... Results of Urine Sulfate Batio Measurement for MEK Plant Markers ........ ................ Dust Counts at Lube Filter Plant ............... Rienol Measurements ................. .......... Concentration of Oil Mist in Vicinity of Pusps at Thermal Cracking Unit ......... Concentration of Oil Mist in Vicinity of Puzps at Thermal Cracking Unit ......... Results of Determinations In Urine of Lead Burners and Helpers ............... Mercury Vapor Measurements-- Meter and Instrument Shops ................... ................. Dust Concentrations in Vicinity of SandblastShed .. Mer cury Vapor Determinations-- Laboratories ..... 10 16 19 26 JO 31 33 35 4o 43 67 71 78 88 E PQ 01610 INDUSTRIAL ETCH U E SURVET MADE FOR ESSO STANDARD O H COMPANT BATON ROUGE, LOUISIANA FEBHUAHT 23 - APRIL 20, 19^9 ' Arrangements for this survey were made in 19**8 through the office of Dr. R. C. Page, General Medical Director, Standard Oil Company (N.J.). It is a part of a larger study which will include four plants of the Esso Standard Oil Company, Sarnia Refinery of Imperial Oil Limited, and the Aruba Refinery of Lago Oil and Transport Company. Field work at all the plants will have been complet ed before the submission of this report. The field vork at Baton Rouge embraced the period February 23 to April 20, 19^9- Mr. J. F. Morgan was present at the refinery for the entire period of the work, Mr. W. C. L. Henson spent two weeks at the refinery, and Mr. George F. Haines, Jr., of the Foundation staff, assist ed during a period of two weeks. Persons in Standard Oil Company (N.J.) directly concerned with the work are Dr. Joseph P. Holt and Mr. N. V. Hendricks; in the Esso Standard Oil Company headquarters, Dr. John S. Denholm and Dr. Clyde M. Berry. At Baton Rouge, the official contact was Dr. Howard Hansen. During the course of the survey, close association was established with Mr. E. Stauvennan, Jr., Mr. Roy E. Brady, and Mr. Stanley Day, of the Safety Department. The important conclusions of the survey are highlighted in the "Summary" section of the ensuing pages. E HO 01611 ii. SUMMARY There are four principal classes of materials of significance in the present considerations. (1) Materials which are known from experience to cause slowly develop ing toxic effects when workers 'are chronically exposed to atmospheric concentra tions above certain levels, as lead dust, silica dust, benzol vapor, and the like. The severity of exposure to this class In conventional manufacturing processes in factory buildings can usually be appraised quantitatively by analysis of the workroom air. Situations in the oil refinery where this could be done were few. (2) Materials whose primary action is acute poisoning from short-time exposures. The acute poisoning may be effected by a single exposure incident. They usually have no chronic effects at lower concentrations. Carbon monoxide is an example. Asphyxiant or narcotic concentrations of carbon dioxide and aliphatic hydrocarbon vapors are in this category. (3) Materials, as acid gases, which are irritating to breathe, re pulsive, and hence, obvious in their presence; therefore, these warning proper ties tend to discourage exposures to injurious concentrations, except as they occur in accidents. ( M Materials as PER, C^, and related aromatics which, because of their physical or chemical relationship to classes of known physiologically active materials, may be suspected of haying deleterious health effects but about which there is no evidence from human exposures to permit of their accurate classification. In the following tables, exposures of refinery employees to materials which are classified above are separated according to the evaluation arrived EM001612 ill. at 1b the course of the survey. Table X sumsnrizes the exposwes where it was -ossible to conclude that a definite health hazard existed. . Table H summarizes potential exposures to substances definitely taown to be hamful, but where our observations indicated the intensity of exposure to be within safe limits. Table H I describes the largest and most isartant class of exposures where there is no'experience to guide one to any definite conclusion, but wherein by inference (necessarily somewhat tenuous), we are led to suspect the possibility of hazardous conditions. In these cases, medical supervision of workers is indicated, so that by means of periodic examination of special design, any incipient health effects will be detected before widespread development occurs. We have included in Table H I the already recognized potential car cinogen hazards in exposures to the high boiling cut from catalytic cranking, wax pressing, OLA tars, and untaovn substances from alcohol manufacture. Hot heretofore recognized is the possibility of oil mist inhalation in various localities. Some measurements of oil droplet concentrations in atmospheric suspension have been in various locations. Table IV summarizes exposures to materials which are conservatively estimated to be innocuous or of negligible toxicity at the levels of concen tration encountered in practice. Table V summarizes recommendations fear mechanical improvement of con ditions in several locations. In general, and to the credit of the executive attitude at this refinery toward safety and health, many of the hazards discussed in this report had already been recognized. Corrective measures have been instituted widely. E '"'001 613 iv. Table I h a z a r d o u s e x p o s u r e s to m a t e r i a l s o f Know t o x i c i t y Operation or Location Substances or Conditions Employee Group Affected Paracril Plant Catalyst Plant Sandblast Sheds Pipe Shop in Chemical Pro ducts Division Srici grinding Shed. Acrylonitrile-- by inhalation in vicinity of latex and coagulation pots. Chromic oxide, various other rsv materials and products-- by inhala tion and skin contact. Silica dust-- by inhalation. Metal fumes have produced symptoms of metal fume fever. Silica dust enters shed from sandblast. One or tvo process men. The 13 catalyst plant vorkers. Sandblaster helpers Boilermakers, velders, and burners. One man of Mason Department. EM00161 U V. Table II EXPOSURES TO HAZARDOUS MATERIALS JUDGED TO BE WITHER SAFE LIMITS Operation or Location Substances or Conditions Butyl Rubber Butyl Rubber 'Finishing Building Butyl Rubber Reactors Alcohol Plant Anti-freeze production in Alcohol Area. Paracril Plant Methyl chloride in vicinity of reactors and in finishing building Safe usage 'by reason of process control, ventilation, and dally air analysis. Talc dust at packaging. AluginuB chloride exposure is controlled by wearing respirators. Inhalation of acetaldehyde is at present prevented by use of respirators. Methyl alcohol exposures are con trolled by informed personnel and natural ventilation. Acrylonitrile-- in control rooms and in finishing building beyond coagulation pots. Light Oil Treating Plant Shell Still Batteries No. 16 and No. 17. Ho. 2 D. 4 S., Hydrogen Sulfide Recovery Unit Tetra Ethyl Lead Blending Plant Lead-- mist at ground level from aeration in doctor regeneration. Hydrogen sulfide exposures slight in receiving houses. Leakage of hydrogen sulfide is effectively prevented in the process equipment. Tetra ethyl lead-- satisfactory control measures are practiced. Gasoline anti-oxidants-- skin contact is unlikely in present mode of handling. Process and mech anical workers in these areas. Packers Process workers in the reactor area. A few procesB work' ers in alcohol denaturing. Process workers and pipe-fitters assigned to the area. Machinists, pro cess workers, except attendants at latex and co agulation pots. Process workers at ground level. Still operators and helpers at the units. Blending plant em ployees, machinists pipefitters, and laborers. EH001615 vi. Table H (Continued) Operation or Location Substances or Conditions Employee Group Affected Wax Presses-- Plate Repair Shop Method of removing suspecte<i carcino genic material from plates before re pair acts to prevent a n contact. Plate shop personnel Wax Presses-- Re- .Paraffin Distillate, Foots Oli frigeration Unit no important exposures occnr. Grease Manu f*acturing Plant Dust of dry grease Ingredients. Hot significant by reason of low toxicity or Infrequent occurence of exposures. Process workers Light Ends Plant and Gas Conpressor Houses Hydrogen sulfide is generally not a chronic toxic hazard at those places where it occurs In the process stress because of the degree of confinement ma the ventilation of such places. Machine Shop Metal spray and nitrogen oxides, safe by reason of infrequent use of toxic metals "ri outdoor location. Lead Melting Pot (portable) Trm-tgn^fleurit, exposure by reason of low frequency. General, at Process Units Mercury, with reference to akin contact with liquid. Underground Lead- Lead fuses. Infrequent occasion sheathed conduits for fuse evolution. Machinists 1 Boilermaker helper. M. & I. workers Electricians General, In fur naces of process units end boiler houses. Silica dust in furnace breakdown and repair. . Masons, Laborers Underground Pipes Heavy aromatica boiling above 700*?, vfaere digging is skin contact. required to locate leaks. Barges, repair of Lead fumea from welding. Laborers-- exposures are fairly well eliminated by pre sent control * practices. Welders Tanks in Tetra Tetra Ethyl Lead and residues. Ethyl Lead Service Refinery Lab. Aniline. Mercury vapor. Printing Standards Volatile solvents and process liquids. laborers Lab. personnel Machine operators E*001616 Table III EXPOSURES CLASSIFIED AS SUSPICIOUS BUT ABOUT WHICH EXPOSURE a n d /or TOXICm DATA a r e INCOMPLETE OR RON-e x i s t e n t . MEDICAL SUPERVISION INDICATED. . Operation or Location Substances or Conditions Employee Group Affected Nature of Possible Effects Paracril Plant Chemical Pro ducts -- Steam Cracking Diolefin Ex traction Unit Butyl Rubber Finishing Building Iso-propyl alcohol plants Flare Stack at No. 2 D . L S. Light Oil Treating Plant Acrylonitrile, in sampling at reactors. !Process men Unknown Benzol in aromatic distillate. Process workers at OLA-1 and OLA-2. Upset of urine sulfate ratio in simple exposure cases; blood changes in cases of intoxication. Aromatic tars in Bottoms fractions, skin contact questionable. Procesa workers; pipefitters as signed to the area. Cancer (?) Benzol in aromatic Procesa workers distillate. Gee above descrip tion for benzol. Sublimation of (IP3N j About one-half of Bladder tumors are from ertruders t=-- * the workers in the caused by finishing building. /S-naphthyl amine. Skin contact or inhalation of suspected carcino genic agents of unknown composi tion may occur. Procesa workers and pipefitters in the iao-propyl alcohol plants. Cancer (?) Exposures to hy drogen sulfide from the base of the stack are un certain by reason of variableness of output, vlnds, and vork habits. Procesa workers at new light ends plant and mechan ical workers called occasionally to this area. Irritation of eyes and respiratory tract. Litharge-- possible exposures at ground level to mist from aeration. Procesa workers of the treating plant. Increased lead in urine and blood after exposure. iii. Operation or Location Table IU (Continued.) Substances or Conditians Employee Group Affected Hature of Possible Effects Wax Freeses Wax, Paraffine Distillate, Foots-* Oil, Pressed Oil-- as liquid or In the form at mists. Lube and Paraffine employees, machine ista, and pipefit ters assigned to this area. Cancer (?) Wax Presses-- Refrigeration Unit Paraffine Distil late, a suspected carcinogen. Machinists pipefitters in repairing coolers. Cancer(?) Crude Scale Wax Sweaters Crude scale wax and oil, possibly carcinogenic, de pending on prior treatment of the stock. Pipefitters. Cancer(?) Solvent de-waxing (MEE) Plant Vapor of benzol, occurs in low con centrations In working areas. Process workers, machinists nd pipefitters as signed to the unit. Upset of urine sulfate ratio In simple exposure ' eases; blood changes In eases of intoxication. Grease Manufac turing Plant Inhalation af mists and akin contact with grease Ingredients and products. Grease Plant employees. Unknown Lube Oil 'Treating Sulfur dioxide or sulfuric acid mist. The problem of Irritation may be critical In employees In agitator area having unusual pre-dispos ition. Abnormal tooth decay; upper re spiratory Irritation. Phenol Treating Plants Phenol vapor Workers at Phenol Plant, especially sample takers and pipefitters. Unknown ; Thermal Cracking 1 Units Oil mist and vapor, including clarified oil from catalytic 1 cracking. Sample takers and other process people, pipe fitters assigned to the 'units. Cancer (?) EMO 0161? lx Operation or Location Table HI (Continued) Substances or Conditions 'Employee Group ' Affected Nature of Possible Effects Steam Cracking Aromatic distillate Sample takers and Iht same signs of Units in Petro because of benzol other process exposure and in leum Products content. . % people, pipefitters toxication. outlined assigned to the for benzol units. previously. Aromatic tars and clarified oil from catalytic cracking. Cancer (?) Catalytic Clarified Oil and Process people and Cancer (?) Cracking Units slurry oil when mechanical crafts encountered either assigned to these as liquid or as units, especially mist at hot oil pipefitters. pumps. Silica-alumina catalyst-- dust inhalation, also entry into eyes. Significant for pipefitters, welders, masons, and laborers. Eye irritation;lung abnormal1ties (?) Power and Boiler Houses Noise Full-time employ ees of these places. Impairment of hearing Barisol Plant Carbon tetrachlor ide, ethylene dichloride. Former proceas workers and pipe fitters and machinists former ly assigned here. Liver abnormalities Machine Shop. Disassembly to re-asaembly Shop Pipe Shop in Petroleum Pro ducts Division Aromatic tars and oils boiling above 7 0 0 % spilled from undrained equipment and ac cumulating an the ground. Machinists. Lead fumes may be encountered in future work on bonded lead pipe. Boilermakers, welders, and burners. Cancer (?) Increased lead in urine and blood as evidence of exposure. H0 01619 x. Table ITT (Continued) Operation or Location Substances or Conditions Employee Group Affected Nature of Possible Effects Lead Burners Shops at No. 3 A d d Plant and In Chemical Products Area Lead fumes, espec- Lead burners and ially from bonding. helpers. Main Electric Shop Varsol and Zyienes Shop electricians General, through out refinery Solvent vapors from cements for Insulating materials. Insulators. Disposal Dump Oil smoke, fumes, and mist. (Heavy aromatic wastes) Laborers Bubble Towers throughout refinery Hydrocarbons from Laborers gas oil to heavy tar. Skin contact. Tube Cleaning, general Coke dust Laborers Vertical Soaking Drums at thermal Cracking Units Skin contact with tar and coke from thermal cracking. Laborers Condenser Boxes at Thermal Cracking Units Skin contact with tar. Laborers Paint Shop Inhalation of ben zol in nae of paint remover. Frequency is unknown. Painters General Benzol occurring in other paint products. Asphalt Processing Mists and vapors Painters Asphalt workers Increased lead in urine and blood as evidence of ex posure. Irritation of eyes end nose, nervous and digestive dis orders. Cancer (?) Skin effects. Cancer (?) Respiratory disorders Skin effects. Cancer (?) Skin effects. Cancer (?) Upset urine sulfate ratio in simple exposure cases. Upset urine sulfate ratio In simple exposure cases. Cancer (?) E H O0162 0 EZP0S3ES OP LOW im 'KNSPvr TO MAIffilAIS OF A LOW ORBES OP TCDOEC1T? Operation or Location Substances or Conditions Eaployee Group Af-'ected Faracrll Plant Butadiene taper Process and Butadiene Srtracn tlon Holt < Isoprene Ertraction Unit Mono- and dl-olefins Butylenes Diolefin Extrac tion Unit Acetone Butyl Bubber Plants Zinc sulfate, stearic acid, and zinc stearate. Alcohol Plants Hydrocarbon feed stocks and lowmolecular veight products and by-products. Light Oil Treating Plant Petro Green D Dye. Tetra Ethyl Lead Blending Plant Perroleus dyes Propane de-vaang, dopane de-olling, de-asphaltlng. Wax Pllter Plant Bauxite Lube Pllter Building Dust of Attapulgus clay. Specialty Stills (1929 Plant) Petroleum vapors Generally, throughout refinery. Welding fumes Generally, throughout refinery. Fmes from burning coke deposita. Good ventilation is provided. Process and mechanical. Process workers in reactor group. Process and m*chr\ical. Treating Plant porters. Blending Plant workers. Welders and burners Welders EMO 01621 r Operation or Location Catalytic Cracking Sait TABLE 17 (Coxrtlaaed) Substances or Conditions Asbestos * M. it I. Shops UOP Poly Plant Railroad Car Unloading Bricklaying sites Varsol vapor El Sil Dust Brick Dust Brick Dust xU Employee Group Affected Placed in t M i table with reference to exposures at turnaround for welders, masons, laborers. Laborers Laborers Masons E PO 01622 zi Table 7 RECOMMENDATIONS FOR MECHANICAL IMPROVEMENT OF CONDITIONS Operation or Location Substances or Conditions Remarks Type of Mechanical Remedy Applicable Paracril Plant Acrylonitrile vapor Improved hood over coagulation pot. Butyl Rubber FBN Plant Inhalation of dust Bust respirator on a during preparation exposed vorker. of solution. 'Butyl Rubber Finishing Building Catalyst Plant Talc dust. At packaging of finished product. Bust of chromic Multiple dust oxide end a variety sources throughout of other materials. the building. Improved hoods to capture dust at scales. / An extensive ex haust ventilation , \, system for the ^ plant. Tetra Ethyl Lead Blending Plant. Gasoline dyes. Busty for short periods during preparation of solution. Use of respirator by the one person ' vho shovels dry " dye. Grease Manufac turing Plant Mist of grease In gredients and products. Improved hoods yi' over heating, -C saponification, and mixing kettles. Lube Oil Blending 71 hhl Bis agreeable Exhaust hood. ^ odors and mist at r solution prepara tion. Machinists' :Liquid material Disassembly andM^' spilled from pumps, Reassembly Shop etc., some at vhich may be carcinogenic Installation of floor drain beneath s* disassembly loca i tion. t' M. & I. Shops Spilled mercury Exposure not hazardous at present. Chance for future accumulation. Improved floor ~ surfaces to facili tate cleaning. Main Electric Shop ^Varaol, and Xylol vapors fjr Exhaust hood for spraying. EMO 0162 3  *4 V Table V (Continued) Operation or Location Substances or Conditions Remarks Type of Mechanical Remedy Applicable Sandblast Sheds Silica dust. For'protection of sandblast helpers end others in vicinity. Confinenent.of silica dust. Paint Shop Paint removers likely to contain benzol. Exhaust booth. Pipe Shop, Chemical Products Area Metal fuses. Welding nonferrous alloy pipes. Local exhaust aysten. (V; v1 C atalytic Cracking Units Catalyst With reference to velders' verb at turnaround. Respirator should be worn beneath velder's hood. Lead Burners Shops; at Ho. 3 Acid Plant and in Chemical Products Area Refinery Laboratory: Gas Analysis Room Lead fuses Mercury rapor General room ven- Local exhaust tnation does not system. effect dilution of fuses betveen torch and burner's nose. W Improve floor surface to facilitate cleaning. Old Boiler Shop Puses from pre- Question of nickel Extension of hood 4- heating Hastelloy carbonyl foraa- over furnace. c D tubes. tion. EM00162 4 L PROCESS WORKERS CW'-'TCAL PRODUCES DIVISION CRACKING BEPARiMEnT Paraeril Plant. The principal process involved, here is the polymerization of butadiene and acrylonitrile. t Other substances besides the reactants are: Daxad 11 PI hhl (di-tertiary-butyl-para-cresol) Caustic soda ' Acetic acid L o r d mercaptan Hydroxylamine hydrochloride Candellila wax Superloid Number of Employees nfl Their Principal Stations. In the finishing building, three or four per shift spend most of their time at the sxation alongside the drying oven. One or two men are active at the conveyor line where rubber enters the drying oven. Three or four men are engaged fairly steadily at the packaging end of the conveyor. One man intermittently tends the control panel behind the coagulation pot. It is estimated that he is in this locality approximately bnlt of the time. Reactor Control Room. One man per shift works here fairly steadily. Control Room Over Strippers. One man works here full-time per shift. In addition to the above locations, there is intermittent attendance by the per sonnel already mentioned to the reactors, pumps, refrigeration unit, feed drums, storage shed, etc. Exposures Incident to Normal Operation. Attention was directed prin cipally to the possibility of inhalation of vapors of acrylonitrile. This was done for two reasons: First, the probable toxicity of acrylonitrile to man, as E ^0 01 625 2. indicated by .rHmai experiments, is greater than vith ether materials present in' this plant; secondly, the properties and the quantities of acrylonitrile, and the conditions of its use in the process, indicate a greater chance for absorp tion of this substance by the men than for the other substances used. Appreciable .concentrations of acrylonitrile are most likely in the vicinity of the coagulation pot in the finishing building, because at this point the product and reactants first reach an unenclosed vessel. stands several feet over the top of the pot. An exhaust hood Measurements of acrylonitrile vapor on the platform near the control panel shoved 90-180 parts per million in samples collected over a period of several hours on two different days. Samples collected in the following locations shoved negligible or trace amounts of acrylonitrile vapor in air: (1) control room at reactors (2) control room over shippers (3) entrance end of drying oven in finishing building (4) operator's desk in finishing building Concentrations at other, outdoor locations, such as the vicinity of re cycle pumps, charge pumps, knock-out drums for compressors, and charge drums would also be expected to be negligibly low. The question of the possibility of fairly high exposures at repeated intervals in the act of sampling the reaction mixture for completeness remains open. Sampling commences at the reactors about four to five hours after the start of reaction and continues thereafter for the duration of the reaction. Samples are taken vith increasing frequency until the rate of once every 20 minutes is reached. We obtained an estimate of an average frequency of approximately once an hour. There is undoubtedly some vapor expos ure at sampling, as evidenced by the strong odor in the vicinity of the sampling *0 0162 6 2- Information 1b laeWng on the effects of prolonged or repeated inhala tion of acrylonitrile in Imovn concentration ranges by man. Die published maxi mum allowable concentration for this substance is 20 parts per million, 'p m s figure was arrived at after "?