Document XOJkrvpajVZyrrgoEJNDDgZwd

Q rT^.- J03PCBJ NO. 2970 nrn mm? ON AROCLQg IN OASES Job No. 171-1089 File No. 141 March 15, 1954 H. D. Richards, Jr, RESEARCH DEPARTMENT Phosphate DlvWon EXHIBIT jJ- 0 * t> OSH 143758 987 WATER PCB-SD0000054554 Report No. 29*70 FINAL REPORT OK AROCLOR IN GASES Job No, 171-1099 File No. 141 farc$\ Jkff>rUt\et$ 4 // irork started: fay. <^*953 Prepared By: H. B. Richards^Jr* fork completed: grower 3.fe.aaag teport Submitted: ojA-i2*--LSa Chemists: LtJXUJilSiMxz. EUJU. ULgtefla.t...Jx.t .oopiei were made of ibis report end distributed s follows: File - St, Louis Library A. H. Bllenborg B. X, Naaca Duplicate Pile - St. Louis Library Safe Deposit or C, F, - St. LoirLa F. B. Zienty C. A. Hocbvalt M.ii.T. Saaaras Research Library File - Anniston P, O. Benignus - gt, L i. ?. Kelly - St..L p. L. Hubbard - St. L X. 6. Allen * Extra for MCL (England) Extra for HCL (England) Extra Extra Extra DSW U775.9 This is Copy No.^AL siimemimskmaausisaiattt^UBKIS Tiis resort and the information contained herein is tho property of W ^ MONSANTO CHEMICAL COMPANY WATER PCB-SD0000054555 C 0 HFIDSHmi This report end the information oontained herein is the property of Honaanto Chemioal Conpany, end should be considered confidential. It should be retained by the recipient, and not oopied or loaned to others. DS U"` WATER PCB-SD0000054556 cotfrmrs Za IlltrOdUCVtAdi MtM************t*'*** Paga 1 II . StfitV My III. JEflftrenoea )4*BB**^ft>***B****a>t**'* XT. Ebqxriaental Ifork .................................. ............ 1 2 2 V. Discussion YI. OoiioXiisioQS TXT. EeocWondations .................................. ................ S n n Appendl* operating Procedure for Hills on Products, 3jncorporated Chlorinated Hydrocarbon' Sampling Apparatus ..........a...*.......*.*....*...... 13 Data Sheet Aroolor Tapor Detectioa ........ 17 Ssapling Positions 12 Diagnusoatio Sketch ........................ . 18 Photograph of Saaples I DSW :U7761 WATER PCB-SD0000054557 I introduction* Dov Chesd.c<;al Company is interested in using Aroolor as a plasticiser in sannfaotue?re of their Saran (vinylidine chloride) plasties, hut is hesitant for fear that the Aroclor vapor sight produce toxic affeota upon the personnel in their plant. - At tho rofliost of the Sales Dopartaent this work was undertaken to deter mine the .Lroclor tapor concentration in the Anniston plant under usual working c mditions, This data would then be used in an attempt to con vince Dow that the uso of Aroclor in their plant would be safe. An outgro rth of the problem was the determination of the Aroclor vapor present ii a room which had boon painted with a styrene latex paint using Aroclor a i a plasticiser. This work is of interest to the Plastics Pivision, and was undertaken with this projeot since the sane apparatus and analytical procedures are used as in the Aroclor vapor tests in the plant, . H. SUHKARTi An Interims Bepert, No. 2892, covers the work up to July, 1053. This report subpleaents the Interim Report. Air sampling was continued in the plant under all normal operating condi tions . f je ohlorin# concentration in. the air varied greatly giving cal culated Aroclor concentrations ranging free about 0.35 *g. per ou. aeter up to 5 t> 8 ag, per ou. aster. The filtering and drumming operations present tie most severe exposure to the Aroclor vapors. No definite average daily exposure was dotreined. A small rxw, 14' x 13* x 14', was painted on four walls and on the oailing with Lust rex Latex Paint, Lot No. P-0988 containing Aroclor 1248. The rota has inly one door and a mall 12" ventilating fan with