Document 10qB3B5ka6XVpXXRXd8g93Epa

INTERNAL CORRESPONDENCE RECD. k'&i 2 ' 'Q~~ CHEMICALS AND PLASTICS TO (NAME)Dr, A. B. Steele, NYO company Dr* N* L. Zutty, NYO LOCATION DATE rt t C ElVcO uc AUG 2 0 1974 , PLANT MGRS. FI' S i P. O. BOX 471, TEXAS CITY, TEXAS 7750 August 16, 1974 copy TO Mr. J. L. Carvajal, 514 Mr. R. N. Wheeler, 514 Mr. C. E. Fry, 514 Mr. J. E. Giffin, 514 Mr. R. L. Frantz, 515 Mr. K. E. Ross, 515 Mr. R. W. Sesler, 515 / Mr. J. B. Leverton, 515* Mr. D. E. Deese, 515 Mr. J. W. Whittlesey, NYO Dr. W. R. Manning, 511 Mr. R. W. Martin, 511 SUBJECT VCM Exposure All of the PVC producing units have now been operating VFA continuous monitors for at least one month. Based on the data from these Instruments It does not appear that we will be in serious trouble with any of our operations provided an instrument of this type is allowed as the area monitoring tool and pro vided that an 8-hour TWA level of 15 PPM is allowed. There are frequent readings over 50 PPM on the monitors in all of the PVC operations. Many of these occur in known trouble areas; however, frequently a reading that, over a 24-hour period, might never exceed 5 PPM; will spon taneously show a reading of over 50 PPM. Sometimes the causes can be determined, but just as often the reading returns to normal as fast as it went up and the cause is never known. What this says is that the concept of establishing a ceiling excursion level for personnel is poor since it probably cannot be monitored. An individual can pass through 200 PPM of VCM and never be aware of it, and unless there is some monitoring instrument at that precise point at that time it would never be known. If OSHA publishes a permanent standard containing an excursion level, this will be a passage that we should examine very closely before accepting it without a contest. In the production units there are several very troublesome areas that may require significant expenditures for permanent correction. In all units the compressors used to recover unreacted VCM are old and of the reciprocating type. The newest compressor around is probably a 1948 model. New concepts in compression are definitely needed; some of the other PVC or VCM producers might be helpful in this matter. In the Suspension and Dispersion units improved systems for removing unreacted monomers from resin slurries and latexes UCC 090750 Drs. Steele and Zutty -2- August 16, 1974 are certainly in order. An expenditures of $2,000,000 might be expected, but If one considers the value of the monomer recovered the projects would undoubtedly have a reasonable payout. Without significantly improved systems we will certainly be in constant trouble with EPA and OSHA. 1 fully support the thought of taking the government to task over a standard that is unnecessarily restrictive or one that is worded so as to raise questions about enforceability. The real-life data on personnel here at Texas City certainly gives no cause for alarm and any overly restrictive work standard that would necessitate massive expenditures or cause unemployment should, in my opinion, be contested. MEE/ebm M. E. Eisenhour UCC 090751 INTERNAL CORRESPONDENCE UC T 49-- 2 CHEMICALS AND PLASTICS ! to (name) Dr. D. H. Glenn COMPANY location Texas City Plant copy to Mr. D. E. Deese Mr. M. E. Eisenhour Mr. R. L. Frantz Mr. J. L. Hockersmith Mr. R. W. Sesler Mr. G. F. Tacquard Mr. J. W. Thompson DATE P, O, BOX 471, TEXAS C1TV, TEXAS 77590 Aug''.at 20, 19 74 subject VCM Exposure In response to your request dated August 8, the Solvent Vinyl Resins department offers the following comments: (a) Respirators are worn for sampling autoclaves at Bldg. 115, and for analyzing these samples. These are the only two tasks that routinely expose operators to more than 50 ppm