Document 39bpKykKD4R5jx5dnBXREqZO

4 Industrial Hygiene in the Petroleum Industry By A. C PABST Industrial Hygienist* Socony-Vacuum Oil Go, Inc* New York, N. Y. Industria! hygiene is a field that is closely The typical industrial hygienist usually interwoven with industrial safety. In fact, started ouKanr chemist or chemical engi- it can be regarded as a medical engineering neer who became interested, and studied phase of safety. toxicological effects of chemicals on man. Unfortunately, many people do not know what`industrial hygiene is and the functions of an industrial hygienist The reason for this is that industrial hygiene is a compara tively new science and practically unknown twenty years ago. . Today there are only about 800 industrial hygienists in the United States, and a brge number of this group "are not in industry, but working for the federal govc^nmenfsor state departments. Usually, people hearing the word "hygiene" recall they, had a hy giene course in high __ school which - dealt with personal habits such as bathing, clean ing the fingernails, teeth, and so forth and immediately jump to the conclusion that an industrial hygienist in industry must be interested in keeping employees clean. In my initial visit to many, refineries, it seemed that the first place I was taken was to locker rooms to inspect .shower and lav Consequently, he has a good background of chemistry and engineering combined with some medical knowledge--a sort of onethird doctor, one-third engineer and onethird chemist. His objectives are protection and improvement of health and safety of workers in industrial environments from all ` manger of harmful exposures related to occupation. Industrial hygienists and safety engineers have pretty much the same objectives and should be regarded as-members of the same team. Actually, the functions of each are. sometimes so inter-related it is not pos sible to draw a clear line of separation be tween the two fields, nor k-dt necessary to do so for if a man's health is endangered , by working conditions it k-afiT important part of his safety picture. In many indus tries, safety and Industrial hygiene are combined in the same department. I atory facilities. In some degree, industrial In the petroleum industry, however, in- . hygienists are interested in the employee's dustrial hygienists are usually attached to cleanliness,-but only so far as it is neces the medical department and work as closely sary to protect his health. We are more interested in keeping an employee's lungs, skin, and other organs dean and free from as "possible with the safety department for the protection of the employees. There is good reason why, the petroleum industrial hazardous gases, liquids, and other harmful hygienists must lean heavily upon the safety substances. . department In the petroleum industry the Hygiene is defined as that branch of med ical science that relates to preservation of health. Therefore, industrial hygiene may be defined as the science of prevention and control of occupational illness. It resolves concept of industrial hygiene is relatively new as compared to the chemical and other* industries, consequently, the number of pe troleum industrial hygienists is exceedingly small. . itself into the problem of finding factors or conditions in work places that may cause or contribute to the illness or serious dis comfort of employees, and of devising meth ods and means^of eliminating or controlling such conditions. Another term that may- On the other hand, safety departments are well established, well acquainted with and dose to every day problems of the petroleum industry. They have considerably more cov erage and manpower. ' best describe industrial hygiene might be To illustrate, the American Petroleum In industrial metrical engineering. stitute's roster of safety and fire protection The industrial hygienist has done much `personnel list some !,,2K) names, probably1 toward bringing medicine and safety engi not all, in this occupation. Contrasted to neering into dose cooperation partly because this, to the best of my knowledge, there are his interests overlap these two fields. at present, only 17 industrial hygienists Petrolrum Industry S working for petroleum companies--an indus try ratio of approximately 70 safety men to one industrial hygienist. Most of the major oil companies now have at least one indus trial hygienist and anywhere from 50 to 100 safety men so you can see it is very neces sary for us to work with ami through our safety people Basically, the practices of. industrial hy giene in the petroleum "industry, is the ^amc as in any other industry and it can be boiled down to four general principles: ' 1. A knowledge of the toxicology) of chemicals and materials. 2. A review of all chemicals or.materials used and how handled and tabulation of toxic of potentially hazardous $ui*Tinccs. 3. Measurement of worker ext>osure to Siazardous substances. 4. If required, recommendation and in stallation of adequate control measures and evaluation of the effectiveness of such cor rective steps. ` ' 2. It can 'be harmful by direct contact with the skin or parti of thg. bddy.