no windows that con be open. Most of the tine the roc was dosed, especially, during tbe early tesjting periods. ' A hood, 2* x 8 1/2 x 71, was also painted on three walls, Tbe exhaust fan on tbe hood vas not operated (hiring tbe test period. Two 1000 watt eleotrie hot plates were turned on in the hood to heat the air (hiring tbe sampling operation. Sstapling Jof the air in the rooa revealed that the Aroclor vapor concentration rapidly ijeaohed a mtrlnm and then generally decreased to a relatively safe loi# level after three days. In the heated laboratory hood the concentration remained on the 1,0 - 2.0 ag. .per eu. aeter range over a period of about one saonth. In a heated room it appears that the concentration of Aroclor 1248 vapors say remain high for a long period of tise. DSW 147762 WATER PCB-SD0000054558 nx RjSFBRSNCESl -2- Report No, 2892, Intori* Report on Aroclor in Bases, June 17, 1953, H. B. Richards, Jr. IV. BtCFEgTHENTAI. WOBXl 5oRaepppoarrtaNtuos. and operating procedure 2892. This description are described in the appendix is supplemented in this r^port by a photograph of the teat apparatus, Willson Product*s IIt*corporated, Chlorinated Hydrocarbon Sampling Apparatus. The s juapling positions in the plant are the same as described in the Interim Report No. 2892. ' Analytical Procedures Anniston Test No. 20-25-41, Nephelometric determination of Cl" ion. San 6* 5 120 nicrograos in 20 ral. maximum volume. Apparatus! 1. Fieher Bleotrophotcaeter vith bine filter and 25 ml. sample tube. 2. 25 ml, glass stoppered volumetric flask or graduate. 3. 10 ml. measuring pipette and 10 ml. transfer pipette. Solutions! 1. 3N Nitric Acid - 190 ml. CP cone. HWO3 diluted to 1,000. 3. 0.5$ Silver Nitrate - 3 grams dissolved in 1,000 ml. dis tilled vater. Store in dark bottle out of light. 3. !# Phonolphthalein. 1 gram solid in 100 ml. CP Methanol. Procedure! 1. Pipette required volume of water solution into 25 *1. volumetric graduate. Adjust sample site to obtain 10 120 miorograas of Cl in less than 22 *1. For testing sorubber solutions of Aroclor vapor tests use 10 ml. ' 2, Add 1`drop Pbenolphthaleln and neutralise vith 3 N nitric aoid (or dilute caustic if sample is acid), 3. Dilute to 22'ml. vith distilled water. 4. Add 1 al. HNOg and 1 si. AgNOs in this order. 5. Mix by inverting Only Once and set in complete darkness for 30 Kin. ' ................ ' 6. Balance Electrophotometer with distilled water la both tubes, using blue filter and 25 si. cylindrical sample s tubes. DSH l**7763 WATER PCB-SD0000054559 -37, Transfer sample to the Eleotrophotoaeter tube quickly vith minimum exposure to light and read density or "A" scale, lead 'quickly without prolonged exposure of sample to the beam of blue light. 8. Compare the soale reading with a calibration chart made from identical determinations of standard chloride solutions. 0, Hake a blank 'run on all reagents and subtract from reading of step (8) or plot data of standard runs to include the chlorides of the blank, in which case the reading say be taken direotly Frosa the curro. However a new curve must be made when reagents ohange, 10, Jo calculate parts per million (ppm.) of chlorides, divide answer in miorogranw by volume of sample. pps. " Kjcrograas Cl Volume of Sample f * Ml programs Cl Toiune 1 10,000 OSH It?76<> WATER PCB-SD0000054560 lost No, 10 29 80 81 45 46 47 ' "4 TAMS I ASOCLQg 1242 VAPOK COMCEMTSATION IN THE PLANT F-s! Position I No. Concentration, Chlorine ag/cu.B. Arooior" Remarks 5 0.14 4 1.5 6 1.6 6~S 2.2 i 0.85 2 0.34 3 0.85 0.33 3.6 3.6 5.3 2.0 0.60 2.0 Still rented on top. Still la operation Press not