VCM that we know. (b) Employees are notified the results of all personnel VCM exposure regardless of level, and have been notified since the week of July 8. See attached sample notification sheet. Note that the operator's initials are secured on the original copy which is returned to me. (c) A respirator will be required for sampling autocLaves in the future probably. An exhaust system is possibly an alternative but may not be justified in view of planned revisions noted in item (d) below. (d) Analysis of autoclave samples under an exhaust hood may preclude the need for respiratory equipment. Additionally, instrumentation is planned to reduce the frequency of sampling and analyzing autoclaves, but there is no plan to eliminate sampling and analysis of autoclaves. UCC 090752 Dr. D. H. Glenn -2- August20, 1974 Mr. Deese has agreed to note when respiratory equipment is worn in his reports. Please advise if further information or documentation is required by the Medical Department. KER/st Attachments K. E. Ross UCC 090753 UNION CARBIDE CORPORATION Chemicals and Plastics /f (date) Texas City, Texas TO: cc; -f/1?. -Mr--R W. SeslPt-- -Mr. M. Et Eiocnhoug--> (Vinyl Area Shift Production Supervisor) (Shift Superintendent) Here is information on VCM exposure of people at the Solvent Vinyl/ Phenolic Resins Unit on your shift obtained by our Industrial Hygiene Department for the week of 7/2^7 Please convey this information to the individuals listed. Have the4n initial the space provided and return sheet to me. Of particular concern are those exposures which exceed 50 ppm - the present ceiling that has been set by OSHA. Until methods can be devised to reduce these exposures,,below 50 ppm, please see that your people wear proper fresh air equipment while performing these tasks. All exposures over 50 ppm are marked with an asterisk. Elapsed ppm Employee's Bldg. Sampling VCM Inytials Employee_____ No. Date Task Time Exposure 4 f ^ --- * L --------------------------------, J)Q 0 ----------------------------- tJf.CL t Jr\ 'S -Lria >, /1 ^ r. (' V 'v' ti f> ~~-- " $///"? ii~t---- -- --" 1 fj 1 1-----! 1 fk> 6$) ---- ' , 7~^ vr~7~m o 0 / ^O 0 ft '/ ft 1' If '/ ft '/ /Vj 7^Mir A0C*#*e*A*f 0 o & Thanks, K. E. Ross UCC 090754 Jft /C INTERNAL CORRESPONDENCE -------------------------------------------- -------------- :^CiVcu-------- HEMICAL5 AND PLASTICS m P. O. SOX 8361, SOUTH CHARLESTON, WEST VIRGINIA 25303 ,Njme, sion Ati<?n Mr. R. N. Wheeler Mr. D. E. Deese Mr. R. E, Graebert Mr. N. H. Ketcham Dare August 20, 1974 Originating DeOt. Chemicals and Plastics Safety Sobiect Comments on Monitoring Requirements Contained in the Proposed Permanent Standard for Vinyl Chloride Technically speaking it will be impossible (utilizing existing industrial hygiene techniques) to establish and maintain a program of mon itoring which will assure, with 95% or any reasonable level of confidence, that all authorized employees working in regulated areas are never exposed to more than a "no detectable level" of vinyl chloride (whatever that happens to be at the moment in question - based on the acceptable more sensitive techniques available at that time). I will concede that it should be possible to achieve such a goal, with existing techniques, if performed in a laboratory under controlled conditions, but I do not support any contention which infers that this could be duplicated in the field. The two key elements, which make up this proposal, i.e. , no detectable exposure and monitoring at some speci fied confidence level, are not compatible when tested in the field unless tested in conjunction with a personnel monitoring device (mounted on each man) capable of continuous, direct readout with sensitivity, specificity and immediate, preset, alarm capability. We