-i v X It can be inhaled as w gas, vapor, mist or dust |/ ` Ingestion V.^"' * Fortunately, petrolctun materials are not commonly or intentionally taken internally 'and therefore, trouble from this is rather rare in a refinery, although it does occa-` sionally'occur unknowingly. 1 recall watch ing a worker who had been, complaining of' stomach trouble, whose duties involved the compounding of litharge or lead oxide in a doctor solution. This man proceeded to emptybags of litharge into an outdoor mixing tank and because of the dust and mists generated he correctly wore a respirator. Of course, .his hands were covered with lead oxide, and to my amazement, the first- thing lie did when lie came down off the catwalk was to take an orange out of his lunch box which lie started to peel ami cat--probably .one of the most effective ways to get' lead poisoning. _ Toxicology of Chemicals In regard to tht toxicology of chemicals, it is'(usually difficult to adequately define a Juuaruous material because practically any thing \can be safe or harmful depending upon now it is used or .where it is used. ' Unfortunately, when petroleum products get into the hands of customers ingestion is more frequent, usually, by small children whose parents carelessly leave products within easy reach. You know that every year there are fatalities reported from chil dren drinking kerosene. We have had hurry For vexample. air and water are not re calls from doctors involving children drink gardedlas harmful, but both arc quite deadly ing such products as penetrating oil and ' certain conditions--air iX injected fly sprays. , " int^f the blood "stream and,' wdter jif intro- Some times adults arc even worse as into the lungs. \_J there are* many eases of anti-freeze poison In- the same manner, the use of carbon ing, drinking of brake fluid and one I recall tetrachloride in a' process having properly of our radiator flush which contains muri designed ventilation would not be hazardous, atic acid and Chlorinated hydrocarbon. How while the use of carbon tetrachloride for ever, this product is fully labeled including mopping floors would be quite dangerous. .poison warning with the skull and cross Most safety people- are aware that carbon bones. . tetrachloride is a hazardous chemical because there has been considerable publicity regard ing itS toxicological effects, and in some cases, restrictive labeling requirements have l*een passed, for example, in New' York Gt\V Many other, chemicals used in the petroleum industry have inherent toxic qual ities of the same magnitude, yet are not so well known. In regard to toxicology, there are three ways in which a substance can cause adverse effects upon man: It should be- emphasized' that hardly a substance exists that is not capable of pro ducing effects on the human body if taken in sufficient amounts or under the. wrong circumstances. Even common table salt if used in sufficient quantities is toxic It is reported that many years ago the Chinese used table salt as a means of committing suicide Every chemical substance, there fore, has a non toxic dose for. man and a toxic dose for man. This can be well illus trated by the following slide on a widely 1. It can be ingested or swallowed. used commodity : 6 1954 National Safety Congress Effect of Alcohol Level in Blood* Ounce* at Whiiker Coa turned in l Hr. or leu Percent Alcohol in Blood Behaviot /* A primary irritant is a chemical that may , 1 caus^ dermatitis in' individuals frequently-, after only one contact. They may have a strong chemical action, such as adds, alkalis, amines, and so forth or they may have a ~4 t 2-3 ' 5 <5 S 10 36 24 30 O.Ot 0.02 0.03 0.! O.tJ 0.2 0.3 0.4 . 0.3 0.6 - 0.7 Normal. * Peelinx of warmth * utt aorial bctirior. E 3seoe Mooted, fai. tmoalsirc. Otfid*H]r atm aobcr. Fumbling. itaggering gait, durasiness. tiurred speech. O&ctMllr oruak. Responm tad motor coordination itronaiy affected. Helplot, nausea. Stupor. Coma. Paralyiia of the retpiritory center -- Death. weak chemical action but.require prolonged contact to cause dermatitis. Most petroleum . hydrocarbons are primary irritants but are. classed in the latter category in that pro-' longed or extensive contact is usually re quired to came skin irritation. Sensitizing agents, on the othw- hand, 'are chemicals that are innocuous to most skins but capable of producing dermatitis} in a few susceptible individuals following .re peated contacts over a long period vof time. ' Pfixer Spectrum, JAMA. March 27, 1934 Sensitization may require weeks, months' Skin and Body Contact or even years of contact with the material before dermatitis develops. ' '1 Approximately 60 per cent of all com plaints received by our department are con cerned with dermatitis and skin irritations resulting from contact with petroleum mate rials. ',, The petroleum industry is now handling large quantities of chemical additives and inhibitors, many of which are strong pri mary .irritants and wry active chemical