-ml experimentation by the D. S. Public Health Service. Guinea pigs and other species showed kidney damage. An observation was made that the action of acrylonitrile resembled that of inorganic cyanides for which 20 p.p.m. hmi previously been accepted as the limit. ' We conclude from our observations at this plant that there is some possibility of chronic intoxication from prolonged work in the vicinity of the latex and coagulation pots. Extension of the exhaust hood face to the level of the top of the pot would effectively reduce acrylonitrile concentrations on the working platform. Close medical supervision of men working in this area is ad visable. Steam Cracking Plants. Ho. 1 and Ho. 2. Materials and Processes. Gas oil is cracked in the presence of steam to produce ethylene, propylene, butadiene, an aromatic distillate containing lsoprene, aromatic tar, heavy fuel oil, gas oil, and some residual gas. A clay treating plant at QLA-2 removes a gimry polymer from the aromatic distillate. Exposures. In the routine operation of these units, exposures to in halation of vanor are infrequent. The men spend most of their time in and around the control houses which are isolated from process materials. Bie necessity for collecting sasples, valve adjustments, inspecting equipment, and making changes in operation takes the men to areas where vapors may occur, Tfris process equipment is out-of-doors. Tine spent in such areas is of short duration. Vapor exposures are of short duration and infrequent. EM 001627 Skin contact with the process material does not occur in normal ii. operation. Unusual events may cause spills and leaks necessitating contact/ principally with the hand gad feet. Significance of Scsosures. The aromatic distillate is important tcxicologically because it contains benzene, toluene, and xylene to the extent of approximately 29 volume per cent. Another 12 per cent of the fraction consists of aromatics boiling betveen 302*F. and approximately 1*50*F. It is impossible to obtain a knowledge of concentrations of these substances in air which may be encountered in those infrequent occasions when exposures occur because of their transitory nature. Since benzene is the most toxic and most volatile compound _ in this group, evaluation of exposures to it is of paramount importance. Eval uation under the supervision of the medical department, on the basis of urine sulfate ratio determinations for the grctp of process people most likely to be exposed is recommended. A discussion of this evaluating technique occurs in the appendix. The aromatic tars produced at these units are included in the program for control of suspected carcinogenic materials. Pumps, vessels, and lines con taining the tars have been labeled and precautions have been put in force. Con tact with these tars by process people is infrequent, according to our observatim of normal processing activity. Butadiene Extraction p i - Materials and Processes. A product stream from steam cracking con taining C4 mono and diolefins goes to butadiene extraction units 1 rift 2 for re moval of butadiene. The process includes the preparation of cuprous f^rrmnn-turn acetate, its reaction with the hydrocarbons, oad the subsequent separation of butadiene. One ammonia refrigeration unit serves the two extraction plants. E r O 01628 Tertiary butyl catechol is added to butadiene as it goes to storage 5- in the relieving scanner: The inhibitor is removed from the can or fiber drum in which it is received; it is melted in a pressure drum, dissolved in butadiene to , make a concentrated solution, and is then metered into the butadiene on its way to storage. A control house for the extraction plant is isolated, materials of great toxicity are not present, and exposures of men by skin contact or inhala tion are not 'frequent in normal operation. Isobutylene Extraction Units Nos. 1, 2. and 3- Materlals Process. Butylene streams iron the petroleum products division and from the butadiene extraction units -undergo sulfuric acid estrac- tioa. Isobutylene and butylene are the products. Exposures. Prolonged vapor exposures do net occur in the normal opera tion of this plant. ' Significance of Exposures. The feed stock and products are simple asphyxiants and anesthetics. Very high concentrations for a prolonged period would be necessary for the anesthetic effect to be noticed. Heelth hazards at these plants consist only of the accident hazard connected with the of sulfuric acid. Extensive precautions are taken. Diolefin Extraction Unit. Aromatic distillate disc.-ssed under the heading "cracking plant" is treated at this unit for the removal of isoprene. It will he recalled that in ` this stream, benzene, toluene, xylene make up a fraction amounting to 29 volume per cent of the total. Opportunities for exposure are approximately the - seme as at the cracking plant. Similar medical control is recommended for the ; men who work here. Vapor concentrations in the air at breathing level of workers at the "unit are too transitory' to permit appraisal of the hazard on the oasis of 6. EUTZL RUfrBSR OTIT5 f * I There are three similar polymerization units, two of which are operat ing- One finishing building is in operation. Materials and Process. Isobutylene and lsorrene are polymerized to farm butyl rubber. Aliwi^un chloride is used as a catalyst. Spent catalyst is hydro- lized, neutralized, discarded (2,000 pounds of aluminum chloride are received and used every 10 days). $ Methyl chloride: This solvent finds large scale use as & carrier for the reactants and as a solvent for the catalyst. Methyl chloride is stripped, from the polymer slurry, purified, and reused. (Loss of methyl chloride is in _ the range of 12,000 to 15,000 pounds per day. Of this amount, 4,000 pounds re presents the unaccounted-for loss.) Caustic solution: Caustic is used in neutralization of hydro chloric acid. Zinc stearate: stearate is formed at the plant from stearic acid, zinc sulfate, and caustic. Its production is on & small scale, amounting to sin batches in a 24-hour period. Zinc stearate for both polymerization units is formed in one location. Phenyl-beta-nanhthvlflcine is added as an inhibitor. It is re ceived as a dry powder and about six times a day, a solution containing six shovelfuls of powder is prepared. Its use amounts to about l8o pounds a day. Xylyl mercaptan is used as a plasticizer. It is made up in kero sene solution Ajnd is added to the rubber at the extruders in the finishing build ing. Talc is dusted onto the finished product prior to packaging. . EM001630 Exposures. X. Control houses for the two polymerization units are isolated from the process units. The 12 men per shift who control the polymer units spend the greater part of the time in and around the control houses. They are, therefore, isolated from exposures to vapors escaping from the units. Instruments in the control house are of the receiver type except for the spectrophotometer room in etach house, which has stream lines bringing small amounts of the volatile re action mixture into the instruments. These rooms are well-ventilated by both exhaust and supplied air systems. 2. Manufacture of zinc stearate. This batch-vise process is perform ed twice a day by one man. Technical stearic acid and zinc sulfate are added by shovel to a reactor. Stearic acid is non-toxic and aon-dusty. The technical grade contains other fatty acids as impurities. They are likewise non-toxic. Zinc sulfate is a material of lov toxicity. The actual time spent in moving it to a reactor is so short that,even if dust arose, exposure time would be practi cally negligible. 3. Preparation of PE5 solution. Twice per shift one man moves six shovelfuls of the powder into a solution drum. It might be expected that in so doing there would be some contact between the material and the skin, and that he might inhale some dust. PHH itself has not caused any acute toxic effects at this installation. The possibility that one or more of its cancer-forming homo logues might be present as an ispurity is sufficient to advisable the use of a respirator during the time the material is being transferred. Preparation of aluminum chloride solution. This irritating and dusty operation, for which a respirator is worn, is performed by one man in aboux 10 minutes every third day. Handling this material is a nuisance, but not a health hazard. E HO 01 631 8. -5- Supervision of reactor performance requires periodic visits several times per shift on the part of the process men to the pin? and reactor areas. The perm areas have roofs, hut no side vails. The reactors vere formerly en closed in a building. These buildings have had a section of the side walls re moved for increased ventilation. At the. time when we vere searching for areas of possible high methyl chloride concentrations, there van great air movement through these reactor buildings, vhich precluded the possibility of accumulation of high concentrations. 6. Finishing building. (a) Attendants at Oliver filters and vibrating screens: This is the location vhere one would expect most intimate association of men with the vapor of methyl chloride. Vapor concentrations are controlled by proper vacuum on strippers preceding this step in the process, and by exhaust ventilation over each filter nd screen. Two men per shift spend part of their time at a distance of about 50 feet from the line of filters and screens. Occasionally each day, men mount the platform at each of the units. Routine spot checks by the chemi cal products laboratory and our ovn analysis of the sarnies collected over one and one-half hour periods shoved less than 10 p.p.m. in the immediate area of screens and filters. We are satisfied that the efforts vhich were made to control methyl chloride vapors, after the poisoning cases of 19^3-^, are effectively operating today. (b) Tunnel dryers. These are exhausted and vapors discharged outside the building. In our experience, men are seldom close to the dryers. (c) Extruders and "rfVHng machines. There is full-time attendance by several men at those machines. Visible atmospheric contamination probably consists of water vapor, oil mist, FBH fumes, and possibly kerosene and xylyl E MO 0163 2 9- A deposit of scan was observed on the overhead roof structures in this vicinity, representing the accumulation 6ince the plant was put in operation. Examination of the scum by the chemical products laboratory showed it to consist essentially of phenyl bet&-rutphthyT*TTrine. To-obtain an estimate of the amount that night be put into the air by sublimation from the extruders in the course of a day, we learned that 180 pounds per day are used. Of this amount, the major portion leaves the product in water drainage to the sever fron water-rubber slurcy and by separation of fine particles for subsequent burning. The loss by subli mation is considered by the process heads to be minor, probably less than 1 per cent of the amount added, or 1.8 pounds per day-- equivalent to 500-700 milli grams per minute. Considering the vastness of the room, the exhaust ventilation at some points of escape, mil the convection currents from the hot machinery and materials that would tend to remove sublimed material from the breathing zone of workers, it is difficult to believe that vapor exposures are significant. let the demonstrated carcinogenicity of several aromatic amines elcsely related in structure and physical properties to phenyl-beta-naphthylamine, specifically B-naphthylanine, and the possibility that some of these may occur as impurities in the commarcial product, make it advisable that this situation be carefully evaluated. In medical examination of workers from this section, particular at tention should be directed to detection of cancerous or pre-cancerous manifesta tions of bladder abnormalities, until it is finally clear that no such hazard exists. (d) Talc dusting and rubber packaging. About five men wor time on the packaging line. There is a dust exposure on the part of the men who remove slabs of rubber from the conveyer to the paper cartons. Concentrations were found to be in the range of 9 to 16 million particles per cubic foot. Hoods provided for this Job are ineffective because of their size and contour; for ex ample. each man must weigh each package as it is filled. The scale is -et EMOO. 10. enclosed in the hood. He mist frequently add a piece of rubber to the package on the scale. Talc dust is dispelled into the air by this operation and is not captured in the exhaust line. The results of dust counts iron samples collected at the breathing level of each of the packagers are tabulated in the Table. Table 1 DUST C C B C S m S A n Q U -- Tili: DUST 33 BUTTL HUSHES rniSBXHS BUHDXDU sample Elassed 1 Designation Time Sampling Location 65 8 min. At breathing zone of 3rd packer in 16 line of 3, packing at normal rate. 6k 5 min. At breathing zone of 2nd packer in 12 line of 3, packing at normal rate. 65 6 min. At breathing zone of 1st packer in 8.6 line of 3, packing at normal rate. 66 *+ min. At breathing zone of man dusting cut 8.5 slabs of rubber for re-run through extruder, dusting by means of broom dipped in dust. There are U men working together, dusting and sawing slabs of rubber. This is about 60 feet from the talc dusting machine. 67 5 min. General air sample throughout the area 2.6 described in 66. It is probable that concentrations of talc dust which were found in this locality constitute only a nuisance. It i6 true that there have been re ports of pneumoconiosis from inhalation of dust in talc and milling, but concentrations responsible for these occurrences were in & much higher range than those we found. Some state codes require that concentrations of talc dust be kept below 15 n.p.c.f. Elimination of the nuisance by improvement in ventilctio* - E KO 0 11. (e) Utility men. Several men work at such Jobs as preparing stock for re-run. They are frequently In the immediate vicinity of the talc dusting and tVHrtg machines. (f) Miscellaneous groups of supervisors, physical and chemical testing men, etc., vork at various places around the vest end of the finishing building. Their exposures to dust, mist, and vapors vould be infrequent and of short duration because most of their time is spent in areas remote from the processes. ALCOHOL PLAITIS Complete protection of the health of workers in the production of ethyl and propyl alcohol requires that three separate and distinct problems be recog nized, evaluated, and controlled. Accident Tfa^n-nd. The first of these is an obvious accident hazard connected with the use and handling of large quantities of sulfuric acid. This problem is veld, understood at the plant. Effective controls are practiced. They consist of provision of protective clothing, safety stovers, and certain mechani cal features of process units. Blending Agents. The second problem is connected with the use of cer tain toxic materials as blending agents and dnaturants. Acetaldehyde is the principal dnaturant for ethyl alcohol produced at this plant. It is Irritating to the mucous membranes when inhaled as a vapor and, for this reason, will not be tolerated by men for periods long enough to give *any evidence of systemic damage. Denaturing with acetaldehyde takes place in a building under govern- ~-er.t supervision. We did not see the denaturing process during the course of our *' e fU - t M 0G 12. for uae in the building, vfaich has only natural ventilation. We believe that use of respirators is sufficient precaution against inhalation of acetaldehyde vapor. Methyl alcohol is used occasionally as the dnaturant for ethyl alco hol and is used quite frequently as a blending agent vith iso-propyl alcohol in manufacture of antifreeze. Continued exposure to vapors of methyl alcohol may lead to chronic 4 poisoning -which is characterized by irritation of the mucous membranes, possibly leading to bronchitis and pulmonary affections vhich nay be associated -with headache, tinnitus, -tremors, local and multiple aeuritides, and more or less severe visual disturbances (Flury and Zcmik, 1931). The toxicity of methyl alcohol is veil-respected in this plant. We sav the precautions vhich are provided at the blending site and at the loading racks. Most of the work connected vith blending and loading of methyl alcohol takes place out-of-doors. The possibility of prolonged Inhalation of signifi cant concentrations of methyl alcohol is remote. The hydrocarbon feed stock far both alcohol plants and the principal products of these plants are toxicologically in the class of narcotics. Inhala tion of concentrations necessary far narcotic action does not occur. There is no evidence of systemic poisoning from ethylene and propylene or from the alco hols and ethers vhich are derived from them. Carcinogenic Problem. The third problem at these plants is one vhich has risen in the Bayvay alcohol plant and in the plant of one other company manufacturing iso-propyl alcohol frcm propylene. Statistical studies have r e vealed an abnormally high incidence of cancer among men vho have -worked in these plants for more than ten years. Cancers of larynx, pharynx, and nasal sinuses have occurred. The locations of these lesions suggest that there might be some 13. way in this company m one other company to determine, if possible, what substances in the occupational environment nay be the carcinogenic agents re sponsible for these lesions. Without going into details of these research pro grass, it will suffice to TMrvfrian that the possibility of air-borne nickel car bonyl haring its origin in some of the nickel alloys in the process equipment is being investigated. Another path of the investigation leads to an attempt to identify certain poly-cyclic hydrocarbons -which are known as carcinogenic agents in the by-products of the action of sulfuric acid on propylene. Uhe current problem at the Baton Rouge alcohol plant is to determine, if possible, whether the same conditions which give rise to atmospheric contaminants in the working environment at the Baywsy alcohol plant exist at Baton Rouge. Several notable differences are readily apparent. For example, the propylene stream coming to the Baton Rouge alcohol plant is much purer than the stream processed at Bayway, at present and in the past. Secondly, a lower concentration of sulfuric acid is used at Baton Rouge. mvi. results in a lesser amount of high molecular weight side products. Thirdly, the physical arrangements of the plant at Baton Rouge, which is a new m o d e m plant incorporating all improvements in design op to seven years ago, are cospletely different from Bayway's plant. The matter of the en closure of process equipment is the most striking difference. Whereas at Baton Rouge ve find a mini m m of enclosure, Bayway has all processing equipment follow ing the hydrolysis step indoors. At Bayway, the control rooms and stations for performing tests on product and reactants are in much closer proximity to strip ping stills than at Baton Rouge. Maintenance at Baton Rouge is more successful in keeping the process materials in closed systems because of the nevness and improved quality of the equipment. These remarks serve only to illustrate the kind of differences that might be significant in the final determination of whether two plants have a 14. If, Indeed, the cancer problem &t Baywsy has an occupational origin, the condi tions vhich permitted its occurrence nay hare existed in the earlier years of alcohol operations at Bayvay, and changes in equipment and process material over the years may hare eliminated the causative factors. Occupational cancer more frequently than not requires a long period of time to reach the stage where it is recognized clinically. Even if there are conditions at Baton Rouge favorable to 'the development of cancer, it cannot be expected to be recognized clinically at this time. Investigation now for possible causative factors is aimed at the pre vention of illness in future years. Success, even if completely attained, will not be known. On the basis of our observations at both Bayway and Baton Rouge, we can suggest that certain steps be taken: First, that investigation of alloys in use at the plant, their products of corrosion, and the possibility of air-borne nickel carbonyl be carried on si multaneously at Baton Rouge. Second, ve recommend that d o s e attention be paid to the manner of drawing samples at the various sampling locations at the alcohol plants. Because of the frequency of drawing samples and the obvious splashing that occurs, we con sider the saapling act to be one of the most Important sources of contact between operating personnel the materials that are being processed. High tempera tures and obvious splashing suggest the existence of mist and vapors at the sampling locations. Third, frequent physical examinations of all the employees at the alco hol plants and selective placement of men are essential. What is apparently a localized site of attack suggests that persons with upper respiratory affections and chronic sinusitis are unacceptable for work at the alcohol plants. 