must protect our employees against overexposure to vinyl chloride. However, I do not see that any purpose is served in establishing a standard which cannot be consistently and accurately verified except that it be used as a tool for harassing employers. Existing techniques, when applied against a T. W.A. value as well as a ceiling number, can be relied upon with confidence and I maintain that more good will be realized, in the way of defining and preventing exposures, through application of that tech nique than through application of a "no exposure" approach. In the meantime we must direct every effort toward development of capability for producing continuous, direct readout on the man. REP/map Robert E. Peele Program Manager - Industrial Hygiene UCC 090755 BUSINESS CONFIDENTIAL c<Jti V c l) . MEMORANDUM '.jrf 23 137*4 VINYL CHLORIDE ODOR RECOGNITION THRESHOLD IN AIR AUTHORS J. R. Loy J. N. Dermit SUPERVISOR! F. H. Small DATEi August 20, 1974 PROJECT NO.t 510A20 PILE N0.i 19785 The odor recognition threshold (ORT) of vinyl chloride monomer (VCM) in air was determined to be between 450 and 530 ppm by a five member R/D odor panel. The odor panelists were Mr. G. ff. Bott, Mr. H. E. Gabany, Mr. C. L. Edwards, Mr. H. E. Persinger and Mr. D. B. Snyder. These panelists have been qualified and routinely used by the R/D Department as being the most consistently sensitive to UCC petrochemical compounds of all of the panelists screened. These panelists established the ORT's reported in "The Characterization of the Odor Properties of 101 Petrochemicals using Sensory Methods," File No. 18541, July 10, 1973. Tbe odor threshold of VCM in air was determined by starting with a 5000 ppm VCM standard prepared by the Technical Center Precision Gas Laboratory. Subsequent dynamic dilutions of the primary standard were made in the R/D odor laboratory. The odor panelists were initially exposed to a 22 ppm VCM concentration. Most of the panelists agreed that the odor was characteristic of burnt rubber. As the VCM concentration was increased to the 75 to 100 ppm range the odor became sweet. At VCM concentrations between 160 and 280 ppm there was no characteristic odor to the panelists. A faint rubber odor re appeared at VCM concentrations of 360 ppm but the odor of VCM was not recognizable. The odor of VCM was not disagreeable in any of the test concentrations used to any of the panelists. Manuscript Date: July 26, 1974 Date Typed: August 15, 1974 gc RESEARCH AND DEVELOPMENT DEPARTMENT CHEMICAL$ AND PLASTICS UNION CARBIDE CORPORATION SOUTH CHARLESTON, WEST VIROINIA UCC 090756 BUSINESS CONFIDENTIAL DISTRIBUTION Dr. C. P. Carpenter - (Carnegie-Mellon) Mr. R. A. Conway, 511 >Mr. D. E. Deese, 515 Dr. C. U. Dernehl, NYO-4 Mr. M. E. Eisenhour, 515 Mr. J. F. Erdmann, 515 Mr. J. A. Fisher, 511 Mr. B. R. Guest, 511 Mr. R. J. Hanna, 511 Mr. H. J. Jahnes, 511 Dr. G. F. Johnson, 511 Mr. N. H. Ketcham, 511 Mr. R. G. Lilley, 514 Dr. W. R. Manning, 511 Mr. B. L. Murray, 514 Mr. R. R. Patrick, 511 Mr. R. E. Peele, 511 Dr. A. B. Steele, NYO-28 Dr. T. T. Szabo, 511 Mr. R. N. Wheeler, 514 Mr. J. W. Whittlesey, NYO-46 Information Retrieval Library, 525 Authors (5) MEMORANDUM 510A20 Ucc 090757 ' UNION carbide, chemicals and plastics LABORATORY MANUAL INDUSTRIAL HYGIENE METHODS 38C-9Cl-R2aJ Page 1 of 5 August 23, 1974 - VINYL CHLORIDE DETERMINATION IN AIR BY ADSORPTION ON ACTIVATED CHARCOAL AND ANALYSIS BY GAS CHROMATOGRAPHY . 1 PURPOSE AND LIMITATIONS This paper describes a procedure for * measuring the exposure of personnel to vinyl chloride in the working environment. The method describes the preparation of standards which will determine vihyl chloride in the range of ^to 90 parts per million by f volume in air, based on a 4-hour sampTe' at a flow rate of 28 ml per minute. Lower or higher ppm ranges can be determined by preparing additional standards to cover the range desired, (Vinyl chloride can be determined to at least 0.05 ppm'by volume in air by this procedure, using more dilute standards.