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SAFETY COMMITTEE O. B . L e w i s CHAIRMAN Et h y l Ga s o l i n e Co r p o r a t i o n Ciih y s l e k B u il d in g - t o 5 Le x i n g t o n Av e n u e N EW 'Y bR K O ctober l p , 1937 Dr. R. A. Kehoe K ettering Laboratory of Applied Physiology College of Medicine Eden Avenue . C in cin n ati, Ohio. Dear Dr. Kehoe: We are a tta c h in g h e re to copy of a re p o rt from Chuck Colvin concerning the handling o f T e tra e th y l Lead "by th e Dow Chemical Company, which you w ill f in d s e l f explanatory. We should a p p re c ia te your comments and sugges tions . Very tru ly yours SW:GCL Enclosure 0009970 \1 A REPORT OH USE and HANDLING o f TETRAETHYL LEAD tv . - ' DOW CHEMICAL COMPAUI, MIDLAND, MICHIGAN ****##- General -- THe purpose o f the follow ing I s to describe b r ie fly the present use and handling o f tetraeth yl lead by Dow Chemical Company a t Midland, Michigan, end to suggest certain recommendations for sore sa fely handling the m aterial. Purs tetra eth y l lead i s being used as one of three c a ta ly sts in a polym erisation process designed to produce a particular p la s t ic . The process so fa r , and probably for the next several months, i s on an experimental b a sis, housed in a large laboratory room 40* x 40* with 50* c e ilin g , v e n tila te d by one 46* c e ilin g v e n tila to r , (Dimensions are a l l approximate, merely giving r ela tiv e sizes) Five other experi mental projects are housed in the same room* The experimental work i s under the coordination d irection o f Dr, W. R, Veazey and d irectly under the supervision o f Dr, Grebe and h is a s s is ta n t. Dr, I r is h i s the biochemist cooperating with th at department in studying problems of toxicity. Dr. Fe&zey acquainted me with the Dow personnel in terested in t h is p roject and with the d e ta ils o f th e ir use and handling o f te tr a eth y l lead* He asked th at some such report as t h is be prepared for th e ir guidance in drawing up a se t o f in stru ction s for th e ir handling of the material* Description of Present Handling -- Wooden cases containing l i t r e cans o f TEL are delivered to the room in which a l l present handling takes p la ce. Un opened cases were stacked ju s t in sid e the doorway. L itre cans from opened cases are shelved in the room in the open. Four operators, one per s h i f t , do a l l subsequent handling, Attached hereto i s a copy o f in stru ctio n s fo r th a t handling} however, as w ill be noted from toe follow ing, these in stru ctio n s were not being followed in e l l d e ta ils . The operator on duty, when necessary to charge the reaction chamber, opens a l i t r e can under a general hood, pours 55 cc TEL in to a 100 cc graduate, caps toe l i t r e container, carries the graduate 50 f e e t or so to the equipment, pours the TEL in to a f i ll - p i p e through a funnel, returns to the hood, washes graduate and funnel with kerosene.. The operator i s careful to avoid s p illa g e , wears rubber g lo v es, and holds the graduate at arm* s length when carrying and pouring. The f ill- p ip e i s one-inch with two brass globe valves between open end and chamber. The open end i s not capped. This routine i s a daily occurrence and the operator interviewed stated to st he occasionally got e whiff of odor during it* HE 0009371 - 2-- The hood ia e n tir e ly open In fro n t, v en tila ted only at the top , and was quite crowded with b o t t le s o f various m aterials. In i t was also a wooden rack holding a steam bath arrangement and quite a b i t o f an absorbent cheese cloth m ateriel* I t i s constructed o f wood, with the bottom faced with metal* The s is e i s approximately 2* x 4* bottom area, and about the same open fron tal area* The p la s tic polymerising equipment in which TEL i s charged c o n sists o f a 15-gallon round, v e r tic a l reaction chamber equipped with a motordriven stir r in g device operating at very low RFH* The chamber i s charged with reactin g m aterials and three c a ta ly s ts , one o f which i s TEL. The 55 cc charge o f TEL i s about on e-h alf o f one per cent o f the to ta l charge* After charging, the system i s a closed affair* V o la tile m aterial escapee through a pipe out o f the top, goes through a small drying tank, condenser, charcoal absorber, and back in to the reaction chamber. About 30# pressure i s maintained on the reaction chamber during polymerisation* After a batch i s fin ish ed , i t i e dropped out th e bottom, carried 10 or 15 f e e t to a washing container .