00163 8 The fourth suggestion is that the medical department establish close 15- cancer problem would have been greatly facilitated had the medi rai department, upon becoming cognizant of the problem, had recourse to a log of process and equipment changes over the course of the years. At Baton Rouge, it is still early enough to establish a system vhereby all important changes which might have a bearing on future health problems can be made available for Joint stud;* by the medical department the process heads. CATAL75T PLAHT This plant is engaged in the batchwise production of a variety of solid, granulated, powdered, and pellet products for catalysis of reactions carried out in several refineries. The type of product depends upon current demand. Produc tion of a specific catalyst may last for several days, several weeks, or several months. About a dozen are employed in the plant. A list of eViwtrfrwin and other raw materials used at the catalyst plant during the last five years appears as Table 2, below. A brief discussion of the toxicity of several of these compounds follows. Toxicity of Same Chernies ttgcd in the Catalyst Plant. Molybdenum Trloxide. powder: Ingestion, injection, and inhalation experiments have indicated that acute toxicity of molybdenum compounds, including molybdic oxide, is appreciable, but fairly low. Its toxicology in industrial use has not been sufficiently well studied to warrant an assumption that it is non hazardous. Uncontrolled dustiness of this compound should not be permitted. *' Tungstic Acid: Ingestion and injection experiments with animals have led to the conclusion that this metal is more toxic than molybdenum. Toxi cological data from industrial dust exposures to tungsten cospounds is lacking Uncontrolled dust exposures should be avoided on the basis of uncertainty of effects. EH001639 16. Material Table 2 iro r n tr .i! AHD ffl'HFH RAW MATKRTAT TEED AT CAIAUST PLABT LAST FT7E XEA2S Approximate Weight of Materials Used Activated"Alumina, 2-1 Mesh Iron Oxide, Powder Chromic Acid, Flakes Chromium Nitrate, 50 Percent Concentration .Activated Carbon, Pellets Molybdenum Trioxide, Powder Superfiltrol Clay ' Ball Clay Nickel Nitrate, Crystals Nickel Carbonate, Powder Tungstic Acid Hydrofluoric Acid, 60 Percent Magnesium Oxide Phosphoric Acid, 85 Percent Cobalt Sulphate, Crystals Naphthenic Acids Nickel Sulphate, Crystals Anhydrous Ammonia Sulphuric Acid, 98 Percent Sodium Hydrosulphide, I5 Percent Solution Potassium Fluoride, Crystals Caustic Soda, 100 Percent NaOH Copper Nitrate, Crystals 1,500,000 Lbs. 1*00,000 Lbs. 50,000 Lbs. 50,000 Lbs. 100,000 Lbs. 200,000 Lbs. 100,000 Lbs. 60,000 Lbs. 80,000 Lbs. 20,000 Lbs. 100,000 Lbs. 15,000 Lbs. 15,000 Lbs. 15,000 Lbs. 80,000 Lbs. 130,000 Lbs. 150,000 Lbs. 50,000 Lbs. 75,000 Lbs. 1*50,000 Lbs. 500 Lbs. 25,000 Lbs. 7,500 Lbs. Nickel Salta: Animal experiments hare shown definite tcad.city of nickel salts. Oiey cause inhibition of growth of young animals, changes in the \ pancreas, effects on the respiratory and cardiac nerve centers, and liver and kidney damage. On the basis of lethal doses in injection experiments, nickel is about 50 per cent more toxic than cobalt. --Co--ba--lt-- s--ulp--ha--te: Cobalt salts are recognized as skin irritants. Toxic manifestations following ingestion include abnormalities in the blood forming organs. Effects of prolonged exposure to cobalt dnstB free from other toxic metals have not been sufficiently well studied to be understood. Ho oer- IT. Chromic A d d : Dermatitis, chrome ulcers, and. perforation of the p b b *-T- septum have long been recognized as being incident to exposures to hexa valent chromium compounds. Decently, a high incidence of lung cancer was dis- - covered among workers in a plant manufacturing these cceqpounds. Exposures for prolonged periods to low cascentr&tions of dust and short-time easosures to high concentrations are to be scrupulously avoided. She aaurimrnn allowable concentra tion on the basis of injury to the **1 tissues has been established at 0 .1 milligram per cubic meter of air. There is good evidence in the recent occurrence of nosebleed among several esployees that the catalyst plant is in need of effective dust control equipment. At the time of the nosebleeds, the plant was engaged in the produc tion of a converter catalyst from chromic acid flakes and iron oxide powder. Bxe principal dust sources are the dry grinding and mixing vessel on the third floor, the_ ball mill in which imperfect pell ets are ground for re-extrusion, and the various operations of d r y ^ g wrtfl screening the pellets. In the case of the chromic acid, the irritant effects becsme apparent in a matter of a few weeks after the production of this catalyst was begun. ' Effects of inhalation of dust of other chemicals over a period of a few weeks or a few months may not always be so apparent as in the case of the chromic acid. Hare subtle effects could go undetected until serious illness and dis ability resulted. Additional evidence of the need far a permanent exhaust ventilation system for dust control is the amount of settled dnst on overhead structures throughout the building. Ihe present use of propeller fans in vail installations is ineffective. The use of respirators is impractical because of the discomfort associated with continued wearing through the often prolonged cycle of a dust- producing operation. EM001641 18. Skin Contact. Irritation a the skin of workers by chemicals used, in this plant has occurred in the past. Effective dost control will greatly reduce the amount of akin contact with these materials. At the present time, skin con tact occurs even in the locker roam used by these workers because of the inva sion of dost into all Quarters of the building. JSts use of protective gloves and jackets is effective in pr" ^ " g skin contact actually transporting materials. EH0C1642 19. F8TBOLEOM HtQDOCTS DIVISION miim m c ASD O U K07ZKEST Distillation. This department operates pipe stills and too shall still batteries; 96 men are employed in erode distillation and some 68 on re-run. There is no in dication of any potential >-- n * hazard in the routine operation of refinery pipe stills. Attention vas drawn to the possibility of petrolenn vapor or hydrogen sulfide exposure on the part of the operators of Still Batteries Ho. 16 Ho. 17. Three or four men per shift operate each of these batteries. At these loca tions, product streams flow through the still house which is the principal statlm of the operating personnel. Look, boxes are provided for each stream. There is a possibility of leakage of vapors from the look bores or their lines. On two occasions, we were to detect the presence of petroleum vapor with a sensi tive combustible gas Indicator. Details of these tests are given in the follow ing Table. Table 3 PETBOIZUH VAPGB HBASURBOEBTS XH HO. 16 ASD HO. 17 w s t t o r t am i Date k/6/k9 k/6M Location and Operations Concentration (p.p.a.) Ho. 17 Battery Still House. Ho. 1 system charging after turnaround; Ho. 2 system running crude; Ho. 3 system running adzed gas oil. Several measurements made. Less than 10 Ho. 16 Battery Still House. Ho. 1 system running mixed gas oil from separators. Ho. 2 and Ho. k systems hwwniTig lov octane distillate feed; Ho. 3 system running heating Oil. Test made at 6 lmesViorys among the look boxes. 0-10 e roo 20. Plans are underway and sort h u already started an pran< w g an en closure for operating personnel separate iron the location of the loot boxes. Side vails vill be removed roa the present enclosures. Shis is in keeping vith the general tendency to open up buildings vhere there are sources of from process equipment. Other sre various pusp roams that have been opened up and some gas compressor houses from which the side vails hsrre been removed. In the case of So. 16 and So. IT Battery Still Souses, execution of these plans should result in eoaplete elimination of any potential health or safety hazards from vapor or hydrogen sulfide. Ho. 2 D. & S. and Hydrogen Sulfide Secevery Unit. Biese tvo units are under the direction of the same operators. Hydro gen sulfide comes to the recovery unit from various sources. Pros this unit, tri-potassium phosphate solution is pumped to So. 3 D. 4 S., operated by the Light Ends Department, far use there In scrubbing gas. The hydrogen sulfide-laden solution is sent back to the recovery plant for regeneration. Biere is no punp the spent solution, therefore, leak age at puspa does not put hydrogen sulfide Into the air. ttis scrubbing unit is exceptionally tight. So odor of hydrogen sulfide vas detected. At the base at the flare stack, there is & rater seal drum to prevent flash back. Under the operating conditions that ve saw, there la aase spillage end leakage from this rater-seal drum, permitting an appreciable escape of hydrogen sulfide at ground level. This vas formerly In an isolated area, but now the new light TCn* Plant stands in close proximity to the source of leakage. A . high local concentration of hydrogen sulfide seems possible under weather condi tions producing little air movement. We consider this the most important poten tial site in the refinery for acute accidental or chronic exposure to hydrogen sulfide gas. Accidental exposure to high concentrations niche >>* c-.--- *.-.- 21. persons entering the ianediate vicinity of the flare stack base to perfora . mechanical York. Sub-acute effects, such as conjunctivitis or upper respirator Irritation sight be suffered by process people constantly la the nearby Light Fnris Fiant. Oil Movement. Oil Movement has control of pusps, gauges, pipe lines, storage tanks, barge loading, car loading, tetra-ethyl blending, nae of inhibitors, and dyes. Tetra-ethyl lead b l ^ ^ ^ g . This operation is performed under safe practice rules, prescribed by the suppliers of tetra-ethyl lead. Medical control by the refinery Medical Department la rigid. Protective equipment and clothing, as veil as facilities for personal sanitation, are provided the employees. Two men are employed per shift. Aside from the normal routine of blending lead tetra-ethyl Into gasoline, there are periodic calls far cleaning of tanks, pumps, and pipe lines. Daese jobs are do under the supervision of the suppliers' safety people. Equipment la rcEV-l ^ l y flushed vlth lead-free gasoline before it is turned over to the it department. We knew of no additional precau tions or changes In procedure that are necessary in the handling of tetra-ethyl lead. Addition of Dye to Finished Gasoline. Two men work on each shift. A dye solution is prepared from the dry dye about three times In 2k hours. The dye is removed from the drum in which it is received by means of a scoop. It is ` weighed and scooped into the solution drum. It is a dusty job, as ahovn by the deposit of dye on all structures in the roam. Infrequency end short duration of `the dust-producing job suggests the use of dust respirators for the prevention of dust inhalation. Prevention of Inhalation is desirable, since the exact effects of such inhalation, where a variety of dye materials are used, are difficult to 22. AfliHtion o f l nhibitor to Finished Gasoline. She Inhibitors that are currently in use are UCF-5 and DuPont-5. Inhibitor is drawn by T a m m from the drum In -which it is received into mixing and m etering drums and from there Is bled into the streams, ft-iii procedure offers only the remotest chance for a man to came in direct contact -with the Inhibitor. Light Oil S e a t i n g . *^ia includes acid and alkali ta-eating, calcium hypochlorite treating, doctor sweetening. Of these processes, only the doctor sweetening involves the use of materials or processes that are of Interest from the standp oint of employee-health. Litharge Handling. Fresh litharge la added to regenerated doctor solu- ticn by dumping directly from drums into the open regenerator tanks. The si2e of the tank and the location of the platform and crane prevent free movement to the vindvard side -while dumping. Respirators are -worn by men doing the dumping for the prevention of inhalation of fine lead dnst. All litharge dumping is done by ' two porters on "A" shift, with a frequency somewhat leas -than once a day. These men are an the Medical Department's schedule for twice-yearly examination. Doctor solution regenerator tanks are in a crowded area in this refin ery, differing in this respect from the situation at Aruba. With the thought -that employees in the treating plant, other than those who actually dump litharge may be exposed to toxic amounts of lead as dnst or as a mist from tanks being aerated for doctor regeneration, we sought to learn the concentration of lead in the mist escaping at the tap of the tank. The opportunity to make such measurements pre sented itself at Sarnia. The results showed that two samples of air, collected in the heaviest concentration of mist at the tank top on the downwind side during aeration following litharge addition, contained 0.17 and 0.27 milligrams of lead ?er cubic meter, respectively. If we consider lead in a range of 0.1 to 0:5 milligrams per cubic meter to be present at the tank top, we may safely assume that,vith dilution occurring before it reaches ground level, and with variation 23. is vind direction, that no wi are constantly exposed to concentrations of lively to prodsce spasima at lead poisoning. Eie validity of this assumption night be tested by performing urinary lead deteminations for the group of esposed persons. Such measurements vili serve to indicate, far better than atmospheric sampling and analysis at this outdoor location,-vhether absorption is occurring in these individuals. Addition of Dye to Tractor Fuel. The treating of tractor fuel includes the addition of a dye known as Petro Green 2 Dye, vhleh is a product of Patent Chemicals Company, Patterson, Pev Jersey. She same tuo porters vho handle litharge and doctor sveeteniag occasionally make up tvo-pound packages from the bulk dye In drams. A Tfurfr at dye deposit on the floor and structural members of the room in vhich this packaging is performed indicates a lov order of dustiness in the p erf ormance of the job. E MO 0164 7 24. TITOBTPATTTT. jSD PAEAFTISB DEPAE3KSBT Wax Presses. . a The fact that there is ' t . statistically significant high incidence of cancer among wax press cleaners ess demonstrated in another refinery. Cases of scrotal cancer hare been discovered among the press cleaners at Baton Bouge. In vestigations are no? underway by the company to identify a specific carcinogenic agent or agents in the material which esters the presses. lanediate steps were taken to prevent any further contact with the material that may be responsible for the pathologic changes In the men. The first step was logically to prevent the obvious contact between the skin of the pressmen *** machinery or implements on which there was a deposit of paraffine distillate, paraffine wax, or foots oil. One particular zone of con tact to which attention vaa directed is the anterior surface of the g* and the pubic region. was baaed an the observations that pressmen sometimes lean forward against a waist-high, horizontal bar that runs the length of each press on both sides, and that some of the cancers occurred on the scrotum. To prevent such contact, all press cleaners sre now provi ded with d e a n work clothes and aprons far each shift and sre required to take a shower dally before leaving the plant. Siese precautions sre effective in preventing this particular type of contact. A shower roam far press man is conveniently located end maintained in a sanitary condition. Other skin contacts with wax and pressed oil most have taken place in past years, in the cellars where press cleaners go daily to clean the floors, remove sawdust, etc. preparatory to the entry of pipefitters and machinists. In spite of the precautions taken to date, there remains full-time op portunity for absorption of caterials through the akin of the press cleaners' EHO 0164? 25. bands. Such, absorption cannot be ruled out as a node of entry of the suspected carcinogen. Its prevention has not been efected because of an Inability to find a satisfactory glove material that will exclude the costaninaut from the hands and, at the tine, pend.t efficient manipulation of the flat steel blade with which wax is ream ed from the presses, Frequent washing and wiping with clean cotton waste are temporary, but not wholly satisfactory, precautions. Another node of entry of carcinogenic material Into the body of TM<n is ' by absorption through the lungs following inhalation. Following inhalation of chromic acid, cancers were formed in the lung Itself. Inhalation of beta naphthalamine results In the formation of bladder tumors. Shin cancers have occurred In workers with arsenic, where at least a part of the exposure has been to inhalation of arsenic confounds as dust. Vith this thought in mind, an effort was made to learn whether oil mist might be present in the air in wax press rooms in sufficiently fine particle size to permit of passage to the deeper portions of the lung. Samples of the air were collected by means of the midget inpinger with water as the collecting medium. Microscopic examination of the water suspension definitely shoved the presence of oil droplets of lesB than 5 microns diameter. Table k, which follows, shows the locations where samples were collected and a rough apprcadmation of quantities present, on the basis of counts that were made in a manner analogous to that used in making dust counts. As shown in the Table, mist was discernible In rooms with both doors closed and filtration in progress, and alao in roams with doors open and actual press cleaning taking place. A demonstration of Hie presence of oil droplets in the air in wax press rooms is significant of the fact that inhalation of a potentially carcinogenic material occsus. The importance of this occurrence in relation to the present cases of illness and to the prevention of future cases is a matter that can be evaluated only by a broad investigation into the reasons for mist formation, the 26. Saj^le Humber 77 < 78 79 80 81 68 69 70 71 72 73 7* Table k OIL EBGEIET C0UHT5 -- PAHAFET5 ISESS BUILDUP Sampling Tine Location Evaluation (Particles per cubic centimeter of air) 10 mill. 10 min. 8 min. In "hot" press rooms Bos. 5/ **4 3, in yfrHch the pressure is on. Bo men vurJdng in these rooms during the sampling time. Sample m i va U d n g arnTmd the filter presses. In "hot" press Bos. 13 and lh, pressure on. Bo men vcrUmg. In "cold" vaz press rooms Bos. y> and 31, pressure on. Bo men vorking. At conclusion of saaple period, too pressmen entered for the purpose of cleaning the presses. 11.3 21.2 0.0 1 1 min. "Cold" press rooms Bos. 30 and 31, during 6.k beginning irfe*g* of press cleaningr starting vhen pressure is vithdravn and ending vith four mimites of actual preas cleaning. 7 min. Outdoor aample in vicinity of lube agitators 7.8 directly north of tank 3 3 1 vlnd of moderate Telocity from the south-east. 10 min. In "hot" press room Bo. 11. Pressure an. 7.1 10 min. In "hot" press room Bo. 9 Pressure on* 2.8 Many Tlsible oil-vaz leaks. 