} ' 2 PRINCIPLE The sample is collected by passing air through a glass tube containing activated charcoal which adsorbs any vinyl chloride vapors present. The vinyl chloride is then desorbed from the charcoal by carbon disulfide, extrac-* tion and analyzed by gas chromatography. 3 INSTRUMENT PARAMETERS Chromatograph Column Column temperature Injection temperature Detector Carrier Hydrogen flow rate Air flow rate Sample size Retention time AID (Analytical Instrument* , , - ,, Development, Inc.) Portable Chromatograph, Model 511.,. or equivalent chromatograph, with . flame ionization detector. Six-foot x 1/8-inch stainless steel, packed with 10% di (2-ethylhexyl) *' sebacate on Chromasorb P, 80/100 mesh, NAW. 100C isothermal 100C flame ionization detector', helium or nitrogen 23 cc per minute ' 133 cc per minute 2 pi solvent flush technique 0.5 minute (adjust carrier flaw until vinyl chloride elutes at this time) Note: If this column is used in a conventional chromatograph, better separation of vinyl chloride from other light boiling impurities will be obtained by operation of the column oven near ambient temperature L'30C. The AID portable chromatograph cannot be used at ambient temperature without modification since the heat from '* the flame ionization detector will cause the temperature in the column oven to rise to 60 to 70C UCC 090758 38C-9C1-R2a p2 of 5 LABORATORY MANUAL Alternate Column - Better Resolution I ns trument Column Detector Column temperature Detector temperature Injector temperature Carrier gas Air flow Hydrogen flow Sample size Approximate elution time Hewlett-Packard 5750 gas chromato- ' graph - dual column, or equivalent. 25-foot x 1/8 inch stainless steel. . packed with 25% by weight 75% C0880/25% ' Tergi tol E-35 on 40/60 mesh rescreened Chromosorb P. flame ionization 40 to 100'C al 4"C per minute 125 C 125 c ; helium, 30 ml per minute 350 ml per minute 30 ml per minute 10 jil '' 6.5 minutes 4 REAGENTS AND APPARATUS a) Personal sampling pump. MSA Model G or Bendix Micronair. Insert an in-line orifice made from a cut-off and restricted (pinched) hypodermic needle in the sampling line to the pump in order to obtain a 28 cc per minute flow on these pumps. b) Hypo-vials, 15-ml size, Cat. No. 12911; Neoprene septa, Cat. No. 13233; alumina seals, Cat. No. 13214; and hand crimper, Cat. No. 13212, Pierce Chemical Company, Rockford, Illinois. c) Carbon disulfide, spectrophotometric grade 4 d) Activated charcoal, Cat. No. 580-26, Barnebey-Cheney, Columbus, Ohio e) Soap film flow meter, 10-ml size f) Stop watch 5 PREPARATION OF THE ACTIVATED CARBON ADSORPTION TUBE a) Prepare the activated charcoal by placing the charcoal on a 40-mesh sieve and wash with demineralized water until no visible fines-appear in the washings. b) Dry the carbon in a drying oven at 110C until dry and free flowing (overnight). Store in a screw-top, glass' bottle until needed. c) Cut 8-mm O.D. x 6-mm I.D. Pyrex glass tubing into 6-inch lengths and fire polish the ends. ' d) Insert a Pyrex glass wool plug two-thirds of the distance into the glass tubes. The longer section of tubing will be designated as the primary end, while the shorter side of the tubing is the back-up end. e) Pack the tubes with the activated carbon, using a length of 60 mm in the primary section and 35 mm in the back-up section. Retain the carbon with glass wool plugs. f) Seal the tubes with a red rubber septum or parafilm until . ready for use. .'