-here c a ta ly s t and end products are washed out* Acetone i s one o f the washing m aterials* The wash i s dumped in to an open sump sewer four or fiv e fe 9 t away* There i s continually running water through th e sump to the plant sewer. The concrete flo o r around the washing arrangement i s hosed down tw ice a day, but at the time o f say v i s i t there was quite a b i t o f wet m aterial covering the flo o r at the washer. The fin ish ed m aterial i s e n tir e ly free o f lea d , but there i s no in formation on e ith e r organic or inorganic lead content o f the ash. Their estim ate i s that about h a lf o f the 55 cc charge o f TEL i s broken down during the process* hr. Ir ish i s sending a sample of the rash water to Dr. Kehoe with a l e t t e r asking for an an alysis of i t for organic lead content* Before l i s t i n g ay personal recommendations for future handling, there are several poin ts to which p articu lar atten tion shou .d be directed* 1 . Storage o f l i t r e containers i s not now under p o sitiv e control so th at i t would be r e la tiv e ly easy for anyone so minded to take TEL out to another part of the plant. Also, in the event of fir e or mishap, q u an tities of TEL are stored in a spot too intim ate with personnel* 2* Present hood i s inadequate fo r safely handling TEL, both in design and because o f i t s other general use and contents* 3* Present handling in str u c tio n s, dated Kovember 9, 1936, are not being followed* 4* Frequency o f handling i s almost, i f not, d a ily , and a second, larger o u t f it i s being set up so that future frequency w ill be doubled and quantity probably trip led* 5. Probably our b est Ethyl Fluid handling safeguard, v iv id color, cannot be employed here due to n e c essity for the TEL being color-* less* 6 Actual knowledge o f the properties o f the TEL when actu ally in the equipment and during washing i s v ir tu a lly im possible, due to th e complex chemical reaction s going on* Bo attempt whatever has been made in the follow ing recommendations eith er to lim it th e hazard because o f p o s s ib ility o f TEL being reduced to l e s s hazard ous fora or to magnify the hazard in case circumstances e x is t in that direction* ' 7 . TSL i s handled in much smaller quantity in another laboratory in th e same b u ild in g, one cc at a time* A spacious b affled hood i s provided fo r storin g the sin g le l i t r e can and fo r measuring out th e quantity to be used* Since that i s en tirely a research matter presumably in the hands o f a trained technician who works continu a lly with many to x ic compounds, no attempt i s being made herein to cover tn s t handling* Safety Eecggrandations -- 1* In is o la t e d , / e l l v en tilated , firep ro o f, and locked storage space _Cs- vd provided for unopened l i t r e cans, the keys to which to be entrusted to a minimum number o f responsible persons. lm A separate hood should be provided for TEL handling, constructed from our hood p rin t #L-H* The hood should be provided with a ouasrtity o f kerosene for washing, and running water for flu sh in g, I vuuld suggest th at a pan or trough b b u ilt in to the hood to hold as open quantity o f a non-inflammable TEL reducing agent in t o which a l l v e s s e ls and equipment can be immersed a fte r TEL 'xsm-m (Sr* Schaefer can probably name such a m a teriel.) 1 A s o s p le t e se t o f handling in stru ctio n s should be framed and p e lte d a t the hood* 4mm Both polym erizing u n its should be gone over thoroughly to elim i n a te a l l leakage through j o in t s , packing, and v a lv es, and a slic k f I r i s h applied which can be kept absolutely clean* T ill-p ip e s sn ou ld be kept capped* lusher th e washing containers a pan should be in s ta lle d sloping t th e soap. The running water at the sump should be changed so i t i s introduced in the pan, thus at the same time keeping b oth peas and sump continu ally clean. 5m Tz m ite e i o f p erio d ic medical examination o f operator.*? i s hereby r e fe r r e d to Dr* Kehoe fo r h is opinio, as to both frequency and rrocecare* 7, Rubber gloves, rubber aprons, and rubber face-p iece can ister masks should be provided for operator' s use in handling TEL. Routine fo r keeping such equipment ab solu tely clean should be estab lish ed . 8. Following i s a suggested routine for operators* handling of TEL assuming that there are four necessary operators: Since the same 55 cc quantity o f TEL i s used each time in the pres ent u n it, and a constant, though larger amount w ill be used in the second u n it, exposure can b decreased m aterially i f those quanti t i e s are measured out several at a time* For instan ce, operators taking turns could* in a few minutes, measure into several small b o ttle s a su ffic ie n t number o f charges to la s t perhaps ten days. Thus, measuring exposure per man could be lim ited to perhaps once per month. I would suggest heavy g la ss, glass-stoppered b o ttle s with pouring lip s - of two s iz e s to correspond to qu an tities o f charges Routine for measuring then would be: operator dons clean rubber gloves