10 min. In "hot" press room Bo. 6, shortly after 0.0 presses hare been cleaned. Both doors open. 10 min. In "cold" press room Bo. 18. Pressure an. l.k 10 min. In "cold" press roam Bo. 21-. Pressure on. 7-1 10 min. In "hot" press room Bo. 9 during dennlng of 2.8 the filter presses. Both doors open. 10 min. Outdoor sample in Tlcinlty of lube oil agita 0.0 tor tanks. E MO 01 650 27. nature of the material in droplet fota, Its carcinogenic actlTlt7 under experi mental conditions, and methods a esposurea to Inhalation of the seLsh Scone observations were made at the was presses In the Bayonne Befinery for the purpose of conditions there elth those at Baton Bouge. It vas noted that aalntensnce effar La at Baton Bouge are acre successful In preventing leakage of aaterlal JSroa the presses. Gross leakage, in the form of voluminous sprays against.the press room sails and ceiling sere seen at Bayonne, hut not at p&ton Souge. The nature of the sax-containing stock and the percentage recovery of sax that Is desired have, of course, been the factors that govern the ertent of the maintenance effort nay account in shole for this observed difference in performance. T a m i n g of Sas Joaquin distillate, responsible at Bayonne far most af the press room contamination, has not been undertaken at Baton Bouge. Another notable difference In the operations at the two plants la the fact that Baton Bouge has but one press per roam, shlle Bayonne has some multiple installations. may that Bayonne press cleaners experience a contact vlth material as a mist, spray, ar leak from presses adjoining the one on which they are working which is irv< r^g in the Baton Bouge operation. These differences, both of which would seem to indicate less Intimate contact at men with material at Baton Bouge, may or may not be significant when applied to forecasting cancer incidence. Tiey may assume some ng when the Identity of the carcinogenic material and Its mode of entry are better understood. Plate Across the road from the wax press roams is a shop consisting of one room In which plates filters ore cleaned by means of steam, two other rooms In which repairs are to the canvas filters. About 8 m** work in this shop on day shift. Filters are brought by the press cleaners to the cleaning room. 3hey are placed on a rack, the room is closed, and live steam is turned i. C * 28. onto the filters os the racks and left as. oversight. As each filter Is put os the rack for cleaning, the others which here been exposed to steam are pushed dovn toward the far esd. Is this m^Trn|`*, of rotation, by the time a filter reaches the end of the rack it has been cleaned and la ready for repair. The time actu ally spent la the room is only the time required to -rearve a clean filter from a rack and the time required to turn on or shut off the steam line. Exposure of men to the vapor and mist arising from the steam elowning is, there * fore, infrequent. The actual work of repairing filters occasions no contact with contaminating wax or oil. Refrigeration Unit. . * . ' W''* At this unit, actual contact with the materials being handled is limited to the machinists and pipe fitters. Bo hazardous exposures on the part of the process operators can be foreseen. Crude Scale Wax Sweaters. > . v. w Feed for the crude scale wax sweaters consists of wax and oil after pressing has removed same oil, flash-topping at Bo. 1 vacuum pipe still has re moved still more oil, acid treating and caustic neutralization has improved It. Men are not exposed to the mixture in the sweating roam during actual opera tion. Maintenance men do in contact with the material when effecting repairs. These will be discussed elsewhere. Refined Wax Sweating. This process is similar to that described above but handles vax vith much lower oil content. E PO 01 65 2 29. Prpsans Tte-rar-fng, Rronane De-olllng, and K m o a n e Dc-asphai'MTtg. These three processes of the lube and paraffine drpartnent appear to hare no health significance. There Is Intermittent exposure to propane in un known concentrations, Son-volatile materials at these units consist of lube stocks for further treatment and the residues which are wax, oil for cracking feed, and asphalt for fuel. Occasions for aJdn contact with these materials are infrequent in normal operation. There is no evidence of danger from fc-tn contact, however frequent. MEK Plant. c \ * r ' Processing materials. The solvent employed in this process consists of methyl ethyl ketone 50$> benzene 30$, and toluene 20$. The solvent is stripped from the oil and returned for reuse. The separation of precipitated wax from the oil solution is accomplished in six large rotary filters. Since this is a low temperature process, the filters are enclosed as completely as possible and sur rounded by insulating material. The refrigerant is propane. Personnel. This unit is operated by five men per shift. One of these men spends his full time in a "tt room in the filter building. The remainder divide their time between the isolated control house and various parts of the plant. Control of Scoosurea. The extremely toxic character of benzene and its volatility make its complete control a prime concern in the operation of this plant. Protection against accumulation of solvent vapor was built into this plant by design engin eers. Storage tanks and pumps stand in the open air, leaving the filter room as the only enclosure for benzene vapors. A phase of operating procedure vhich is of ^reat significance in the control of solvent exposures, al though it probably had origin in precautions * 4_ * 50. the draining of units prior to repair or replacement and their flushing vith inert gas prior to disconnecting. The ventilation system in the filter building has recently been rade the subject of a thorough investigation by the Petroleum Technical Service. The survey indicated, that solvent vapor concentrations (as aeaeured vith the MSA Benzol 7spor Indicator) in excess of 100 parts per million could, not be detected anri that the most commonly encountered, vaine vas 20 parts per million. In viev of these results,and our ovn vhich ere similar and appear in Table 5 (following), ve conclude that in the present mode of operation of this plant, loss of solvent to the atmosphere in the places vhere men varie does not result in excessively bigi concentrations in the breathing level. Table 5 MEASUHEHZET OF SOLVES! VAPCE 15 MEE FLATO Date V5A9 h/5A9 V5A9 V 5A 9 V5A9 V5/b9 W6A9 k/6/U9 h/6/h9 W6/to W6/k9 k/7/k9 k/j/Us Location ! fiesult * 1 Lover level of filter building, 10 feet inside the S.V. door. On steps of West ladder to upper level. Beneath Filter So. 1. On steps of East to upper level. In filter roam control roam vhere the filter operator spends most of his tiaa. Lover level; over drain to stop. Beneath Filter So. 2, near sump At pump friTsdUng van-solvent from So. 2. Beneath Filter So. 2. At southernmost sump. At susp beneath 5o. 5 filter. On upper level. Vest side. Inside operators shade. At 10 locations on lover level beneath filters. At base of pipe discharging vaste to sump, not at man's breathing level. 20 0 Less than 20 Less than 20 15 - 20 30 Less than 10 20 0 0 10 0 0-20 100 - 200 * Total vapor, in ppm. EH001654 31. Urine samples from a group of five process men were examined during our sisvey and sieved normal values for the sulfate ratio. 3he results are given in Table 6, which follows: . Sample Number 12007 1541 59I0 11374 12279 Table 6 Bvyrnr.'V! Qy ttp-htc gnrPATg S A H 0 MEASUH2MEET PQH MEK PLANT WORCTRS Ratio of Inorganic Sulfate to Total Sulfates j Organic S03 1 gn/liter 0.85 0.84 0.90 0.84 0.90 0.259 0.269 o.no 0.400 0.273 The high degree of tonicity of bennene and the fact that leakage of solvent does occur, requires that continuing checks be made on the concentrations in the air. The FTS proposal that routine measurements with the Benzol Vapor In dicator be made is a sound one. tte frequency of the measurements should be fixed through correlation with the production schedule and results obtained. Bie in strument Itself is satisfactory, provided that it is checked about once a month against known concentrations of the solvent mixture in a test chamber. It Is desirable also to periodically examine the urine of the 21 pro cess people at the unit mechanical people regularly assigned to the unit to detect any variation of the ratio of inorganic to total sulfate from the normal range. Such a variation will be detectable in advance of symptoms of poisoning, should excessive exposures ocean and will supplement the atmospheric tests as a f *o o i * * 32. method of measuring exposures. A discussion of urine sulfate ratio determina tions as a of evaluating benzene exposures is included in the Appendix. Wax Filtering. In thls"procesB of filtering vax through bauxite and bauxite roasting, a dust source Is the base of the regenerator tubes, where the heated bauxite falls to a conveyor belt and Is carried to the hopper. The only excursions into this dusty area are for the purpose of replacing wooden pegs on the shake-out ' apparatus and for loading fresh bauxite from sacks to hopper. The former re quires about five minutes serverel times per shift, possibly hourly. The latter is done Infrequently and requires relatively ter minutes. Occasional inspection of the operation and replacement of belts accounts for other trips into the dusty places. The regenerator runs 24 hours to fill one charge. Two 24-hour re generator periods may follov one another closely and then not again for the re mainder of the week. About seven or eight men are present at this unit daring a 24-hour period. They spend most of their time in the roam an the northwest corner af this building, ground floor. * roam is closed off Traa the dusty area of the building, but some dust enters to settle on desk, ledges, instruments, etc. Typical dust counts are: 1. At base of bauxite chutes during regeneration: 23 m.p.c.f. 2. In control room, immediately after bloving out the chutes vlth compressed air: 4 sup.c.f. 3* In room containing hopper to receive nev bauxite, during regeneration: 1 m.p.c.f. 1656 . , ,, This dust contains no crystalline free silica, therefore, no silicosis hazard exists. Dust concentrations where the men spend the major part of their 33. Lube Filter Plant. ' Tiltr&tlon of lube stocks through fixed beds af Attspulgus clay and the regeneration of the clay by the downward passage through a kiln Is a process which has no industrial health Clay dost occurs in some parts of the . buildings which house the two filter plants and the clay regenerator. This dost contains no erwtiVTi ree silica. There Is no silicosis hazard. Our observa tions and dost counts in the plant ahov a low degree of dustiness most of the tine. Concentrations are not sufficient to constitute a nuisance. Results of the dust counts are given in the Sable that follows. Sample Htrnber Sana ling Tine Sable 7 DOST COURTS AI LOSE J U I E R PIAHT Location Lust Counts (m.p.c.f.)* 79 3 nin. 80 10 sin. 82 8 sin. 83 6 min. Sanple taken at level of elevator actor in 1.0 regenerator building. So men working in this area at this -tine, except two carpen ters at a lower level. On floor level beneath regenerative furnaces, 0.0 around the base of So. 2 furnace. General air sample on level around top of 0 .1 filters. So visible dust sources. General air sample on level around base of 0.0 lube oil filters. So visible dust sources. EM001657 31*. fhtnol Plant. - V *,,* V. V'* j .- At the Phenol Plant, adequate precautions far the prevention of contact vlth phenol are in effect. They consist of provision of all the neces sary protective clothing and emergency showers. She personnel at the plant are svare of the accident hazards. Our attention was drawn to the existence of phenol vapor In certain areas of the plant, as evidenced by the odor. Chronic phenol poisoning from prolonged a low concen trations of vapor has been de monstrated in experiments. It results In respiratory difficulty, diges tive disturbances, and central nervous system disorders . Damage to liver and Kidney also occurs. Toxicological data for man from. industrial exposures are lacking. It is difficult to say, on the basis of available information, what con centrations of phenol In the air of work places can cause chronic illness. The principal sources of phenol vapor are leakage at pusss hand! 1ng fresh phenol feed, de-phenolizer feed, etc., and a tank which collects drainage from all sources of liquid leakage. The need for heating the leakage as it is collected and drained item the units, in order to keep it liquid, causes greater vaporization than would be expected from cold phenol. These sources of phenol leakage are outdoors. Two revs of pumps which serve these plants are in open areas adjacent to the control room. Eight men per shift operate the two phenol plants. They spend approximately equal time in areas where phenol vapor la noticeable. In all easea, the amounts to approximately no more than one hens: per shift. Most of their time is spent in the control roams which have fresh air supplies and in outdoor locations around the plant, remote from the sources of phenol vapor. The following table shows the results of measurements of phenol vapor in the air in various locations. E HO 0165 8 Sample Number 66 -6b 71-67 73-72 1 2 35. Location Table. 8 phenol measurements Date Phenol Concentration (parts per Billion in air) South pump group No. 2 plant. k/kfk9 At drain to sump. No. 1 plant. k/k/k$ h Control room. No. 1 plant. b/b/b9 South pump area. No. 1 plant. k/Q/hs 11 Same as 1. k/B/hs 6 In air samples collected at a point between two pumps whieh were visi bly leaking hot phenol mixtures, concentrations were found to be in the range of 6 to 11 parts per Billion. These concentrations exist in the area where the greatest amount of phenol would be expected. On the basis of these results, one can reason that in the control house, where the men are present for aost of the working day, the concentration of phenol vapor will not exceed 1 or 2 parts per Billion. The occurrence of detrimental effects from continued inhalation of this range of concentration would not seem possible when one considers the ability of the n o m a l hrTM* body to detoxify phenol by means of sulfates and glycuronie acid. Scrwerrer, it is advisable that d o s e medical supervision of these nen be exercised. Any nervous disorder or history of chronic digestive or respiratory difficulties among the phenol plant workers should be sufficient to raise the question of occupational origin. E MO 0165 9 Lube Oil Treating. d e plant area, containing a d d agitators, d o d g e kettles, caustic vast, and water vash ressela is noted for the presence at sulfur dicolde and sulfuric acid mist. It is evident that the treaters' exposure is the greatest of all per sonnel, for the7 oust supervise the Seating and sludge hydrolysis. d e y are re quired by these duties to nouat several times a day to the top of the agitator vessels. In so doing, they eaanct always resain to the windward side. d e i r re action is typical of personnel at operations of this Idrid. They become inured to irritant concentrations that would offend persons not constantly exposed. As a group, if there are effects on their health, these might be expected to manifest themselves as Increased Incidence of tooth decay and upper respiratory affections of an acute nature snserisoaed on predisposing conditions, such as asthma, ca tarrh, etc. Permanent systemic damage from such exposures are not known. d e other category of exposed persons, those who work in the neighbor hood and are intermittently exposed to somewhat lesser concentrations, are more apt to be irritated by occasional high-exposure Incidents. d e a e exposures are nuisances rather than health hazards, except in cases of individuals made highly susceptible b y predisposing illness affecting the respiratory or heart functions. Such individuals are known in other refineries, d e y can suffer respiratory dif ficulties and dlstreas bordering on prostration. Their transfer to plant areas uncontaminated by acid gases is the simplest solution to their difficulties. Lube Oil up. . d e manner of transfer of lube oil additives from tank car, to storage, to blending tanks by pumps does not furnish occasions for intimate contact of these substances with the men. An exception is the weighing and addition of PX -iii to small batches of heated oil to make a concentrated solution. The high 37. temperature causes fane evolution la disagreeable. Installation of a can opy exhaust hood ore- the task vould eliminate the obrlous cause for cos- plaint in this operation, <*h is perfarsed frequently. Grease Manufacture. Erposurea'on the part of the fire to eight sen per shift who operate the grease manufacturing plant consist of: (1 ) inhalation of mists rising from heating tanks, and vith steam from saponification kettles, and kettles; (2) inhalation of dust during the receipt, storage, and addition of dry ingred ients; (3) skin contact vith grtaae ingredients and products. The evaluation of these exposures must take into consideration the fact that many products are pro- dueed only occasionally nd vith great variation in amounts. Inhalation of Mists. Much of the mist arising from heating of the starting materials in grease manufacture is traceable to tanks containing purified vegetable oils and animal fats. For such exposures, there is no indication of hazard. The saponi fication reactants likewise are regarded as Insignificant. At the mlTing tanks, there is occasion for entry into the air of same of the large variety of chemicals and additives, in *ny cases, these are harmless. An exception if that of the suspected carcinogenic agent whose presence is known to the medical department. These exposures are ao unpredictable in duration that medical experience with the men involved will have to be the baaia for their evaluation. . . It is a fact, as illustrated in other grease plants within the company, that mist escaping from saponification and miring kettles en be effectively captured by properly designed i-n w . - t n t w exhaust ventilation systems, ihere such systems exist, inhalation of mist becomes negligible in the plant. F *0 0166 TnViwljttlon of Dust. Dost exposures in grease manufacture are of minor inportease because the dusty materiel which is handled, most constantly and in greatest mount (lime) is non-tazlc in quantities absorbed as dust and other materials of higher potential toxicity (lead, asbestos, mica) are handled either in email amounts vlth negli gible frequency or in a " m that does not cause the dispersion of great quan- < titles in the atmosphere. Asbestos, far example, after receipt and storage, is added to grease batches vlth a frequency that vas estimated at to 8 times per month. Its handling does not require violent tearing apart in the dry state vlth consequent dispersion of dust. Occasional exposure to the moderate dustiness of normal hand! ing is not the type of exposure that is blown to hare caused asbestosis in workers of other industries. Bed lead comes in small cans and is added infrequently to grease batches. The act of dimp-ing from the can into the "rtftwg ressel is the only dust dispers ing operation in its handling. It is difficult to conceire of toxic amounts being absorbed by any vorbaan in this manner. Skin Contact. EM00166 2 Contact of the ingredients and products vlth the abLn of the hands, arms, and faces of the vorkers in the plant occurs frequently. Its occurrence is due chiefly to deposits of these materials an equipment from misting. Dele terious effects from such skin contact be predicted merely from a bicw- ledge of the effects of the individual compounds an the win* of for, in the 'case of a grease mixture, the inclusion of the additives and in a matrix of soaps and oils makes the chance of their unobstructed contact vith the skin questionable. Evaluation of the dermatitis hazard rests, therefore, in the oeccro of iucicer.ce of skin effects wiring crease 'plant vrrrir**. v- --W4 -- ^''I r 59. department. In the absence of any evidence tram, this source, It is safe to assume that no problem etists and that the company meets Its responsibility to Its varier by prpriding them vith adequate cleansers and cashing facilities. EMO 01663 rptnrrm mgpaH^nw1!1 Thermal Cracking uo. 1,000 pound Colls: So. 21 and go. 22 Units. Materials and Proceas. Feed stock Is gas oil tram various sources, clarified oil from PCLA, nd pitch, bottoms (from pipe stills). Products are gas (C-l to C-l), naphtha, cycle gas oil, sad tar. Exposures. Exposures to Inhalation of vapor and mist from the mater ials that are being processed can be expected to occur in the act of sampling process material, In the neighborhood of pumps where leakage occurs, in the neighborhood at pumps vhlch give rise to oil mist. Such exposures are signifi cant health-vise vfaen the material consists of clarified oil or the tar produced from cracking clarified oil. Biese are suspected carcinogenic agents. The con trol of oil mist Inhalation In a program, for cecplete prevention of occupational tumor formation is discussed In the section dealing with Wax Press Booms. Collection of oil mist In an lmpinger and evaluation of the results by a procedure analogous to that used in dost counting gave the following results: Table 9 CONCEm ATIOB OF O U MIST IB VICJH I'TI OF POMPS AT THERMAL CRACKING OBIT Sasple Humber Sampling Time Location Droplets per Cubic Cent!