operating and cold. 1242 in No. 2 B. T. at 110* C. Both stills operating on 1242 . - Filter press replaced with Sparkler leaf filter which was cold at tine of test. t I ,l^b5 DSV4 WATER PCB-SD0000054561 IASPCLOR 1254 TATOa CONCENTRATION IN THE PLANT Teat Position Concentration. ag.cu. a. No, W. Chlorine Aroclor Remarks 24 1( 25 S 27 5 32 6- S 33 6- r 34 8 35 4 36 4 37 5 38 5 39 It 40 7 42 6- N 43 8 44 8 0.68 0.41 0.50 1.45 1.04 0.75 0.61 0.37 1.80 1.98 0.40 0.73 2.4 4.3 1.3 1.4 0.76 0.92 2.68 1.93 1.39 0.94 0.68 2.40 3.66 0,80 1.46 4.5 8.0 2.4 By ateaa recorder Still operating on 1254 Filtering 1254 at 110-115* C. Punping 1254 frres receiver to B. T. By ateaa recorder Filtering 1254 at 110.* C. Druraing 1254 at 150" C.' KOTBt Th( analytical procedure on samples 37-40 inclusive wj carried l/2 the nomal easple sixe. DSW i^766 I WATER PCB-SD0000054562 I f'IJ/ nsis m ABOCLOR 1260 VAPOR CONCENTRATION IN THE PUNT Test No. Position No. Conoentration % g/eu. a. Chlorine Aroolor 11 5 13 4 14 S 15 6-S IQ 6-N 18 5 10 4 20 4 0.32 0.65 0.52 1.5 1.2 0.22 0;91 0.75 0,53 0.92 0.87 2.5 2.0 0.36 1.5 1.2 21 4 28 8 22 7 0.63 2.8 1.1 0.88 4.6 2.2 Remarks Still in operation Still open ' Filtering 1260 at 125* C. Still operating Still open Still charged and started Still operating Bnnaaing 1260 at IE By operator's desk assuming 50^ Cl. 6S l^6*7 WATER PCB-SD0000054563 I ( -7 TABLE XT AROCIjOa 3-Z4B TABOR FROM LPSTREX LATBX PAINT. LOT P-0938 n Test No. 63 64 66 66 67 68 69 60 61 62 63 64 66 67 68 69 70 71 72 73 74 76 78 79 80 Ml 7/20 20 21 21 21 21 21 22 22 22 23 23 24 24 28 28 6/12 12 18 18 18 6/10 10 10/5 5 Concentration, mx./ora. a. Chlorine Axoclor 0.32 1.28 0.93 0.92 0.63 0,98 0,52 0.67 0.30 0.65 0.12' 0.14 0.11 4.9 1.14 2.6 0.34 0.21 1.8 0.62 0.67 0.23 0 0.18 0.43 0.67 2.68 1.93 1.93 1.11 2.0 1.1 1.2 0.62 1.1 0.25 .29 0.23 9.6 2.4 5.2 0.71 0.44 2,7 1.1 1.2 0.48 0 0.37 0.89 Eeaarks Teap. At sample Intake Center, east. SO min. after painting Center, 1 l/Z hr*. after painting Center, south Center North east eoraer In laboratory hood Corner Center Corner Center Corner Center^ Corner/ Anoneloua deviation, Center) probably air contaa. ination. Corner Center In laboratory hood at 60* C. Corner,fan off 4 hr*, after . ventilating. Center Center Corner Center Corner 32* C. 32 31 81' 32 46 45 60 33 : 3? 40 33 33 84 33 34 38 35 37 41 37 85 35. 34 I { DSa - I<>7768 WATER PCB-SD0000054564 TABLE BLANK AND MISCFLLAiSOUS DETEEHINA.TIONS Tost No, 1 otal Cl" ffle* Concentration, mg,/cu, a. Chlorine Aroclor Remarks 12 0.006 26 0.007 41 0 62 0,007 65 0 77 0.006 17 m -- -r23 ,.. 48 49 50 61 -- 75 to.1 m 81 ---- --- --- 0.21 0.32 0.32 0.89 0 0.64 0.10 0 ---- 0.42 0.64 - - r, - -- ---- ---- - Reagent blanks. Total 01 In reagents to be subtreeted frcas vapor detenainationa. atm, blanks on 5-19 and 5-20, on aroclor tank at North end of building. Assuming 5C$ Cl. Blanks on air in instrussent rooa before painting. Testa made on July 17, Air blanks in instrument roe* No heat on coabustion tube. Teats Bade on 9-10, and 10-5, respectively. ( WATER PCB-SD0000054565 / -9- V. MSPUSSIONi The conditions of the tests and the llaitations of the apparatus are such that absolute determinations of the chlorinated hydrocarbons are not possible. Comparative determinations of the total chlorine in the air during any specific test period can be made. The chlorine dotpcted by this apparatus can bo attributed to `three sourcest 1. Chlorinated hydrocarbons in the air (Aroclora, or any other chlorinated hydrocarbon). 2. Chlorine in the air as free Cl2 or as BC1. 