and apron, lin e s up h is clean b o ttle s in the hood, uncaps the TEL can, measures by graduate into the b o ttle s u n til the lin e i s f i ll e d , caps the l it r e can, stoppers the b o ttles, washes the graduate eith er by dipping i t in to the trough of reduoing agent or with kerosene and soap and water, flu sh es o ff the can and bottom of hood with kerosene then water, arranges the hood, c lo ses and locks i t , and then thoroughly cleans h is gloves and apron and washes h is hands. Suggested routine fo r charging: operator dons mask, rubber gloves, apron, obtains b o ttle o f correct siz e from the hood for the p a rti cular u n it, removes cap on f i l l - p i p e , unstoppers b o ttle , ca refu lly pours in the contents, recaps f i ll - p i p e and stoppers b o ttle , re turns to hood and drops b o ttle and stopper into the trough o f re ducing agent, cleans h is equipment, and washes. I t would probably be best to put the TIL into the fill-p ip e ahead of the next m aterials so th t the follow ing additions would act as a wash. 9. A practice should ba establish ed whereby each l i t r e can as i t i s emptied i s rinsed out with kerosene, m utilated, and burned immed ia te ly . I would suggest th t the above recommendations be examined by Mr. Schaefer and Dr. Kehoe, and th t th e ir thoughts pro and con be in cluded in a fin a l report which I could turn over to Dr. Veazey. He asked for such a report, w ritten ex a ctly as though i t , the problem, were our r e sp o n sib ility , and i s rather anxious that he receive i t as soon as p ossib le so that a p ossib le danger period can be reduced to a minimum. .000 93' C. E. Colvin October 9, 1937 PHYSICAL FK3L HCH LABDSATOHT Tl Bow Chsmical Company subject ElSUCTIONS FOB HANDLING TSTRa ETKXL LEAD F ile 6138 Chg. 223 Bee* &. Fin'd. 11-9-36 By H. 3. -inrllcki equipment n-sd f o r h andling t e t r s e th y l le a d s h a ll ho , <5 -1 tim es, in th e w hite enameled d is h , which should ! |p 'i .,,r i' taken from underneath th e hood. M;o. '- ' " 2. in o b tain in g t e t r a e th y l .le a n f o r a b a tc h , th e fo llo w in g :roe.inure should be followed Ja 5u t rub b er g lo v es on b efo re to u ch in g an y th in g in :he enameled d ish . b. Place g la ss stoppered fla s k in th8 g la ss d ish and out them both upon th e sc a le s. c. Weigh out th e re q u ire d amount o f t e t r a e th y l l- a d in the g lass stoppered fla sk , and then stopper the fla sk . ' d. I f you s p il l any t e t r a eth y l lead upon th e ta b le top, sc a le s, or anywhere e lse , be ab so lu tely sure to wash i t o f f w ith kerosene im m ediately. e. Put th e con o f t e t r a e th y l le n d buck in to th e enameled d is h a f t e r you are th r u u sin g i t . Do not -et i t down any p la c e , o th e r th an in th e enameled d is h , a t any tim e. Bo sure th a t i t ia wall stoppered. f . Leave th e g la ss stoppered f la s k under th e hood u n til you are ready to pour th e t e t r a eth y l lead in to th e p o ly m erizer. Bo n o t weigh out th e t e t r a o th y l len d u n t i l you a re ready f o r i t . Avoid allowing a batch of te tr a ethyl lead to stand in th e g la ss stoppered fla s k under th e hood fo r any length of tim e. g . When pouring th e sample in to th e p o ly a a r iz e r, use a fu n n e l, and be a b s o lu te ly su re t o wash o f f any t e t r a e th y l le a d th- t you may s p i l l . Wash th e fu n n el by pouring soma d ic h lo r e th y le n e t h r u i t in to th e polym erizer. h. Besovs th e funnel and th en wash th e fu n n el, th e g la ss stoppered weighing b o ttle , and th e g la ss d ish w ith kerosene, p re fe ra b ly out o f doors, th en wash o ff kero sene w ith acetone and d ry w ith a i r , th en put them back in to th e enameled d ish . HE 0009375 3. Always wear rubber gloves when handling tetr a ethyl le a d or anything th t comes in d ir e c t contact with i t . Personal Precautions 1* Avoid coming In contact with te tr a eth yl lead* 2* Avoid Inhaling any fumes of tetra eth yl lead* 3 . I f you s p i l l any on you rself, even a drop* wash i t o f f immediately w ith plenty o f kerosene, and i t i s your duty to see th..t a f ille d b ottle of kerosene i s always kept in the enameled dish* Remove any cloth in g th -t comes in contact with te tr a eth yl lead , and do not wear the garment again u n til i t has been dry cleaned. 4 . Keep yourself and your clothing clean* Take a shower as o ften as p ossib le when you are working with that material* I f thei-.e procautions o f cle a n lin e ss and care are follow ed , there should never fee any danger* Tour carelessness may not o n ly endanger you, but every man that i s working on t h i s problem* Be sure to report to Bay Boundy any accidents in handling t h is m aterial, so that proper a tten tion may be raid. H. S. imiicki MR 0009970