- meter at Air 6k 8 min. Bo. 21 - 1,000-pound cracking coils, in doorway to control house near hot pitch feed pump. 65 Min. Adjacent to hot pitch feed pump, two feet from shaft which appears to be chief source of oil mist. 1-59 0.0 kl. These evaluations serve only to demonstrate the presence of oil mist in the location cited. Number of Men. Operating personnel consists of six men per shift. Location and Features of Control Sense. Die control house in which the men spend most of their time consists of two rooms adjacent to one another and close to pumps. Mist, ffoa hot oil pumps can enter through open door on vest side of control room. Punp site is covered by a roof and enclosed an two sides. Be flux pumps handling light fractions (naphtha) have fair amount of leakage, but are located good distance from control house and are not enclosed. Materials for measurement are brought into the control house (no transmitter-receiver type instruments here). Activation of recorders is by means of natural gas. Brovn and Fcxboro instruments In shop bleed tests shoved escape of 0.02 and 0.32 cubic feet per minute respectively, here is an estimated total of 15 such Inatrm eats for the No. 21 and No. 22 units. Tests vith benzol vapor indicator gave no de flection around the instrument panel. Full scale reading vas obtained when the intake vas placed at the meter face. The location of hot oil pusqps just outside the door of this enclosed control house affords the opportunity for the entrance of fairly high concentra tions of oil mist and vapor of varying composition and of unkaovn significance health-vise. Escape of vapor and gas from instrument lines inside the house is thought to be of Insignificant Importance because of the small amount of leakage that can be tolerated from the standpoint of process control. Ssaml1n s . Helper at the unit takes a sample Cram the "hot bottoms" line about four times per shift. The line must be bled for several minutes be fore draving the sample. The person drawing the sample cannot always stand to windward side because of the location of the drav-off pipe over the drain to the sewer. E MO 01 66 5 The three-sided abed where the gravity teat la made, effectively en closes vapors from the hot oil being tested, causing Increased concentrations In the operator's breathing level. The location of the end of the tanr-cff line, with respect to the open ing to the sever line and to tiie position that mist be taken by the man prior to and during sasplisg, affords too great an opportunity far splashing and volatili zation of the material that is being dranm. * gravity testing ia desirable. Less confinement at the site of Since sampling and testing are the acts providing the moat intimate contact of process vlth the material, an effort towards irproveaent of these .arrangements is suggested. 750-pound Colls; So. 19 and Ho. 20 Units. Process. Feed stock and products are similar to those of So. 21 and So. 22 units. (Sote: When clarified oil foam PCLA. is used as feed, it is sup plied under sufficient pressure by props at FCLA. We have inferred from this that there is no pump here unaltered clarified oil-- hence, no mist of this substance as received.) Humber of Men. About men per shift operate 17, 1$, 19, and 20 cracking coils. Location and Features of Control House. The control area ia not as completely enclosed as that at Ho. 21 and Ho. 22. Instrumentation is the same. Proximity of pumps invasion of mist foam hot oil pinups through open doorway is about equal. Besults of oil mist counts are as follows: EM001666 *3. Table 10 COHCEHTRATTOH CF OIL MIST Hi 7ICHHTT OF PUMPS AT THERMAL CRACEEBG UHIT Sample Humber Sampling Time Location Droplets per Cubic Centi meter of Air 66 10 sdn. Ho. 20, 750-pound cracking coil, near hot sources. 67 8 min. Ho. 20 , 750-pound cracking coil, adjacent running pitch bottoms. Vind is from north-east some mist from hot oil pumps may reach this position through the open doorvay. 68 7 min. Ho. 20 unit, in doorway between hot oil pu~p room "d control room, directly dovn- vlnd from hot oil pumps. 7 M 1.23 7.W- Conclusions Regardirr Bcsosures of Men. Exposures by kin contact inhalation of mist or Taper is possible at samp ling locations. Sie sites vere not inspected, nor was the frequency noted; this is, therefore, an inference from obserratiens at other units. Mist from the hot oil pimps to the north van found to invade the space (semi-enclosed) ehere process *"*> spend aost of their time reading instruments and filling out charts data sheets. This is not a continual exposure, depend ing on vind from the northern (juarter or lack of uind. . Unusual situations, one of vhlch ve vltnessed, such as a broken valve, occasionally vlll cause spillage or leaks that result in skin contact before re pairs can be effected by the pipe fitters. E 0166 7 Steaa. Cracking Proeeaa. '* Feed stock for this proeeaa is wirgin beany naphtha. She products coi sist of a dilute butadiene stream, as aromatic distillate, residue gaa, aromatic tar, fuel oil, asd a C5 cut which goes to isoprese extraction. Clarified oil from PCLA is used as a quenching agent. g<nn>>er of Men, e w n men per shift spend Host of their in the control house which is closely associated with the feed and water pumps. Association with Toxic Substances . She substances at this unit which deserve closest scrutiny are the tar bottoms, clarified oil, and the aromatic distillate. Th* tar fraction the clarified oil are included in the suspected carcinogenic materials for which special precautions against skin contact hare been planned. Shey are discussed separately. The aromatic distillate is described as containing 56 per cent aromat ics. Initial boiling point of the fraction is 300*?. and final boiling point, h75*?> Leaving the cracking coils, this distillate is handled by a purp near the control house. It undergoes fractionation at lo. k D & S; after separation here, it la put through a clay treating process similar to that at OLA. 2, in the chemi cal products area. Zt finally goes to Tank 961 as the western tide of the run down tank area. The boiling range of this fraction includes the boiling points of C9 and higher mono-nuclear aromatics. Ary problem of toxicity of fraction would be of the order of toxicity of cumenes, etc. sad sot of the type of benzene, toluene, and xylenes. Observations at this unit and at Tank 96I failed to dis close any occasion for prolonged breathing of this fraction. EM001668 There are several reasons why the operations at these units are of *5. interest to those concerned, with the maintenance of emp loyee health:. (1 ) Chron toxic effects of Cj sad related aromatic hydrocarbons are not sufficiently vell- understood; (2 ) the exact extent of occasionally repeated vapor exposures of me at these units could not, of course, he determined in the course of this survey ; (3) the process is similar to that at GLA-1 and QLA-2. There is no assursnce th changes in feed stock or processing conditions sill not result in the production of the more volatile aromatics of the type of benzene. Catalytic Cracking Scree catalytic cracking units are operated. Ho. 1 is the first fluid catalytic cracking unit to he put in operation anywhere and differs radically in design and operation from Ho. 2 and Ho. 3> Thich are identical. Materials and Process. Peed stocks for the catalytic cracking units include reduced crude free end-fired stills, virgin gas oil from crude distillate, various residual stocks from the production of lubricating oil, and cycle gas oil from thermal cracking. Products are gas (to C4), light naphtha, heavy naphtha, and heavy cycle gaa oil. A finely-powdered silica-alumina catalyst is handled as & fluid. Humber of Men. 90 persons are employed on three shifts in the operatic of the three catalytic crackers. Significant Srsosures. ' (1) Catalyst dust: Uni finding of fresh catalyst from the cars in which it is received is & relatively dust-free Job. Twenty-seven to thirty carloads of catalyst per month are received. Removal from storage and return of regenerated :a ca ly st are a ll handled - -1---- -------------- k6. units themselves "shea the M gh velocity of the catalyst stream causes corrosion in pipe lines, g occurrence is sot Infrequent, especially on the No. 1 PCLA. Vhen leakage occurs, exposure to the dust is suffered mainly by maintenance men vho are called upon to repair the lines. The toxicological 1 nos available indicates that this mater ial is unlikely to cssse silicosis. Oils nsy be due to its being so lean in very fine dust fractions cospared with naturally produced dust; or to its relatively 4 high rate of solubility. In any case, we conclude that any exposures we learned about are of no significance health-vise. (2) Heavy catalytic cycle gas oil: ttls fraction occurs in too forms at the unit, The first is known as slurry oil and contains catalyst in suspen sion. The second is clarified oil which is the ease oil stock after removal of catalyst. These substances are the principal materials Involved in the program for control of akin contact with carcinogenic oils. This phase of their activity is discussed in a separate section. Two other factors concerning the handling of these oils are worthy of consideration. The first is the existence of fine mist in the vicinity of hot oil pumps carrying either slurry or clarified oil. He demonstrated the existence of such a mist and observed that there 1 s occasion for man to spend at least abort intervals of time in areas where mist is present. An air sample collected by mesms of an lmplnger at PCLA So. 1, three feet from the shaft of a pump hewaung hot clarified oil was evaluated in a aannrr analogous to dust counting and showed 2 1.3 droplets per cubic centimeter. At the time of sampling, there was a visible mist arising from the abaft of the pump with each stroke. Mist also arose from the cylinder block upon which oil had been spilled from a sampling line. UJ Inhalation of oil mist affords equally good opportunity for contact as S T 1____ fc7. carcinogenic agent that nay be present into the body of a man. A careful review of all the localities where such misting occurs and. the correlation of this oc currence with the presence of sen seems to be warranted. The remaining consideration is the immediate formation of blisters upon skin of men where spillage of aV r ry oil bas occurred. It is true that in many cases, these blisters would appear to be thermal blisters from hot oil. There is good evidence, however, that same of the properties af the oil may be responsible. # In those caBes where heat can be ruled out aa a cause at blister formation, ques tion arises as to whether this is a unique effect of slurry oil or whether it is a manifestation common to several other petroleum fractions, notably kerosene. An associated question is whether occurrence of blisters may be related to the irritant effects on eyes and respiratory system following exposure to catalyse dust, a possible relationship lying in the adsorbed oil on spent catalyst. 9 E MO 01671 k8 . tw h t .it res AST U C ST BBS Petroleum Vanor . Bie principal effect of the af rapora of saturated epd un- satur&ted light hydrocarbons la narcoala from prolonged breathing of concentra tions in the range of a fev thousand parts per Trillion. Ve knov from refinery surveys that such concentrations do not prevail far prolonged periods in areas vhere men vcrk. Severer, industrial hygiene codes of same states snd the nation al Conference of Governmental Industrial Hygienists include tolerable limits of 500 or 1,000 parts per million as definitive of good vcrking conditions. It is a matter of Interest, therefore, to obtain seme estimation of concentrations that are encountered in the light plant of this refinery. Pur this purpose, the 1929 Gas Absorption Plant, vhose units sre nov used as specialty stills, vas chosen. The control house of this plant vas described to us by personnel of the light ends division as the most "gassy" in the refinery, the reason being its location in the midst of the process units. . Die fractionation towers at the 1929 Gas Absorption Plant handle prin cipally virgin heavy naphtha, separating C* and C* from Cj end heavier; they also vere handling propylene polymer, separating a small amount of C* from the remain ing heavier polymer. Headings in the range of 25 to 50 parts per million, vere obtained dovuvlnd from a sever opening beside vater cooling colls vlth a sensi tive combustible gas Indicator. Bnevbere about the plant, in the control house, at the base of Ho. Specialty Still, at Ho. 3 Rectifier, and dovuvlnd from a leaking valve 50 yards from the control house, readings vere essentially zero. Uieae readings shew the effect of the mild breeze, vhich vas bloving on the day the neasurenents were made (April 12, 19^9), in diluting the vapor soon after it *9. Th* examples typify oar findings of petroleum vspars around outdoor process equipment. Hydrogen Sulfide. In the coapreaaion and distribution of gases containing hydrogen sul fide and their subsequent recovery for use, the hazard has been reeogclzed and effective precautions to prevent its escape In places vhsre men vork are gener ally quite good. A fairly recent development has been the removal of sections of side vails at Ho. 1 and Ho. 2 Gas Compressor- houses. Ventilation thus provided is In addition to the local exhaust ducts at the compressors. At the various units of the light ends plant, vhen men encounter hydro gen sulfide it is most often as a barely perceptible amount in outdoor pus? loca tions vhere natural ventilation and lack of confinement prevent its accumulation. If ve disassociate from our consideration the necessary precautions against acci dental inhalation of amounts sufficient to cause lraedlate symptoms of acute poisoning, such as vould occur in equipment failure, it vonld seem that there is no problem of hydrogen sulfide poisoning. So areas vhere men vork for prolonged periods in amounts sufficient to cause chronic poisoning could be noted in this ' survey, except as noted in the discussion of the flare stack adjacent to the aev light ends plant. Acid Becovery Plants. Sie processes of hydrolyzing acid sludge, recovering veak acid, and concentrating this acid to 85-90 par cent by vacuum distillation is associated with the obvious possibility of accidental acid burns for vfalch. the proper pre cautions have long been practiced. There is nothing else significant to esployee health about this type of vork. f wo 01673 50 Boiler Houses and Power H o m e s . She beat approach to the question of possible dosage to hearing In places 'here high noise levels exist, such as the power houses, is to sake a hearing Inventory """g the sen ho are exposed., In order to detect any changes vith the passage of tine. Me&ruresents of noise levels In the work places do not give a satisfactory basis for predicting dosage to hearing. Satisfactory standards do not exist, chiefly b e c a m e of great variation In response between individuals at given noise levels. The matter eon be resolved by determining the state of a person's hearing In a pre-placement rani nation and determining in subsequent yearly examinations any changes that occur. E M 0 0 1 674 51. M A I S I Z S A 5 C S AID C 0 5 S T I U C T I 0 31 PIPE ST7ISI05' The Pipe Diviaion of M. & C. Department n s subjected to careful study in the course of the aurvey because personnel of the division ferns a mserically large segment of the plant population and because the p erf ormance of the func`tions of the division places its sen in intinatte contact vith process material. Pipefitters comprise 23 per cent of M. A C. employment and about 9 per eeut of the total refinery personnel. After the General Labor Division, it la the nert largest M. & C. division. The Pipefitters enter into nearly every phase of processing iron the initial installation of a unit through its normal operation, routine maintenance and general inspection, turnaround, dismantling, or change of design. In their worb of blanking off H t w * tar removal or repair of pieces of equipment, they can suffer an exposure to vhatever material is in the unit. The magnitude of the exposure is dependant chiefly on the effectivenees of draining or flushing by the process people before the unit is released to the pipefitters. E p i c a l exposures of this nature range firem the short-time breathing of gasoline vapors In an in stance vhere a pusp or valve on a gasoline line is removed from service to an occasion vhere pipefitters render prolonged eaalatance in removing a large cumber of heating tubes from a crude reboiler In acid service at the alcohol plant. The former is typical of an exposure vhere the hazard to health is of a lev order of magnitude, the latter, cne of doubtful or uncertain magnitude. Of the 765 men employed in Pipe Divlaion, close to 200 ore regularly assigned to process units. These men have fairly steady assignments and are sub ject to fairly steady environmental conditions. Tnmarcnnd verb md shifting de mands of building and reconstruction gives to most of the men is the Ei'*tsior ' 52. Bn-rtrarmuwr+jQ , studies, as a port of the protection of the health of pipefitters, can do so acre describe the nature of materials encountered, their toxicity, rough estimates of exposure time and jftrequency of exposure, and number of men involved or affected. In most cases, nothing can be said about the range of concentrations of an atmospheric contaminant prevailing In a given exposure incident. The random occurrence of pipefitters' lobs makes aaspllng an measurement impractical except as part of a long range program. Protection -sill depend an keeping & complete medical inventry of all men in the Pipe Division who have occasion to spend part of their working time i: areas where exposures that are difficult to classify may occur, t h i inventory should include periodic medical examinations, recording of occupational historic: and application of clinical laboratory analyses for the early detection of signs of exposure. An example of the latter is the urine sulfate test for pipefitters who work about the MZK Plant, to detect exposure to benzene vapor before symptom of poisoning occur. Some tTpical exazpies of pipefitters' exposures are reviewed below. Catalytic Craelrtw Units. Catalyst dust is encountered in fairly-freqpent repairs to the catalyse line from the Cottrell precipitator to the regenerator. lye irritation occurs. Its total effect after repeated exposures can only be determined by medical super vision of the pipefitters and boilermakers who have been longest exposed. Expo sure during repair of i abov^ the ammonia feed should also be studied. Heavy aromatics boiling over 700* are encountered in replacing slurry heat exchangers while the unit is in operation. Flushing cannot be accomplished in the procedure currently in use. Removal of steam generators at turnaround is 53. flushing. These occasions require consideration of mechanical changes to i^rrm the method of flashing sad draining (if it has not already been solved), and d o s e scrutiny of the men involve^ to detect any early pre-caneerous shin changes. Alkylation Units. Vapors of light hydrocarbons and possibly hydrogen sulfide are encounter ed in breaking lines prior to pus, Talve, and pipeline repairs. Infrequency of 1e Job and inertness of most of the materials encountered suggest that these are harmless exposures. Accumulation of a body of medical experience with the vto verb in this area conclusively put it in its proper classification. Vax Manufacture. Pipefitters hare three men full time in the area which Includes the vax press roams, crude scale sweaters, and refrigeration units, lhelr opportunity far skin contact vlth suspected carcinogenic substances probably exceeds that of press cleaners in the vax press rooms and cellars. At the sweaters and coolers, repair verb requires contact which the process people never experience. Biese men should be included in the provision of protective clothing and frequent medical exami nation. . Phenol Plants. Bin two pipefitters who verb full .time in this area hare occasion for infrequent exposures to concentrations of phenol vapors in verb at the hot pumps. Tbe net result of such exposures over an extended period of time an the health of the workmen c m only be determined by paying careful attention in routine medi cal examinations to respiratory, nervous, or digestive disorders. Equipment far protection against skin contact vlth phenol and firstaid facilities are provided. The accident hazard is veil-understood at the plant. MO 0167 7 5*. Barlsol Plant. Almost foil attendance at this plant was required of pipefitters. Since operation has bees discontinued, the pipefitters etc- spent the greatest ; amount of time here *haa3d he uatehed by the Medical Department for sequelae of ' exposures to carbon tetrachloride. It is a matter which will require careful study as the literature is 3gV-jng in reports af prolonged follow-up of acute or chronic carbon tetrachloride exposures. Lube Treating Area. Four pipefitters ere present full'tlae in the area Including veak. acid '.tw recovery and lube agitators. Their exposures to acid slot and sulfur dioxide is potentially great engmgVi to warrant medical supervision aimed at ascertaining whether excessive tooth decay occurs and whether there is abnormal occurrence of upper respiratory affections. Alcohol Plants. c.. The large scale use of sulfuric o d d In alcohol manufacture and its re covery at this plant requires constant combating of effects of corrosion. It Is a place of Intense activity on the part of pipe fitters. About fifteen man spend all their time at ethanol production, propanol production, and acid recovery. H e entire group la likely to encounter all substances at this plant from row B&teriols fed to these units to finished products. As pointed out in the discus sion of process men at the alcohol plant, most of these substances cannot, on the taals of present knowledge, be directly Implicated as detrimental to employee tealth. She possibility of the presence in this area of one ar mare carcinogenic ^Sents dictates the necessity for careful medical supervision of the pipefitters t sod other mechanical craftsmen *gd laborers who spend most of tbeir time in the -fta. The examinations of such employees can be specialized along lines indlE no Cl 67 8 55. H. & C. Machinist Die total number at men Is the Machinists Division is hjk, w t the third largest M. & C. Division after General Labor and Pipe. Like the pipe fitters, they are fairly stable Is assignment to fixed locations. Shop men number 121, the remainder, with a fev exceptions, are outside machinists assigned to a. given area or process unit. Outside Machinists. Die general character of the machinists work at process units is to perform routine duties of inspection and oiling, to move In to a pump in need of repair, replacement, or cleaning after the pipefitters have eospleted b l a d ing off the line and to perform special tasks of installation or repair, again after the pipefitters have been there. In qualitatively evaluating their ex posures to process materials, it is apparent that the sum total of outside machinists encounters everything in the refinery, and individual members of the group experience repeated contacts vith the materials within their osn area or unit. The frequency, Intensity, and duration of such contacts enters into the quantitative appraisal. For purposes of comparison, it appears to be less fre quent than similar exposures at the pipefitters, less intense, snd about equal in duration. With awareness that exceptions to this .rule occur, any accurate appraisal of pipefitters' exposures to process materials should be applicable in judging the exposure of outside machinists. Examples of certain machinist activities in vhlch there is opportunity for repeated exposures to materials processed in the unit follow. MEK Plant. E P 0 01679 Ever since operation of this unit vas started, tvo machinists have been employed consistently, realigning the foundation of the filte r tanks. 