compounds. By nature, inhibitors usually By far, the majority of these complaints have'to be very potent chemicals 'because, are from customers so this- is a subject that while they are used in very low concentra is very important in the marketing of pe tions, they exert a powerful influence on the troleum products. characteristics or performance of the prod Cases among our employees or in our uct, and many of the inhibitors are just as refineries are few when compared with those potent towards nun. among industrial users of petroleum prod One very active class of inhibitors are the ucts, and it is believed that the reason for amines and substituted amines, and we are this is due mainly to the degree or extent particularly concerned abourthem because of contact. they are very damaging to '.Jhr eyes, amLa In the petroleum industry skin contact is not generally experienced to the extent that it is--for. example, in the metal working industries^ where' a daily eight hour skin contact with--cutting oils often takes place. It is definitely established that, skin is not an impermeable terrier to chemical sub stances, and it is increasingly important as a route'of absorption for many materials. Action of chemicalk on skin may he local resulting in dermatitis. Examples we are familiar with are kerosene, cutting oils, and so forth, or a chemical may be absorbed through the skin and cause damage to blood or internal parts of the body. splash can readily result in blindneu/TlW amines are usually strong smelling drastic liquids, insoluble in water, hence difficult to remove by washing. They can cause severe eye bums and necrosis* of eye tissue. In addition, most amines are readily absorbed through the skin; and even tow quantities may cause internal'damage and death. The following will show the effect on skin of one such amine-dimethyl phenyfene diamine: Amoeat $kto Ant , Effect O.OOJce 0.003CC 4.ficc \ tq.cm. Heat -- redo*** -- nth t *q.cm. Biiatrr formation U *q. ifl. Death . Employees should be fully alerted as to Lead tetraethyl as an illustration does not hazards, of such materials and should, be affect the skin or cause dermatitis but can .. educated'to the use of protective - goggles, penetrate the skin and- cause internal pois gloves and aprons when handling such prod- oning. ucts, an activity within the scope of the Regarding external or local skin effects, safety engineer. . . ' chemicals may be classified either as pri The foregoing applies to concentrated or mary irritants or sensitizihg agents. undiluted , inhibitors. Finished petroleum Petroleum Industry t products should and usually do contain such A few of the materials commonly en ; * a small quantity, and the inhibitor is so countered in the petroleum industry an diluted as *to remit in practically no more listed below: . 'harm in the finished product:than 'there would be from the straight mineral oil itself. Industrial dermatitis cases some times .re sult in bizarre and erroneous conclusion^ as to their cause even by those who should know better. } J recall a case of a young man who C'iun end Vutert `, Substance PPK Benzene (benaoi) .................................................. 35 . Guboa dioxide .........................................................500C Cuban auxKMtfde ............................ Cuboa tetrachloride ........ .......... . IOC '........ 21 G*jtioe ............... ........... ...100 Hydrogm wtfidc ......................... 20 Napbtlu {petroloua) ................................... 300 Qctiee .. !.............................................. sof Sulfur dioxide ............................................... .... U worked in a gasoline station and developed a severe dermatitis. He went to a physician who made patch tests on him and found lie had a sensitivity to special gasoline but no reaction to regular gasoline. Apparently, ' Texif Dull. Famtt. and Mini . Subftince M(t. Pe Cu. M Iron oxide lame ................:........... ... . ...13 U*d ............................. . ............. .. .. 0.13 Sulfuric acid ................................ ................. i the, physician had heard special gasoline contains a lot of lead because the case was Subwancc Miami Dam . * MPPCJ diagnosed as resulting from an excess of Aabeato# .........................................'.................... 5 lead tetraethyl in the special gasoline. We Duat (uoiiance. no free silica) ......................... 30 Silica ' thought this strange because while we all ' ` Ucb (abore 30% free SiO) .......................... 3 know that lead tetraethyl is a violent poison medium <3 to 30% free SOi) ...................... 20 . tow (below 3% (ree.SiOi) ............................ 