3. Chlorine ion present in the absorption solution and wash water. . Cotd'ce No. 3 can. be eliminated by use of Cl free reagents, or by making blank determinations on the reagents used and subtracting the Cl I from this source from the total. The latter method was used thrpughout these tests. Thoj chlorine from source No. 2 listed above Insofar as these tests aroj concerned is Indistinguishable from the chlorine from the aroolors. thermore, the concentration of Cl2 and HC1 in the plant area varies greatly and rapidly that the establishment of a satisfactory "blank seapensate for this source is impossible without a statistical evaluoa. It vaa felt that the amount of work involved for such an evalu- vould not be justified. For this reason the results from all the tests include chlorine from Sources 1 and 2. Under normal plant Ltions, however, chlorine from Source 2 should be relatively low and' tbo results are therefore assumed as chlorine fro Aroolor. la soak instances this assumption might produce gross error in the reported results, and must therefore be kept in Hind in any discussion or evalu ation of the reported results. Another assumption was made in the nothod of converting the chlorine concentration in the air to Aroclor concentration. The Aroclor vapor was assumed to contain the ease percent of chlorine as the aroclor from vhioh it was vaporised. For example, Aroolor 1242 vapor was asepjod to contain 42J chlorine. This assumption is probably not true einpe the taper would more likely be rioher in the sore volatile, lower ohlorinatad material. Use of this assumption therefore minimises the concentration of ohlcrinated hydrocarbon (Aroclor) calculated from any given chlorine concentration found in the air. Tables 1, U, and XU are tabulations of all of the tests in the Aroclor plant. The calculated Aroolor vapor concentration was in the O.fr-3 ag. per ou. meter range during the still operation and with the sampling intake close to the still except for the tests during Aroolor DSk WATER PCB-SD0000054566 - 10 - 12^2 operations vhioh gave comparatively high restilts. The average of tha concentrations of Aroclor 1242 vapors tested by the stills (Position^ 1, 2, 4, & 5) ns 2.1 Bg. per cu. m., vhioh is about 2,2 times as uoh as the average of 0,89 mg. per cu, . for the tests of Aroclor 1260 vapors in the sane positions. The most sevjere concentrations were encountered (hiring filtering and 'dntnaing operations ranging from about 2 to 6 ag. per cu. aeter usually, with one test going up as high as 8 g. per cu, meter during drwadng. No (doubt the dreaming operation results is the longest continuous oxpjosuro of an operator to high. Aroclor vapor concentration in the at, but this exposure only takes place intermittently usually with a few days between the drumming operation. The filter operation presents a severe exposure also, especially, if it is necessary to change filter papers during filtration of an Aroclor batch. Shis operation requires 20-30 sin. work in &. heavy Aroolor vapor concen tration. Formerly, thin operation was necessary an average of one to two times per shift if both stills were producing liquid Jroclors. One of the filter presses was replaced by a Sparkler closed leaf filter about July 1, however, reducing the necessity of dressing a hot filtir press to an average of probably less than once per shift. An uverage daily exposure Of the operator was not determined. As may be peon in Tables I, H, te III the Aroclor vapor concentration varies quite widely. Several variable faotors such as location, temperature of (Aroclor, operation being carried out, boiling point of the Aroclor under test, and direction and