56. These men here probably had a greater exposure to the solvents than any of the process people or other crafts. At the conclusion of this Job, they should be given a physical examination related to symptoms of benzene poisoning. The results of these examinations sill be useful In evaluating the exposures of those vho are regularly employed at this plant. Two other machinists spend 30 to 50 par* cent of their tine perfoming regular maintenance duties at the MEK plant. We have no indication that they suffer excessive exposures to solvent vapors. Phenol Treating Units. Onr observations at the phenol plants lead to the conclusion that the two machinists vho work full-tine at these plants and at the Kellogg pipe stills are not exposed to phenol vapors for prolonged periods of time. The low vapor concentrations that exist during normal operation of the plants suggests sn ex tremely low total exposure for machinists. Machinists are in possession of pro tective clothing for prevention of skin contact. Showers are provided for use after accidental contact. Paraffin Wax Presses. , Two machinists spend about 90 per cent of their time on wax press maintenance. We consider that their opportunity for skin contact with paraffin distillate, wax, and pressed oil exceed that of the filter press cleaners. There is contact with various parts of the presses themselves and with the freezers in the refrigeration building. Repair of the stirrers and other parts of the freezers requires entry into the unit through a manhole. This Job re quires assistance from other maintenance machinists. The two men vho are nov assigned to the vax press maintenance and E *001 68 0 57. those tvo vho were formerly assigned (those vith the longest tenure can he identified by the machinist foreman) should be given the routine physical exami nation required of the press cleaners. Equal facilities for the practice at personal hygiene are necessary for the maintenance machinists. Butyl Rubber Reactors and Building. H e r e is a lov incidence of exposures to methyl chloride by the sachlnists. In the reactor building, natural ventilation through the open aide vails is usually good. In the finishing building, routine greasing of the screen shakers and the filter mechanisms requires exposures of short duration. Repair vork on these units is performed shile the flov of materials is shut down and vhile the ventilation system is still operating. Paracril Plant. Exposure of machinists to acrylonitrile and other volatile aubstaneee in the paracril plant do not exceed thoae of the operating personnel, vhich were ahova by air analysis to be vithin acceptable limits, except in the vicin ity of the latex pot and the coagulating pot. Gaa Compressors. Since maintenance of gas compressors in various parts of the Petroleum Products Division and the Chemical Products Division accounts for a large part of the total time spent by maintenance machinists, there is a certain degree of importance attached to the possibility of gas inhalation at these units. In our examination of the compressor buildings, ve failed to see any localities vhere accumulation of amounts of gas sufficient to produce chronic Intoxication vas a likely occurrence. H e r e undoubtedly have been some exposures in the paat and may be occasionally at the present time. E001681 Most of the obviously dangerous 58. exposures hare been eliminated, either by providing exheart systems over the eeespe points or by opening up the building to permit natural ventilation. Methyl chloride hydrogen rulflde concentrations hare been reduced by these two methods, respectively. A review of all such Installations from the stand point of chronic exposures to lov concentrations of gas is recommended. Contact vjth Scary Catalytic Cycle Gas Oil sad OLA Tara. ' The machinists are the crafts vhi oh have had and vill continue to have opportunity in the daily performance of their duties at the process units vhich handle these materials and at field tank pumps for contact vith these substances. Future contact is regulated as a part of the general program. No unusual or unforeseen incidents relating to contact vere observed in this study. Machine Shop Main Shoo. H e main shop vas found to be vlthout any apparent Industrial health problems. Lighting and sanitation facilities are excellent. Use of solvents is limited to 7arsol, which is handled in such a vay that, even though its toxicity and volatility vere great, exposures would not be significant. Disassembly and Reassembly Shop. Pieces of equipment come to this location directly from the process .units or from an Oaklte cleaning in the of the heat exchanger cleaning shop. Those pieces of equipment vhieh have been in service at units t r ^ ^ g the heavy catalytic cycle gaa oil, OLA tars, or re-run tars bear a special E*0 01 682 59. identification tag. Shea they ire disassembled, one of this inspected car- * cinogenic material may be released. We aav sIu z t t oil spill out of a slurry pump vhich had been through the Oakite cleaning. Share is a problem of its disposal. The nearest drain to the sever is shout 60 feet froa the place vhere heavy equipment is disassembled. Metal Spraying. , About 15 different types of metal are sprayed in a shed vith open sides near the machine shop. Stainless and mild steel vires are most frequent ly used. The amount of lead spraying seems to be too small to be of any lm- - portance tcxieologlcally. It vas described to us as consisting of about one small job a month for a part of acid service at the Chemical ?rodueta Area. Bronze is no longer used. Incidents of poisoning by nitrogen oxides generated by the heat of the spraying torch,that are described in the literature, have occurred in enclosed spaces vhere it has been possible for concentrations of these gases to accumulate over a prolonged period. It is safe to assume that such accumu lations could not occur in this open shed. EM0016B3 So. boilbbmakhb oiTZSZcar MS- Ihe vcrk of the riggers , uho numbered 67 In the entire plant, dll not come in for d o s e scrutiny in this surrey. It m i adjudged that in the perform ance of their mission of hotlag and ting heavy equipment, their exposures to toxic and hazardous material are slight. Hlggers are not active on a job until after process men have a given piece of equipment off stream and pipefitters have blanked it off from the flew; actual d o s e work vith the equipment ia of abort duration. Opportunity for n * contact vith acids or high-boiling aromatic hydro carbon exists. For protection, riggers are furnished protective clothing, vhich they carry vith them to a job. Contaminated riggers1 clothing is laundered by the refinery in accordance vith the general program for prevention of prolonged contact vith substances implicated as possible cancer-formers. Welders and Burners. - .-- 106 velders 98 electric velders and 8 gas veldera. Ill of these men are first class mechanics and their work is limited to velding. Fitting of parts to be veiled is done by other crafts. The burners number 66, consisting entirely of first class mechanics. Work inside drums, tovers, etc. amounts to a considerable percentage of the total work of velders and burners. An important aspect of this inside work is that pieces of equipment in vhich inside work most be done ere routinely d e a n e d by sandblasting before the velders and burners enter, ttia practice effectively limits their inhalation of atmospheric contaminants to those products of the velding or burning process, i.e., fumes or gases from the base metal, velding rod. cr coatiru:' 61. Welding os ordinary structural grades of steel vith coated electrodes results Is the escape to the ataaosphere of finnrw e n n t t ^ w g Iras <**** mnA nn Am* at several astals found Is the electrode coating. Manganese, titanium, sill cos are ecnaon. *W' gaseous products cossist of carbon dioxide, carbon monoxide, eater, and nitrogen oxides, these fumes and gases originate Is the exttaae heat of the arc asd are thus given an velocity upwards that tends to disperse them to less than harmful ggftegM t.i'wtlm n in any but the moat confined spaces. Given a fair sized enclosure and some natural movement of uncontasrtnntcd air from outside the eontamlnanta will disperse Is a satisfactory manner. Is eases where the voiding is performed in a confined space vith so ventilation the symptoms ore primarily those of nose ssd throat irritation, asd cough. In velding an galvanized steel, the proportion at zinc ccti.de in the total fume is greater than that at iron cctida. Metal fume fever may result unless total fume concentrations are kept at a mush lover level than la necessary in the case of velding on uscoated steel. Good ventilation of the space is effective In preventing the occurrence of aartal fume fever. Welding on or cadmium-coated base metal may constitute major bealta hazar ds. Cadmium fumes are not believed to constitute a chronic poisoning hazard, but do represent a very serious accident hazard where ccncentratiana sre high due to poor ventilation. Sxposures of only a few hours duration sre sufficient to cause serious lssg involvement and even death. Protection may be provided either in the farm at local ezhaast ventilation as the w a r i n g of a feme respirator be- oeath the wider's face shield. Vo Instances of these types of velding were noted in the refinery. Welding an stainless steel Involves exposures to fluorides from ths rod. coating. Excessive exposure to these fumes causes Irritation of the nasal pass- es, and not infrequently nosebleed. This is generally believed to be caused by `he formation of hydrofluoric acid. In our opinion, there I p m , ' *v 62. fluorosis from such exposures, necrosis is s development of box sbnornalltiea resulting from, many years exposure to large conr.rutratioca of fluorides. We sere to obtain s first-hand Impression of fuz&e eewdf ^ any of this welding work. However, the exposure being basically af nuisance type, scientific evaluation is not required and ordinary Inquiry sill suit ell purposes.' Ventilation tear inside Telling work is provided by Leah "air siphons" furnished by the boilermakers end Installed by pipefitters, in estimated JO or 1*0 "siphons" are available in the entire refinery. Surfaces painted with red leed are encountered In artnor repair work on barges, sn infrequent Job, and on new structural steel, also Infrequent, in el- , eetrlc blower Is provided to furnish local exfcanrt an the barge work. Bed leed is rem oved from new structural steel by burning and brushing prior to welding. The short duration of these Jobs and their lack at frequ ency make it unlikely that there Is any hazard to burners or welders from inhalation at lead fnae from work on steel that has been painted with red lead. Protective clothing is provided tar work in a d d areas. Zt is stored In division tool roaaa or kept personally by Individual welders. Coke deposits are seaetiaea cut from inside equipment by burners' torch. TeatUation equipment is n r f for and used because of the smoke and heat in confined quarters. Cutting and at lead scrap In done by one nan with a portable lead pot, working occasionally at various locations. Several efforts to witness this Job failed because of its discontinuous operation. This man should be in cluded in physical examination schedule for lead burners. file Pipe Shop (Petroleum Products Division) is operated Jointly by Pipefitters and welders. Pipe welding is done in a structure having open sides. An estimated 95 per cent of the work is on new pipe, limiting fume exposures to the innocuous type of black iron welding. Lead-lined rln* < -- * --- 63. shop. Fume exposures sre not serious at thin chop at thin tine, >tngh cer tain position nay pot a welder's head for a tine In the region of heavy fane from the are. earns a more serious nature If in the future the new pipe containing a hooded W * lining, *frich was described to us at the acid plant, should be brought to this shop far catting or welding of flanges, ftrovi- ''' slon of local equipment for removal of the fuses from their point of origin to a distance from the welder's breathing zone would then became neces- aary- Bqitfrwwdrf shop, 572 Area, in Chemical Products Division north of So. h Finishing Building, ploys one welder and one burner. There was nothing in the layout of the shop nor in the description we obtained of its work to sug gest the existence of occupational disease hazards. Pine Shoo, Chemical Products Division. *cT"' / , ^ * . At the welding shop, Chemical Products Division, vest of So. 1 Alcohol plant, five welders and three burners, all an ."d" shift, sre employed at fabri cating and repairing pipe sections. Fume exposures sre limited mainly to fumes from the metal being welded and the rod and coating. Io estimate could be ob tained of the relative proportions of verb on new and used pipe. It was ascer tained. that residnal asteria! in used pipe was removed by burning at a point re mote from the shop In a that results in no fuma or vapor exposure to the man doing the burning. In this shop, welders e m p 1! of illness, from weld ing on certain tjrpea of alloys described as "Bed Copper," "Bed Brass," and , 7 "Everdar." In velding such material, heat is applied by means of a carbon elec- c troie in the usual welder's electrode holder. Pipe sections undergoing this pr-^ cess are of such sizes a shapes'that it la Impossible for a welder to always stay out of the zone of most dense fume from the arc. EM001687 64. The illness they described is suggestive of octal fuse fever, being .an acute illness having its onset several hours after verb has ceased, and being characterized by chills, fever, vomiting, and headache. She Everdnr alloys contain copper, 95 to 98 per cent; silicon, 1.5 to 4 per cent; and about 1 per cent manganese. 'Bed Brass usually contains 85 per cent copper sad 15 per cent zinc. There are no chronic effects from metal fuse fever. The acute illness can be prevented by installation of a local exhaust system in this shop to carry svay the fumes frem their points of origin. Boilermaker Shop. "Old Boiler Shoo." - - Activities in this shop consist of: gleetrie welding-one or two arc welders perform various repair Jobs. Burning-- three burners work In this shop full time. A vari able number of hand torch burners are present. Gas welding-- the gas welding shop In this building is the site of em ployment of the eight gas welders included In the employment list for the Boiler makers Division. The work consists of coy-acetylene welding at non-ferrous alloy parts, using principally un-coated rods of composition similar to the base metal. A considerable proportion of the work load consists of effecting repairs to Eas- telloy D heating tubes used in acid service at the alcohol plants, 3XA units, and acid concentrating plants. & e shop is provided with a local exhaust system for removal of fumes from the actual welding. Bsstelloy D tubes which contain 85 per cent nickel must be pre-beated to about 600*?. in a furnace at the shop before welding. Seme 20 beating tubes per month are handled here, and three is the mmriimm number in any one day. When these tubes come to the shop with a coating of same residue of carbonaceous material from the unit from which it was removed, there is an . 65. evolution, of fuses,'at least la the first stages of to the corr ect tem perature for veiling. ' She possibility of the foraatloa, under these conditions of combustion, of nickel carbonyl has been raised. Hictarl carbonyl, a volatile material poseas ing a high degree of sente toxicity, has been responsible for the development at lung cancer in the nickel refining industry. We are sot In a position to c c o e s t on the possibility of its presence In the fumes from heating these tubes. Inhala tion of these fuses can be greatly diminished by the installation of a hood over the furnace port. Welders at Catalytic Cracking Unit Turnaround. -i _ It turnaround of catalytic cracking units, the services of velders and burners are required for about 3/5 of the turnaround period. Welders vork three shifts a day, sis days a week, and burners on tvo shifts, 6 days a week. An estimated sixty per cent at the vork is inside work and of this, forty per cent is considered dusty work. A high proportion of the vork Inside is on stainless and chrome steel. Dust sources are residual catalyst, especially in the preci pitators vhere it is easily disturbed from its resting places on the shakers, refractory end insulation dnst In the regenerators, and settled dust remaining after sandblasters have left the tover. Dust 1Initiation efforts have gone a long say toward rferring ^ the vessels far the turnaround mechanics. Additional protection from inhalation of these dnsts can be offered these velders ami burn ers by pi'civ'i&inft them with a filter-type respirator designed far dust end fume. Types that will fit beneath the welder's hood are available. The danger at contracting lllneas from inhalation of these dusts In the concentrations p--- during the turnaround is thought to be rather email for the following reasons: (1) Erposure time for an individual welder or burner over the course E MO 0169 0 66. of a year elII snonat to probably so sere than one smith.. (Btere ere about four turnaround, periods of about 15 days n u i u l duration an the three units.) All boilermaker crafts are rotated an catalytic cracker turnaround; (2) Catalyst dust and most of the refractory dust that is encountered is relatively nan-hazardous by reason of its composition and particle size. LegdJforaeCT Lead Burner Shop at Ho. 5 Acid gleet. About four sen verb part-time la a ahop vhieh is open on three sides. ThiB affords good natural ventilation and prevents aceumnlation of lead fuses in the lead shop. It does not prevent the inhalation of fuses rising directly from the burning ar bonding torch. Measurements of atsospheric lead ftnring burning and bonding at Aruba shoved that concentrations la air at the nose of the a m can exceed the recommended U n i t even in outdoor locations, because of the proximity of the Ban's nose to the source of fuse. Yith this experience and vith the results of the urine deterdnatlons that vere made at Aruba, ve recommend, that same exhaust ventilation be provided for lead burning la this shop. Lead Burning Shoo In Crafts 4 Chemical Prodncts Area. Dbree sen vork about half-tine la this shop. Ibis room has fairly good natural veatilatioa. The same remarks regarding inhalation of fuses coming direct ly from, the torch apply here. Outside Lead Burning ma. Bonding. About half of the time of the seven lead burners tad seven helpers is spent p ei'forming jobs at the process units. Many of these Jobs require vork In spaces saseshat sore confined than the shops themselves. Samples are re-bo11era at the alcohol plants. c u n o1 t.oi 67 Medical Control , Lead tamers sod their helpers ere fgaufflned twice yearly by the Medical Department for g'mapinm at poisoning. Ve suggest that the em wi^w ^ w p y be supplemented with urinary determinations, so that evidence of absorp tion say be detected before'ymptems of poisoning occur. I s a part of this surrey, we ob tained crime specimens from 12 1--* burners and helpers. As a group, these xwn showed normal excretory values. She results are shown In the following Table. lane CChharpimstaonf EFilskhinesr KKeelllleeyy,, BB.. AF.. MKealrlteiny, 0. D. SDeiatntlaess V hittey Table 11 RBSTTT/PB QJP T.WiTl HMTOMTTTA'irTflWR U TOTTTP ay Isad BnRSEHS AID HELFKES Baaple A(Cmuobuinct Specific Somber Cent.) Gravity 33021*69 2n3o0 11..002208 31089330 328 111555 11..002257 380 l.a o 1203501 229955 . 