30 and can be absorbed through the skin, it is not a primary skip irritant and has never These values are based on the best avail been known to came dermatitis: A review able information from industrial experience, of records of gasoline shipments into the from experimental studies, and, when pos particular area showed the regulir gasoline sible, front a combination of the two. They actually contained the same or some times are not fixed values but arc reviewed annu more lead than the special gasoline, clearly ally by the Committee on Threshold Limits proving\ that,, lead tetraethyl was not to for changes, revisions, or additions as fur bbune, but that some1 other material was ther information becomes available , Threshold Limits should be used as guides In control of health hazards and should not , "Of the three avenues by which chemicals be regarded as fine lines between safe and can be taken into the body, inhalation prob dangerous concentrations. They represent- ably has received by fir the most study and conditions .only within which it is felt that- investigation because it is the most impor workers may be repeatedly exposed, daj tant consideration in industrial health. after day, without their health being ad The vast amount of research on tlie in halation of materials has resulted in publica tion of very useful data on safe human exposure levels known as Threshold Limit Values-or Maximum Allowable Concentra tions. This is a lis't of several hundred com monly encountered chemicals, solvents, dusts, and so-forth, the toxicology of which has been &a_$enlly studied by medical research and industrial experience. versely affected. It Is felt, at the present time; that workers should not be exposed to a working environment containing any of these substances in excess of the value indicated. -. I cannot over emphasize the importance of the Threshold Limit Values and believe that every safety man should be famlllar^whh thenCiaidTttve copies of the complete table, becausel>*Key have been* incorporated/ in' states' codes and have the force of law in The list is compiled annually by the Amer many states, and therefore,. must be com ican Conference'; of Governmental Indus , plied with. So far some nineteen states have trial Hygienists: and is published by the written Threshold Limit Values into their American Medial Association. It tabulates laws and often management Is hot aware of the maximum amt-ant of the various mate* twch requirements but would be Ih a vul rials workers can safely be exposed to for an eight hour working daj-rwttfiout injury to health. ' f ' V nerable ^position if trouble resulted from excessive exposure to any of the materials. Usually rt-ft up to safety people and Indus- 8 1954 National Safety Congress trial hygienists to alert management to the A hazard U defined at--"the. risk of in existence- of these codes and to institute jury or illness which may be encountered . measures for measurement of air contam during or as. i result of my reasonably inants so as to insure compliance. anticipated type * of handling or use of a Even a common materia! like gasoline has a maximum safe level which is $00 parts per million. The results of exposure to concentrations greater than 500 ppm is shown by the following: J. Gasoline Exposure substance, or during its specified use, if any, by reason of the toxicity of- the substance through ingestion. Inhalation or absorption through the skin, or due to its corrosiveness . or irritating properties, or because of its flammability or explosiveness.TM ' t Simibr kbeiing regubtions already exist Symptoms: Headache, irritation of eyes and throat, dizziness, nausea, loss of con sciousness, death. Putt Per Million ?; Maximum Allowable cootentration for proioniced exposure..................................... tOO Slight symptoms after several hourt... .. 1000 Maximum concentration tolerable foe I hr. '000 Dangerout foe thort exposure................... .1 '000 Fatal for thort expotuie................................2'000 Lower explothre limit......................... I-(000 0,0' O.t 0.' l.' S.4 tn California, Illinois, Oregon, and the Ter ritory of Hawaii and are in the making in Mew -Jersey, New Hampshire, Ohio and Rhode Island. More can be expected. For tunately, most state regulations are guided by recommendations of the Manufacturing Chemists' Association, Inc. and with some few exceptions, conformity in one state results in conformity in other states. - It is recognized that as a rule labeling Produet Labeling regulations of many products are advisable One very important function f the in and result in safer handling of the material dustrial hygienist in the petrolcttm industry* by customers, but it requires extensive work, is precautionary labeling of product. This knowledge of product and toxicological in-, is receiving more and more emphasis as formation to determine what products must state after state passes labeling. regulations. be labeled and how they should be labeled. The most recent is the state of New York In our company's .operations, we use some where the Council on Public Health passed , what over 2,000. basic chemicals or raw on February 26, 1954 labeling regulations materials and manufacture some 3,500 fin which became effective August 24. 