.r.'f. ,fj* 1 UCC 090759  !, f 1 - v- ..'dfAa. 11 laboratory manual p3 bf 5 38C~9C1-R2fl r. 6 SAMPLING PROCEDURE J . . ^ 1 .^ ''-4 . , i a) Remove the.seals from the charcoal tube and attached the' back-up section to a portable pump by means of a length . - of 1/4-inch Tygon tubing. ,V'. , jj b) Set the flow rate at 28 ml per minute through the tube with a calibrated rotameter. (NOTE: The 10-mi soap-' bubble flow meter can be used to obtain a more precise (>( reading of the air flow through the tube if desired). 1 . c) Record the time the air sampling was started and the time: if; when the sampling is completed. A four-hour sample hiay , . be taken with this system. ^" d) After sampling, recheck the flow rate and reseal.the end& ''X.- of the charcoal tube. Return the tube to the laboratory . for analysis. . '. h . . - c. e) Record the temperature and barometric pressure at 'the ;" sampling site. ... , = .. 7 ANALYTICAL PROCEDURE V' a) Make a small hook at the end of a piece of wire and^, remove . the glass wool plug from the primary end of the charcoal , tube. Make sure that no charcoal particles adhere to; the glass wool plug. . ^ '/ b) Pour the charcoal into a 10-ml glass-stoppered volumetric flask and cool the flask and carbon in a wet-ice bath'. c) Pipet 3 ml of carbon disulfide (CS2) into the cooledJflask 7' ; and stopper securely. (CAUTION: Carbon disulfide is toxic and should be handled under a hood.) -7 7 d) Agitate the flask periodically -for at least 30 minutes. v ' e) Solvent Flush Injection Technique. This injection'technique '( is designed to eliminate difficulties arising from blow- 7. * back or distillation with the needle of the microliter , ... . . syringe. .. 7, 7\ s. . f) Flush a 10-^il syringe with CS2 several times to wet the barrel and plunger. 7: \ \ g) Draw 2 jil of CS2 into the syringe and remove the tip of ' *7*7 I the needle from the solvent. Withdraw the plunger an * additional 0.5 ^1 to separate the CS2 from the sample , 7. f with a- pocket of air. ~ .f h) Dip the needle into the sample solution^in the volumetric V ,, $ flask and withdraw the plunger until the air bubble between v| the solvent and the sample has passed the 2-^1 mark on the 7 syringe. , i) Remove the tip of the needle from the sample solution and , * ji adjust the volume in the syringe until the meniscus of .../7t the air bubble rests on the 2-yui mark. Remove the excess | sample solution from the tip of the needle. >. . j) Pull the plunger back an additional 0.5 to prevent tlxe , 7 sample solution from evaporating from the tip of the needle.- 7 k) Inject the entire contents of the syringe into the" chromatd-* f graph. ' l) Measure the peak height and determine the vinyl chloride - 7 content from a previously prepared calibration curve. .-7, UCC 090760 38C-9C1-R2a p4 of 5 laboratory manual 8 CALIBRATION CURVE a) Pipet 10 ml of carbon disulfide (CS2) inu,* each of five 15-ml hypo-vials. Cap the vials witn tne Neoprene septa and aluminum seals, using the hand crimper. b) Place the hypo-vials in wet ice to reduce ohe vapor pressure of CS2. c) Cap one of the valves on a steel sample cylinuer containing vinyl chloride with a 1/8-inch Swagelok tubing nut which has a chromatographic septum installed in the nut. d) Insert a hypodermic needle through the septum on the cylinder, open the valve and allow the vinyl chloride to vent through the needle for about 10 seconds to purge the air from the system. Remove the needle. e) Using the appropriate gas-tight syringe fitted with a number 27 gauge hypodermic needle, insert the needle through the septum on the cylinder and allow the pressure of the vinyl chloride to displace the volume of the syringe. Flush the syringe two times to remove any air which may have been trapped in the needle, f) Into the respective hypo-vials, inject 0.2, 0.3, 