11..001223 183*7*2 3032 117850 11..003200 93 1.025 31*36** *7955 11..0002*5 C(Monilcliegnrtarmatsionof Lead per lite r . ..107907 ..133220 ..005558 ..019583 ...113910252 .095 Periodic urinary 1 deterscLnatlose will r w ^id any changes In the ex* posures, which at the present time are not excessive. . Utility of Lead Ur**iysia. Bie measurement of the amount of lead excreted In the urine Is a useful means at evaluating exposure to lead and, therefore, a valuable adjunct to medi cal techniques in supervising the health of lead workers. T* 68. respirator systems of the members of the grunp of exposed persons ss collecting devices for the lead in the atmosphere. Sr Its mechanism of collection it eli minates soy farms of lead in sir that do not contribute to setnal lead absorp tion, sseh as coarse dost particles. Tnrthezmore, it aTcragea out exposure vith tine, J'fTtHTK'Mrtg the intermittent high or low concentrations that might be found In sporadic air nd analysis* Bie aacnnt excreted in the urine is pro portional to the aaonnt absorbed vithia certain limits of lndiTidoal variation. , 2he influence af individual -variation makes it necessary to use urin ary lead concentrations as measures of group exposures rather than as measures of individual exposures. Die knowledge of exposure obtained from urinary lead de term!nations can be utilized to point out the need for environmental control of the contaminant, and for Indicating the frequency of, or eren need for, medical examinations In the detection of early signs of lead poisoning. formal urine, from persons with no Industrial exposure to lead, con tains 0.02 to 0.10 milligrams of per liter, dependent largely on the dietary intake. Amounts of lead in the range 0.15 to 0.20 milligrams per liter sre con sidered indicative of exposure at a borderline level of actual toxicity, -vith a probable degree of aafety. Srtenslve experience indicates that the collection and analysis of "spot" samples of urine, containing about 100 ml., la a satisfactory procedure for determination of exposure. It has an advantage over the collection of 2h- hour specimen in that its collection can generally be closely supervised and the danger of contamination of the aasple lessened* Precautions against contamination are the use of chemically clean vessels and stopp ers scrupulous cleanliness during voiding of the sasple. In a 100 ml. sample, containing 0.15 mg. of l ead per liter, the analyst will have to vork vith only 15 microgrsms of lead. T*** possible influence of dust or other foreign matter in the swale is obvious. CM001697 69. Ve verc told at the a d d plant of the ccutenplnted use of steel pipe vith bonded l* lining. She use at this pipe say introduce increased exposure to lead fumes because it d l l not be possible to reagre the lead at rill, prior to changes in the shape or length of pipe sections, as can be q ? with the lead inserts nov used. She urinary lead deterdnations d l l be ralnable in detexdnlng whether this expected increase of exposure actually occurs. 1. u- w 6...i.-.st E H001694 70 MESS AED nsnSIMEBT HT7TSIQS ShCt^ .1 'f* Eie shop sen rog fcigiiy overhaul, clean, and repair setera and inr&u- ments. Diere la a <" ahop In the Petroleum Product* Area and a shop In the Crafts Building of the Chemical Products Area, ftaatlrr shops are located In the East and Vest Esso Laboratories Areas, and In the BLA. Mechanical Shops. ' In the shop worh, mercury is the principal hazardous material encounter ed. Measurements vere made of the concentration of mercury vapor In the air of each of these shops, except the BL& Mechanical Shop. In nose could ve find con centrations as great as 0.1 ag. per enbic meter of air, a concentration consider ed a safe upper limit for 8-homr daily exposure. B esulta of all measurements are shora. in Table 12 (page 71). The main Meter and Instrument Shop, vhleh handles the greatest volume of mercury, has a system for collection and recovery of spilled mercury, the ef fectiveness of vhich is shown by the absence of visible deposits on the benches or floor and by the rts'-moiy lor atmospheric concentrations found. The trial of tills system In the main ahop is expected to lead to simi lar Installations in the other shops. Blare is need of such a system in the Chemical Products Area Crafts Building and in the Bast and Vest Esso Laboratories shops. Although lov atmospheric concentrations were found In these places, the difficulty of removing spilled mercury from this type of floor ashes it appear that sufficient accumulations may occur to give rise to higher concentrations vitx the passage of time. . It is veil to remember that the occurrence of mercury vapor in hazardous concentrations In laboratories sad shops Is more H h e 3 y to result from evaporation of spilled mercury having erta1finely large surface srea, than from the actual osnlr pulations with liquid mercury in the shop or laboratory vorh. r u n m os 71. Sample liusber Location Table 12 ywuHrCnUsPYAVHDAPBCRS2MSDBHAESLHBTSfSfiTUOTPSS-- Air Volume (Cu.Ft.) Mercury Concentration (Mg./cu.m.) Main Meter sad instrument Shop. Xn vicinity 20 of meter racks. Sample intake near floor. Main Meter Instrument Shop. 3h room 26 used as office and storeroom. Visible de posits of spilled mercury an floor. Saaple inlet at clerk's desk. Shop in Zast Pilot Plant Area. lev location for this shop. Ho visible deposits on this rough concrete floor. Sample intake on top of vcrk bench at vurkera1 breathing level. . 15 Shop in Vest Ssso Laboratories Area. Shop 10 located here far 3 months. Signs of spill age around mercury reservoir under bench. Bough concrete floor. Ho floor drain. Staple intake moved during sterling to three locations at breathing level. Shoo in Crafts Btrtldlng in Cher-Leal Products 20 Area. Visible deposits of spilled mercury on rough concrete floor. Floor drain has no trap for recovery of mercury. 0.06 0.08 trace trace 0.08 Hie use of Tarsol for eie.rMng purposes in these shops Is not considered, hazardous In viev of the m o u n t s used and lov volatility of this product. Outside Men. The principal duties of the outside men are inspection of thermocouple veils and orifice plates, trouble shooting at instrument locations, including re pair at the site, and inspection and repair at time of turnaround. These routine duties take the meter and instrument into areas of E MO 01696 72. exposure to process aaterlal of highly diversified character. Quantitatively, their exposures are considered somewhat less than that of process operators at the respective units. They are furnished protective clothinr to prevent shin contact vlth heavy aromatic distillate, acids, and alkali. Biat they are some times exposed accidentally to high vapor concentrations is evident from the ac count of a "fainting" incident that occurred in the MZE plant and the fact that cases of poisoning vlth methyl chloride occurred among meter and instrument men vhen its use vas nev. Exposure to Tgpar in confined spaces by outside M & I men is not steady enough to cause any concern. Shin contact vlth liquid mercury occurs on meter and instrument repair Jobs. The frequency of its occurrence vas not ascertained. It is not a serious potential source of industrial disease, because (1) the supervisors and the men knov that it should be avoided and do so as much as is possible; (2) vashlng facilities are available and are used after encountering liquid mercury on the Job. Shift Hen. Shift men of the Meter and Instrument Division verb out of the main shop and the Chemical Products Area Craft Building Shop and on the current turn around Jobs. Their verb does not differ from that of the straight day men in the same area. E PO 01 69 7 73. wrarmraAT. U17IS10E greater pert of the time of these Ben is epest easy from the proxi mity of process material, fiepair of refrigeration units, as In drinking foun tains and air conditioning equipment, wiring and leap replacements in the offices, maintenance of pgver H a w overhead and beneath the ground are Jobs that require no consideration'in a reriev a health factors. * In wcrh at the units,9 such as installation of lamps, maintenance replacement of motors, power and light wiring at turnaround, etc. the electricians1 contact with process material- is generally neither Intense nor prolonged. They work out of the shop and way stations. Two or three men at a unit t.vi'nnyffirr,^ g ^jje usual number. t line Gang. The lin e gang is composed of 13 rated men and one laborer. Sue work is mostly outdoors on overhead lin es. Occasionally they are employed at pulling cable in underground conduits and, in bad weather, they may be employed at lamp ing in and around process u n its. Their esployment is ncn-bazardous from the in dustrial health standpoint. gLectrlelana Aaalgied to Process T.horatorles, and Offices. Tire men are regularly assigned to process units, two at the catalytic cracking units and three at butyl rubber polymerization. Twelve electricians ore assigned to laboratories and offices. They may be excluded from consideration of health hazards. mo 0169 ? 7^. Main Electrical Shfm. " 'w*. u ,Wi ^ * . Four sen are present full time at the mala electrical shop. 2heir work is primarily that of actor nrHeg and repairing. Approximately 100 aotora per month are handled in this shop. Varsol la the regularly used 1 earring agent. Its use in this shop is probably the greatest opportunity that exists in the re finery for toxic manifestations from repeated dally inhalation and shin contact, should there he any such manifestations from this substance. According to a description famished by the fiefinery Laboratory, Varsol consists of a narr ow cut fraction boiling between J00 and UOO degrees Fahrenheit. Its aromatic contest was given as follows: Varsol B (105) VI aI rFsolalshC V(1a0r6s)ol(107) 15.5# 1153*-05## Shis boiling range would indicate that benzene, the most toxic of the aromatic hydrocarbons, la absent and that toluene and lyienes are also absent. Aromatic substance In the analysis would presumably consist of ethyl benzene, propyl benzene, isopropyl benzene (cumene), ethyl toluene, etc. These compounds are In a class about which little is known toxicologi cally, except for the acute effects of single large doses. It would seem that tin low aromatic content, low volatility, and natural ventilation at the shop would result in a toxic vapor exposure of a low order of magnitude. Determination of just what the exposure amounts to and what its effects may be an the men as de termined by close medical observation vould be desirable undertakings. Pedigree Products Bo. 150 Thinner is used in the shop to the extent of about five gallons per week os a thinner far Insulating paints and varnishes .which are sprayed, for cleaning spray equipment, and far cleaning -the hands. This product is described by its manufacturer as consisting of commercial xylenes. Its use constitutes an expoaxxe of undetermined toxicological aignificance. Although EH001699 75- the toxicity and volatility of sylenes are lav, praying of paints containing then as a thinner and intimate n contact In v a a M a g the hands aay produce un desirable effects la the men. Bespiratary protection for the operators of spray equipment and substitution of a less irritant shin cleansing agent are logical starting points for t i w m w r m of any hazard that exists. In periodic aedlcal examinations of these vorkers, attention be directed at discovering any eye Irritation, dermatitis, or central nervous system changes. Skin Contact uith Suspected earr i n g - Skin contact vith heavy aromatic oils and other petroleum products from handing contaminated extension eards and floodlights that hare seen service at process units is avoided by routine cleaning vith steam by one man on "S " shift at the electric shop. d e regular duties of electrical maintenance men do not subject them to eostact vith acida or heavy aromatic olla and tar. Any contact la accidental, Involuntary, and infrequent. Underground Lead Work. Lead hMrfc'Mwg in underground electrical conduits is relatively scarce In this refinery, being used for one voltage. Maintenance vork on lead sheathing in underground conduits is done by one man. It vas estimated that he is engaged for no more than one veek per year at this type of vork. Because of its Infrequent occurrence and the nature of the vork, no lead poisoning hazard can be faraeen In this vork. .Occurrence of nitrogen O r M Vacuum tube rectification at the catalytic cracking units elindnatee tin possibility of exposure tc nitrogen oxides, vhieh is said to occur in other plants. E "0 01700 MASQS IE7XSXQH 76. aj. - < - Shis division workers, and 72 insulators. 65 bride masons, 56 concrete and sandblast Masons. fixe tearing devn s??d removal of furnace bride at the Ho. 22 thermal 4 cracking unit vas observed in order to determine the degree of intensity of dust exposure in this type of vori. Four dust counts made in the breathing zone of man performing this verk shoved concentrations ranging from 0.4 to 2.5 Billion particles per cubic foot, vhieh are beneath hazardous levels. In verb of this kind, there is usually acne degree of natural ventilation. Sie York is inter mittent. Some unit turnarounds require a ***" amount of brick replacement. Dost encountered in this vork venid be expected to contain free silica to the extent of 25 to 30 per cent, as found in the Aruba survey. She job, therefore, is not considered to constitute a positive silicosis hazard. Laying of nev brick requires seme cutting to shape at the site. For this purpose, the division has three clipper s o n . They sre equipped vlth dust exhaust but no collectors, file dost is discharged to the air at the rear of the spparatna. fills effectively prevents the prolonged Inhalation of dost by the operator. Persona in the area are, of course, exposed to the discharged last. Their exposure is occasional since the saar is portable, file nev type of sav } vlth, vet dust suppression, vhieh is on order, vlll effectively prevent this nuisance practice of discharging dust to the air. file replacement of brick in the catalyst regenerators in fluid cata lytic cracking units is known as a dusty job. The greatest source of dust is the disturbance of residual catalyst in the chamber. _ Of secondary importance is r m n a i >/>* 77. asbestos dnst, which is present to an unknown extent. It is probably ainor be cause there is so process thereby the asbestos is bochen doro to fine particle size. She overhanging "Jointless" firebricks used in this Installation can be excluded Croa consideration as an important source of dnst for the method of in stalling then la not dnst producing. Sis longevity of the brick in this service, and the normal frequency of four turnarounds per year serve tc classify this dust exposure as occasional. t Heplaeemeut and laying of brick In a d d areas constitutes a large part of the brick masons' enployaent. Bis brick has a lov free silica content. Cut ting and shaping is dong outdoors, file dust closure is sot considered hazardous. Die of Basalite adhesive can result in exposure to irritant fuses, unless precautions are taken, file Irritant property of the fuse 1s so intense that chronic exposures are necessarily avoided by the men themselves. 'L/-. Concrete and ^"^ T a s t There is an interchange of sen between concrete and sandblasting Jobs which makes it difficult to determine Just bar nany persona In the course of a year spend sufficient time in the vicinity of sandblasting to require physical examination by the Medleal Departm ent, file tendency toward require ments for sandblasting process equipment prior to mechanical work at unit turnarounds makes it necessary that a continuing check on ezposed personnel be kept by or far the Medical Department. At units where ve observed sandblasting inside towers, drums, or other equipment, the dust was well *""gh confined so that only the man h wwaung the blasting hose was In a high concentration. He is, of course, protected with an approved supplied-alr mask helmet. There nay he, and probably are, occasions where escape of dust is in the direction of attendants at the sand blast machines. EM001702 78. This is a situation which can only be evaluated by repeated observation and measurements at the scene. At the sandblast shed next to the salvage yard, blasting of small parts iron the process units, such as bubble caps, is done almost daily. The open sheds provided for this work provi de no conf i nement of the dnst. The shed where men must stand to attend the machine is suff i ciently close to the blasting to receive at most times a h*gh dost concent r ation. The attendants use no respira tory protection. Oust counts Is th is srea, as shorn in Table 13, which follows, ~ ranged from four to I t million particlea per cubic foot. These concentrations'. /*, '/ are excessively high for free slliea dost. Attendants at these units should be required to wear dust respirators during the whole time th at sandblasting is being done. A mare satisfactory long-range solution to the problem w ill be to provide a modern enclosed sand-blast shed with dust recovery system at the pro posed new location at the Hechanlcal Crafts new buildings. Table 13 dost ctacanhAPOBS is txcikiti q? saeeblast seed HSaummpbleer STiammepling 68 5 Mn. 69 5 min. 77 5 min. 78 7 min. 82 5 min. EhO0170 3 Location Around perimeter of brick-crushing shed. Ashteedn. tra*n!*c*e tios tshheedrejugustlaer assttatoifonsaonfdbtlhaestimnagn -tending the machine for the sandblasters. Tnside -the shed mentioned in So. 69. Same location as So. 77* AHolonbglaastidinegthbeeinegastdeornne-minostthsisansdhbeldasat tshthedis. wtimorek.ingDiunstthcoemoesthferromshtewdo. sandblasters D(MusitllCioonunt ppearrtiecule.fst.) 7A lfc lh 7.5 4.2 Brick and Asbestos q h w M w . lA *t'iS In a shed adjacent to the sandblast shed, a crashing g M * g used aereral day each month to provide ground brick to be used as aggregate. Its use for grinding asbestos vas described to us as very infrequent. Although, an ex haust fan and duct are connected to this machine, there is considerable escape of fine dust within, the daring Its operation. Another Important source of dust at this location is the sandblast shed next door. Ve feel thst even in times past, then bride grinding vas a continuous daily job to beep the polymer plant catalyst tower supplied, the high silica dust from sandblasting could have been a acre important health factor the occasional asbestos dust and brick dnst in this shed. Use of a dnst respirator in the bride grinding shed should be re quired. Insulators. Ve ssv no operations in the refinery vhere Insulators would be exposed to high concentrations of dust, harmless or otherwise, from the material with vhlch they sort. They do use a large variety of cements, thlsaers, solvents, and adhesives of unknown composition. There are some occasions vhere high concentra tions of volatile constituents of these products will be encountered. Sae Medical Department should have same of acquiring knowledge of the particular pro ducts that are in use and what the principal constituents are, so that proper medical control can be exercised. 80. GZES3AL LABOR Refinery Disposal Dans. . T' v..' ^ . V* y .y v .