1954 as ished products ^rhich must' be reviewed in Chapter IX-A of the New York State dividually in regard tq tlr above. " ' . ***- , Sanitary Code. These labeling regubtions To illustrate, the following are just a. have the force and effect of. bw and require few of the hazardous materials that are' precautionary labeling on any product which encountered in petroleum refinery opera entails a hazard in a reasonably anticipated, tions or that might tie' cornpotmded into use. finished products: MnierUle Ene**tereet im rttttlemm Refinery, Ofetdiiemi S-cspiratnry Irritants Acrolein Acetaldehyde .. Aluminum Chloride Ammonia . Asbestos Ditertiary butyl para cresol Dusts, physiologically inert, general Dusts, attapeigus day Dusts, bauxite Dusts, catilyst Formaldehyde Fluorides Furfural inhibitors Lime Nitrogen oxides Ozooe Silica Sulfur dioxide Fine Oil Welding fumes Toxic Materials Aniline, liquid Aniline, dyes Benzol (Benzene) Carbon Monoxide Chlorinated hydrocarbons Chrome compounds Cobalt, metal ' Hydrogen solfide inhibitors Lead, metal & fumes Lead, oxide, litharge Lead, tetraethyl Lead, soap* Manganese Mercury Methanol ' Radiotctnre materials, general Toluol (Toluene) Xykrf-(Xylene)' Skin Irritants Acids --* all kinds Anutses Beasol (Benzene) Caustics Osnxzuuni Salts Coal-tar Compounds Cobalt, metal and compounds Dyes inhibitors Nickel salts * * Oil*, general Oils, nigh boiling from Cat * Steam Cracking Oils, insoluble cutting Phenol Pitch Solvents Ultra Violet Radiation Wax, untreattd Petroleum Industry 9 ' The petroleum industry has nude re* /table progress in development of new and better products and in improving proc essing operations. Accompanying this prog ress has been new problems of toxicology and health engineering which must be stud ied and investigated with the same zeal as other types of research.' The advent of catalytic cracking resulted in production and handling of aromatic Hy drocarbons, and of importance to us, healthproblems long associated with the coal-jar industry. The use ?f new chemical catalysts, inhib itors; and other chemical compounds involve health problems flat chemical industries iiave faced for years. To illustrate tiiis trend we need only look at the modem gasolines, fuel oils and motor oils. Years ago motor oils were practically 100 per cent petroleum in nature with little, if any, additives: today they contain up to 15 to 20 per cent of chemicals, additives and inhibitors, awl this trend will continue t<cause there is no question that additive* necessary and Contribute much to im prove -performance characteristics. Every step in this direction, however, does jxisc .new problems of health and safety among our plant personnel and our custom ers. Because the petroleum induitry is be coming more and more involved in the s~ lundling of all kinds of chemicals having I: * various degrees of physiological effects-upon l .man, I would like to quote the following \ concerning chemicals from a publication } issued by Du Pont`s Haskell Laboratory of Toxicology: , - "It Takes All Sorts" , "`Chemicals, like people, can be mild, frac tious and often exasperating. Like people, chemicals are of. many types and disposi tions. Most are uncomplaining, law-abiding citizens who present no special problems. .Some are unstable and unpredictable. Some arc out-and-out neurotics, requiring a sharp and observant discipline. Others, harmless by themselves, may be influenced by bad company. Still others are troublemakers in Military. Init ilocile and helpful in tandem. Some are just plain bad actors." It is my firm opinion that good industrial hygiene in the petroleum industry is de pendent upon combined skills of many and requires earnest cooperation of industrial physicians, industrial nurses, toxicologists, chemists, safety men and industrial hy gienists working together as a team. We all have a very important part in the picture. Safe Handling of Insecticides- ' By F. R. WILLSEY Farm Safety Specialist, Purdue University, Lafayette, Ind. Insecticides arc supposed to kill! Of course; they are supposed to kill only insects liut the fact that they are intended to kill anything at all should be enough to cause us to be alert . In one sense this problem of "Safe Handling of Insecticides" isn't a new prob lem at all. For years, we've had insecti cides that could and occasionally did kill humans. We have also had some that were less dangerous. On the other hand, in a few -hort years we've clianged from a few old landhys to over 5,000 products involving about 70 chemicals. Why all this change ? ; l. Apparently feople don't like to eat worms as well as they did. At least public opinion seems to demand Siigher quality products now that people realize such prod- acts can be produced. 2. And the government doesn't think t>eople siiould eat so many insects. Tliat's indicated by the fact that we have more laws and regulations governing quality of products, labeling of insecticides, spray rcsi- due. and so forth. , 3. Insects travel more. They hitch-hike rides on the very latest transportation facili ties. As a result they get more places and get there quicker than they could a few years ago. ' . ' 4. New chemicals, plus research, makes new insecticides possible. I n fact with each