0.5, 1.0,, and 2.0 cc of vinyl chloride from the syringe. g) Shake the hypo-vials for one minute to put the vinyl chloride in solution. These standards will contain 56, 82, 133, 260, 515 ugm of vinyl chloride per ml. (NOTE: These calcula tions are corrected for the dead space in the gas syringe needle. The cold CS2 solutions in the hypo-vials are under slight negative pressure. Measurements have shown that the dead space in the syringe needle amounts to 0.04 cc, , and 0.02 cc of this volume is pulled into the hypo-vial by the negative pressure.) h) Allow the standards to warm up to room temperature, then inject these standards into the chromatograph using the procedure described in Section 7, paragraphs e through k. Shake the hypo-vials each time just prior to withdrawing a sample. i) Plot peak height versus micrograms of vinyl chloride per ml. 9 CALCULATION A x 3 x 24.5 L x 62.5 vinyl chloride, ppm by volume at 25C and 760 mm A = ugm per ml of vinyl chloride read from calibration curve L = total liters of air sample (flow rate x time) This method was developed by the Industrial Hygiene Department at the Texas City Plant. 10 ORIGIN This procedure is based on a method developed and used by the Industrial Hygiene Department at the Texas City Plant. This stepwise description of the procedure also reflects experience gained during verification of the method by the R/D Environmental Health Laboratory and by field testing at several plants. UCC 090761 'r ,, ii, - , TH'f - J '' V -.,V -. ^ . <,- ' V 54 *: ' -o '" 'V., rfV' v.4%1 t t 4 .r -*V. - "? LABORATORY MANUAL J p' >lv r V> -II - REFERENCES 6-RSC-53 ---f- -- ----- . < .4 - iVtI * r-*: * * ..* * -.j.-Ji-a:1;--, i *. *- 7 *; * -v- -- r p5 of,^.,^:38C-9.Cl^R2a^C ;t ;v W.J'.if?'"'-.-.f-' -,v.,,,,Vr ., V- ;:, ,f'wAV-VA^4 . " /v.>>'.' ' k, . >' . , ;/ A' ^v,^' 'f-".;%'",/ . ,'; (l).Deese, D. E. , "Vinyl Chloride Personnel, Monitor ing^Data' 'fr^ / \Y. ... Texas City Plant Summary and Method", Letter,'February 's,! ,:?|` V ' 1974. / ' (vv/' / -,. . ;. ' (2) Reid, FH. and Halpin,- W. R. , "Determination' O^i'Mklpge-r* ;:^V ^J, i r nated and Aromatic Hydrocarbons in Air` by f-Ch^rcoal-.Tube' ;y. and Gas Chromatography", Amer. Ind . Hyg. ,, Assoc./.Jv;-29,H V;'`: No. 4, pp . 390-396, July-August, 1968. i ! . " *, y`V.,-.., A.'/K '^ . ' - . -A ' 4 -'y? ( ` ' 4' ,> .. . (3) Raskins, J. and Fink, W. W. , "Method for - Dei ermi n ing-.' - 4iJ , 4 V J ` - ... i"', ^Impurities in P- roject Report VinFyil_le Chloride Monomer", UCC>R No. 320610, January 12, and ^1)4 .. , 1966: J.... .............. `f ` .J >, V . 4, j rVt ' V * > * , 4 ;-VJ> *a- , ' * ,, ,4r _j f, r ^ v:h -JL . i.L \ < - ,'v' .r-u , 4 J* * A, 'w # ' :! , V *' ` ` .........* > \ ' ' 1 ^ - . , .>*<.. . ' ,.t . -= . ^ ' *, - f y- /, *'> ^ ' ' ,*: ;i?-y t| ' > ' i* *i' `V l*H . j ' i. ' ,--v .*/:>;. hi '< - \ -. *> A'. 1 . . 'i'"2 :i * ' '? ;. 4-; C. ^'''.-v-.' i i' ^ ; , '/' i'S': t// ' . - * >, (t* *- ,'4-t ,` ~ ' 1, hJ, i 1 7 , , fx ' \ " ; j.' ,v*;, . " . - > , (. r -V V ; r ' J ! V'fJk' -*' - .-1 ^ /-X ` T' .f ' ..* .:- '-T '(!-' / t {*, / f'/ '&'a4' J . 'r .Pjf . V.. - : V ; ..... ' -i ? ^ :/ . u. yv,..'-'<-'3,j-. * \> *1 V* *'/; J1'.' s i;>; *.; J* > fc'A - *'vr` ` !'" i''' rrw * . <4 - Vs ( - ' 44-s*,...* 'i-t. ^ Q ,T" ':/ fc: . 1 ' /, jj5* ^ Tj* , * ` ,t ' [* , ., ^ ^ j u., / ,,, i* a r >. v, . . I,- r . 4. ` i\ 1 `t. : w -e J *''*+ L' ;-..v ;l'>'." f? , ; rjl ' 5' * | .'! V, I.', f> V <t ; r ' U I T* v f w Wi-V? *' -t . \ r , i* 4 !l, ' jf ; v-V'ii-r -vi-v- . RESEARCH AND DEVELOPMENT DEPAftRRTTMMEENNTT ' , TECHNICAL CENTER ' *' ''y j South Charleston, West Virginia , * i ^ '-vy-;: a y v4.;:feyArAv^vT,4,- .,* .V.. d - ' f ^ ?' V - v ' v ;,,-r ; . , K,. UCC 090762 *r t' 'j * ti ^ -Vf 4 , ^ *, t * -y-r - i nf-1