\ A v ' O' V \ Fourteen men are employed snathe majority hare vurked here acre than ten yeare. All types of liquid and solid vastes from refinery processes, to the extent of 100-150 truckloads daily are disposed of here by open pit burning of combustibles. Since combustion is only of ban-fire type, considerable smoke re- sult4 and there is undoubtedly opportunity for major vaporization of materials surrounding the area of the actual fire. Pushing of heavy ara&aties is said to be one of vaste materials, and this suggests the good possibility of exposure of men to smokes containing Injurious materials in vapor or mist form. Obviously, the men vili attempt to take advantage of rind direction to avoid smoke, but this redeeming feature vas minimized by our Informants. At the tins of our inspection the vlnd vas favorable for avoidance of smoke. Ote variety of vaste materials handled and atmospheric conditions makes it impossible to appraise these condi tions on a scientific basis, beyond the suggestions outlined above. General Labor supervisors rate the occupation as one of the verst problems they have. Ethyl Lead TwnVg Cl*rrf . This hazard is recognized and precautions taken to comply vith require ments and recommendations of the Ethyl Corporation (as veil as duFont), vhich In cludes gas testing before entry into tanks, use of special protective clothing, ' supplied-air respirators, periodic medieal examination. Exposure to Povder Catalyst Dust. Cleaning Reactor Chamber (PCLA). A number of are exposed for an estimated average of three months per year. Bie dust is very Irritating to the upper respiratory tract and to the eyes. 8 1. It was generally agreed that asn wear the respirators provided, faithfully, and this is a good at the Irritating qualities of the dnst~#ince voluntary veer at respirators la only done where discomfort it isposea is of lesser extent. Goggles provided are v n m but not as faithfully as respirators and,frequently, minor eye injury eases are reported to the Medical Department. Cleaning Bubble Tovars. ' Inspectors, as veil as laborers, cannot totally avoid skin exposures to various deposits In bubble toner and plate cleaning and Inspecting, even though they vear rubber suits. These men literally must lie in the material vhere space is often no acre than 15 deep. Seme examples of this type of exposures are In the bubble towers of Cracking units 17, 18, 19, 20, 21, and 22, Pipe stills 1-8, PCLA. 1, 2, and 3, ALA. 1, 2, and 3, tc. Baa deposits encountered in such places consist of % vide variety of materials from gas oil sad naphtha used for flushing prior to entry to heavy polymers and coke deposits of unknown eampositioa. Exposures of this type to skin contact vlth materials of unknown com position and toxicity constitata one of the category of exposures of question^* able importance. Puller understanding of the effects of such exposures can only come with continued medical observation. Qie desire for complete health protec tion of refinery dictates the necessity for avoidance of such exposures as much as possible and Hurftring the occurrence of possible ill effects by re storing cleanliness of person and clothing inaediately following each exposure incident. Cleaning Reactors. Light Ends Plant. E MO 01706 Renewal of polymer!nation catalyst occurs at a rate of about once in three months and lasts for about two days. The Job is performed by & group of 82. ten sen at as out-of-doors location. The material they encounter is coarse and . granular, hence non-dusty. Ho significant exposures can he seen In the perform ance of these duties. Tank Cleaning. A certain amount of unavoidable akin contact occurs vixen laborers enter a tank to remove sediment remaining after pumping out the tank. These exposures are in the same category with those described in the section shore, entitled Cleaning Bubble Towers. Respiratory protection is afforded by the use of hose masks. Spent clay from the lube filters is used to "dry up" the las* sediment to_ facilitate its removal by wheelbarrow, This practice constitutes no dust hazard by reason of the granular form of the material used. Tube and Soaker Cleaning;. An important segment of the duties of general labor consists of clean ing tubes at the fnzsaees of the various refining units. Some ^eighty men are esiployed on this job .over three *-Hy shifts. . There is no doubt that this is a dust-producing operation. It is likewise evident that there la no accumulation of duet concentra tion at the breathing level of the cleaners, because their position is open to the outside air an three sides and above. There is usually a fair amount of air movement about their position. Vhen dust production ceases, dust at the breath ing level is quickly dissipated. Die production of dost is fairly constant after the tubes have been opened and cleaning equipment has been put In place. Total exposure time, as for most M &_C operations outside of shops, is variable and. hence, unknown. The effects on health from inhalation of these dxxsts, if sod vhen it occurs, are likewise unknown. F MO 01 7 0 7 83. Cleaning Pragg at Cr**Hwg Units. Clermlng out vertical soaking drum at cracking coll Ho. 22 vaa gp by means of a mechanical anger inserted from the bottom. Water rash flora down through the drum. Shis eirH*g rig is used os 19, 20, 21, and 22 colla. Four lahorera comprise It* crew. There la so dsat exposure beeaoae of the uae of rarer. There is op portunity for akis contact with materiala Is the drum vhile fitting the bit and while clearing the sludge coke away from the rig. We rare told that ase TMw la sometimes put Into the drum from the top for acallng with a tool. These contacts would be as important esposure in cases where the unit has bees feeding clarified oil from catalytic cracking. There la as opinion In some quarters that the aromatics boiling over TOO*?, are not destroyed, but con centrated, in the heavy tar fraction when clarified oil la fed to thermal crack ing colls. This opinion brmia be tested by means of seme **'*.toxicological experiments. Dismantling Cond*"*" Four laborers ware engaged Is dismantling a condenser box on the Bo. 22 unit. There was a copious flow of heavy tar from the colls as end-connectlosa were removed . Skin contact was plentiful. Some pipefitters rare also involved in this occurrence, which was described as usasual by the pipe-fitter foreman, as gas oil is usually encountered in <Mwgtng these colls. In this Instance, the tar may or may not be considered potentially carcinogenic, depending upon its source and prior treatment. The occurrence serves to point up the necessity for establishing some procedure whereby every unexpected incident that results In prolonged contact of material over a large area of men's bodies shall be re ported to the Safety Department or some other responsible agent for determination EH001708 Sk. of whether the regulations concerning clothing, showers, and oedical examination for potential carcinogens shall be applied. Exposures to Heavy ArTM*tics. General Labor foreses hare given earnest consideration to he problem. A question vas raised that, in **gF,*g ditches to uncover pipeline leaks, the men may encounter a,deposit of aromatics seepage. Alertness to this occurrence, which, obviously exists in the division, is essential to success of the program for pre vention of contact. Actual supervision of the use of protective boots and gloves that are provided for such occurrences is the other essential for success. Another question is that of replacement of work clothing which men will wear for long periods in normal practice, fids is one of the many details that must be worked out in the plan for jrrnvim ng d e a n work clothes when there has been contact with suspected carcinogenic material. Skin contacts with heavy aromatics, an the part of general yard labor, has been considerably lessened by the provisions for flushing out lines before work is done on the catalytic cracking units. Similar provisions are being ar ranged at thermal cracking units where clarified oil is cracked. E PO 01709 85. f!AHpKWI'W* ATO PA I wiTO D IY ISIO T Paint Shoo. *t*'n* I ,i-t/ 1 The use of paint remover for stripping office furniture and other itra occurs vlth sufficient frequency to require precautions against injurious inhala tion of vapor. It is urged that special ventilation he provided for this work. It can he arranged by installation of a large propeller exhaust fan, e.g., 2^" to 30" diameter, and pig-twg of all paint remover vork immediately adjacent to this fan. The present system of placing furniture outdoors for removing paint is not an assurance of safety ag***TM* at n*Jyg.*?1.!.. s or ghl^'n^ted hydroearhons vfaich may he present because it depends on the vagar ies of the vinds and is not at all practical during extended rainy periods. Painters. v -- 7 j .--- The relatively minor role of painting by refinery personnel is indi cated by the fact that about 32 men actne*'1,8, . of this number, five or six men are part-time spray painters. (Major on nev construction, tanks, and process equipment is done by contractors.) Besplratars are provided for all indoor spray verb, vfaich is very infrequent. Bo red lead is sprayed by refinery personnel. An item of major interest to the Medical Department is the possibility of the occurrence of benzol In same of the femulations used. Since the sources of paint product^ and even the composition of products from the seme source, are subject to variation, a check on benzol ea^osures can best be obtained by random application of urine aulfate measurements to the members of the group. EMO 01710 86. MISCELLANEOUS LABORATORIES Aniline. Refinery Laboratory Daily routine man in* point tests are Bade. Ve could see no practice in 1e conduct of these tests that would result in 'breathing appreciable amounts of aniline vapor or any shin contact with aniline, except, perhaps, accidentally. Ihe amount of aniline required for a test (approximately 10 c.c.) is dravn from & reservoir in an exhaust hood. It is mixed vith material being tested on a laboratory bench away from the hood. After the test, used aniline is discarded, there being no facilities for re-distillatiaa. Our only suggestion regarding the protection of workers from is that the physical examination of these people be increased in frequency from once to twice a year, to conform to prac tice in the other refineries that ve have seen. Mercury Vaaor. . ' Those laboratories in which metallic mercury is used were visited in coupany with Mr. Day, of the Safety Department, for the purpoae of observing the extent and manner of use and the disposition of spilled mercury. Hygienic prac tice in the use of rH.iry consists of >on*'r'r<1^ Tlg accumalationa of vapor or dust in the vcriing environment. This can be accomplished by providing a reasonable amount of room ventilation and in keeping the floors and work benches free of spilled mercury. Evaporation takes place from finely divided droplets dispersed on & floor surface at a much greater rate than it will from mercury reservoirs on laboratory apparatus, because of the greater surface eaqioaed to the air. The American Standards Association h* adopted the value of 0.1 urn1igram per cubic F mn M 1 87. meter of air as the pemlSBlble concentration. It constitutes & good bench mark for control of mercury Taper exposures. It expresses an easily at tained level or control. The results of m m mnmrtM made in the various laboratories are bnoun to the Safety Department. They are sunsaariced in the Table belov (page 86) for convenience. Only the Gas Analysis Boom of the Befinery Laboratory shoved a con centration bordering on the level of shat constitutes good practice. In this Instance, replacement of the contaminated floor mats and cleaning and painting of the contaminated floor vill effectively reduce the atmospheric concentration to the level prevailing in the other laboratories. Hie Gas Analysis Boom of the Chemical Products Laboratory is in a much verse condition as regards spilled mercury on the floor mr'A beneath the vurh benches, but accusolatlon of concen trations in the air is prevented by the excellent ventilation system.. E HO 01 71 2 \ Sample Busber 5 T 8 9 10 11 88. Table lU MERCURX VAPCR nBHEMniAIIQES-- LABORATORIES Location Mercury Concentration (Mg. per cn.a.) Refinery laboratory. Gas Analysis Boom. Fairly smooth concrete floor. Rubber mats. Rot wnfVi iy} pn T Sanple at breathing level In too locations. Plancor 572 Lab. Sarnie at breathing level near POD apparatus. Ho visible spilled mercury. Refinery Laboratory. Leonard's Lab. Small use of mercury. Good ventilation. Bo visible deposits. Distillation Group Laboratory: (a) Hear vacuum still (b) Hear glass still Fuel Products Lab. Mercury is vashed here for use In test at `treating plant. Sample taken near vashlng apparatus in open cage locker. Chemical Products Main Laboratory: (a) Analytical Lab. In vicinity of Polariaeter at brewthi ng level (b) Gaa Analysis Lab. Visible deposits rubber mats f underneath laboratory benches. Six exhaust ducts vith Intake one foot off floor, good air supply to roam. Sample t w k m at breathing level. (e) Special Problems Lab. B. Small use of mercury; good air mcrmneat. (d) Special Problems Lab. A. Small use of mercury. 0.18* Greater V-frutn 0.1 Less than 0.C2* 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 * Results obtained by a chemical method utilizing absorption in iodi&e and a colorimetric determination. Air volume 20 cubic feet. All other results vere obtained by use of the General Electric Mercury Vapor- Detector. EM001 71 3 89. E E m n r c staedahds She shop, Amitign section, end office of this division employ about 33 persons in a one-story frame building. Materials Handled. The use .of AzO dyes In the Ozalld process and of photographic chemicals constitute possible sources of dermatitis In susceptible Individuals vlth which < the Medical Director Is fully avare. There are several solvents and process liquids lr. use which are of Interest because of the livelihood that these, and similar preparations that may cone Into use from time to time, contain substances of known toxic properties, such as methyl alcohol and carbon tetrichloride. Oiose currently In use are: Ditto Direct Process Multilith BLanhrola Multi lith Bepelex Multilith Bepelex Mnltlllth Flatex Multilith Deceit Liquid Ventilation. t Besides the doors and windows which are usually open, ventilation of the working space Is fu n d eh*d by a W - i n c h attic fan, a wall exhaust fan at the location of the photographic reproducer, and the exhaust fan connected with the hood over the Ozalld Proceaa. It Is estimated that the ventilation rate exceeds 12,000 to 13,000 cubic feet per minute. Thii ventilation rate will suffice to keep concentrations of vapor of liquids g a p w m i y used In formulations of this kind below 100 parts per million In the air, should the total evap oration rate amount to as much as 2.3 gallons per hour. According to our observations of the processes, the evaporation rate of liquids in this shop is much below this EMO 01714 90. figure. Concentrations of vapor in the air are thus maintained at a level safely below that which would cause bars to the personnel. If there were acute exposures to high local concentrations of harmful solvents at any of the machines, these would have manifested theraelves by symp toms of nausea, dizziness, or Irritability. -0 01715 91. i^gpgftTfl1 PTiATTT 5t:-w7 We did not w 1m & study of the facilities at this refinery for oxidiz ing, "blending, and. packaging asphalt. In view of the experiences at other refineries vithin the cospaay, it sould "be advisable to exmrtae these facilities froa the standpoint of prodoctlon of vapors or mists in oxidizing, aroaatlc vapors in cutback blending, and asphalt mist at drum filling, tibT -- such atmospheric ccntaadnaats may for extended periods in areas -where are at York. EH001716 92. APPSHBIX ' pHBV2zrn.au a? biposibb to szbi bott.itb abcmaiics We hare reviewed the basic irifcarnation which indicated the necessity for a program of control of exposure to catalytic erecting or steam crashing fractions boiling above 700*?.; re are also acquainted ulth the exposition of this program to employees an ?ebrnasy 25 and 2fc, 19**9; sod with the general rules for personal conduct end hygiene with respect to persons encounterin g these frac tions in the course of their duties. We here rerieved the Safety Department's survey of exposures to high boiling aromatics in the refinery, which Includes recnrannadatioas for further action mT'* additional precantionary meaat&rea. These studies Indicate that the Beflnery is in a favorable position vith respect to prevention of aldn contact with these oils by employees and early detection of any n * changes brought about by contact. & e first and most im portant favorable point is that the employees are fully inform ed of the reasons for precautions. They have thus been put in a questioning frame of mind. Pos sibilities for exposure that were overlooked is the original directives and survey have been suggested vill ^rrrHrm* to b e brought out by the several hundred alert supervisees verkers that are affected. The list of proposed Im provements in the Safety Department's survey contains several examples, not ably the necessity for better means for flushing out slurry heat ex changers and steam generators at the catalytic cracking units, especially those that mast be vorked an * unit is in operation. Some details of procedure still remain to be accomplished. Slurry props, in present practice, are not satisfactorily drained of the oil before r emoval to the shop for dis assembly. There seems to be a chance for small parts from service In heavy aromatic oils to reach the sand, blast shed for cleaning without yar ning labels. EM00171* 93. With widespread knowledge of the problem, the prospects are excellent for the ' development In time of totally effective procedures. The adequacy of facilities for taking showers and for provision of protective assumes a great Importance in this program for prevention of shin contact. We find that the refinery is well-ecjaipped with shower roams sad that they are well-distributed for easy accessibility by those who nay be in need of such facilities a working day or at the end of the working day. Any tendency toward further centralization will have a detrimental effect on the ready accessibility of the rooms after the occurrence of a spill or a splaah of the oil fractions that are to be avoided. Maintenance of these shower rooms in a clean and sanitary condition is generally quite good. There are a few excep tions: (1) The colored roam at the road oil stills. The location of this washroom under a water tank makes light and ventilation a difficult problem but maintenance on a par with facilities elsewhere could still maks it a good place to take a bath. (2) The colored roam beneath tank lo. 291 (next to go. 2 boiler house) is likewise ill-kept. (3) The colored room at the Plata Shop suffers from overcrowding. General labor foremen say that 99 pins per cent of gegro laborers take showers on thslr own time at the and of the warttng day. i** habit should be encouraged in every pr actical way. Good maintenance of the shower rocaaa is most important. In the matter of dividing potentially exposed personnel Into frequent and Infrequent groups, we question the Inclusion of nearly all process esplcyees at FCLA. units, qHU, and (XU in the frequent category, ***1 the number of Mechanical -employees is minimized. In our experience, the procees employees E PO 01 71 8 9^. speed acre time at places here these oils are handled hot experience less contact than Kechaztieal tpiay eea ho may less frequently he In areas of ex posure but sore often are exposed. A staple time study on these groups hrmi* clarify the respective exposures. ' In addition to that has been dose to lessen skin contact vlth these high boiling aromatic oils, ve propose that a ccaplete .program for prevention of exposure should the prevention of inhalation of vapor or nirt of these fractions. Ve ere able to demonstrate the presence of oil scLst in the i vicinity of hot elarlfled oil poops at the catalytic s a c king onita. Ve feel that there he a concerted effort to identify and evaluate every occurrence of o n alst in placet here men stark end here the stoch eonsista of oils that are presently Included in this progrsn for prevention of akin contact. She toxicological potentialities of inhalation of a alst of a substance that Is potentially carcinogenic cannot at present he adequately defined hut teens to deserve a great degree of lapertant consideration. Initial efforts should be directed to the areas of slurry and elarlfled oil pumps at catalytic cracking units; feed puspa at thenaal s a c k i n g units receiving clarified oil; quench oil pumps at steaa cracking units; tha tar product pusps of steam s a c king units; and the use of steaa lines far flushing a n y surface deposits that hare resulted frem spills or leaks. All locations at units these oils he examined far the purpose of ascertaining bather the person vho d r u m tha sample can accomplish his aission vithout suffering exposure to mist at splashes of the stock he is sampling. 'I*****.I' E HO 01 71 9 95. mnrrrn. gmnKTiBwa . While potential exposures to benzol la various location (summarized belov) aej hare been over-eaphasized, the uniquely tccdLc character of the vapor varraats p e d a l attgnt'iHp- Various -iaveatigatiana la the consuming industries, especially in coated fabric plants, here enclosure of equipment sad Testilatian vere thought , to be good, disclosed esses of benzol poisoning at concentrations of 75*100 p.p.m. The action is particularly Insidious; assy fatalities from chronic ex posure to lor concentrations are kaorea. Tine for the surrey did not permit detailed appraisal of jjajard la the sereral possible exposure locations. We did not feel Hist say vere par ticularly significant, especially far e n r a g e ladirldsala la goo&'haalth. 9ns possibility of unfavorable developments, hovever, la aa occasional susceptible Individual could not be ruled out, sad this is the reason for the general recom- aeadatloa for medical supervision for markers potentially exposed. Urine Sulfate Test. This test provides a convenient method for measurlag Hie degree of a marker's exposure to beazol -npers a given day, and is particularly ap plicable to upraising the exposures of varkers la the listed locations. Suamarr of Potential Benzol Exposure Areas. Solvent De-vaxlng (MSS) Plant Steam Cracking Plants Vo. 1 sad Vo. 2 BiolefSa Extraction Unit qELL Steam Cracking Coils Paint Shop E M 0 0 1 720