intensity of drafts through the still room all affect the aroclor vapor concentration. Furthermore, the time spent by the operator in any one operation or looation varies greatly from day to day. This situation makes establishment of an average daily exposure praotieally impossible". Hovever, from general observations in the plant it appears that the operator spends so sore tbaja 4 to 6 hours n day actually in the Aroclor still room, and of time probably no more than half is spent in localities of severe or vupor concentration. Table IT is a complete tabulation of testa on the Lustrex latex Faint, Lot P-0933, froa Springfield. Tho same limitations and assumptions apply to these tests as to the plant tests. The Aroclor vapor ooncentrasios in the room rose rapidly to a maximum and than decreased. This trend is best-presented graphicly as in Fig. I. Two sampling positions warp employed in the room, one in the approximate center of the roc,and tha other with the intake close to the wall in the northeast corner of tth room. These positions are noted in Table IT. She Aroolor ecm"comration in the heated laboratory hood remained in the 1-2 sg. per cu.I aster at 48-80 C. throughout the. teat. Table T 1b a tabulation of pie various blank determinations whioh were made. The value used for the reagent Manic in all of these testa was 0.006 ag. Cl", 0S 1** 7 in WATER PCB-SD0000054567 -n- /./i; n. eotjcwsiOMSi 1. Ho abaolate deteraimtions of Aroolor vapor concentration can be Bade by the aethod used, due to presence of unknown iptaa- titles of Cla and HC1 in the air* The sasuaptlons made persait eiapllfied evaluation of the data. " .2 The apparent Aroolor oonoeatratioo in the plant varies greatly fro* 0.8 to 1 Big. per eu. neter under mild conditions up to 5 to 8 mg. per ou. aeter under tbe Bost severe conditions. 3. fbe filtering and druming operations present tbe most severe exposure. 4. Ho average daily exposure say be developed frt* these data. 3. the Arcelor vapor concentration in the roc* painted with Lustrex Latex Faint was sufficiently high (greater than 1.0 sg. per ou. meter) to make tbe room unusable fer about 3 days. After this the odor and concentration of Aroolor 1248 diminished to a safe limit. yh. ENEATIOMSl . reocsaaendatiejis on the lack of toxio effects of Aroolor in tbe J;entrailoob found will bar to cose frtta the Hedical Department, aver, based on the present KAC of 1 mg./ ou. mater, it appears advisable to wear a mask or respirator if concentrations of Aroolor high enough to be irritable to the nasal meabraae. , the roc* painted with Lustres Latex Faint containing Aroolor |8 definitely has an odor of Aroolor for several days after painting, ioa should be exercised in recomsehding Aroolor for this use. {!,&, t-- H. . SICSASBS Q,7r\i A. M. HLmflHJBS * ea Hatfch 23, 1954 Su 147772 WATER PCB-SD0000054568 - 12 SAMPLER POSmOlS ri Position .Nuaber 1. 2. 3. 4. 3. 8. 7. 6. e. 10. __________Peserltrfcioa Mo. 1 still, simulating position of operator's bead daring charging operations. 64s frees floor on vast side of still about l$ fros charging bole. No. 1 reoeiver, at sight glass, sisailating position of operator's head. 34" froa floor and 12 west of sight glass. No* 1 filter press} N- northsido, S~ southside. 54 fro* floor and IE* from edge of press -when on south side.or 8" fro edge of .press when on north side. MSorthside location simulate* operator's bead position when redressing the filter press. , No. 2 still, sane as position labors. ' No. 2 receiver, sane as position 2 above. No, 2 filter press, sane as position 3 above. At operator's desk, 54" from floor and 8* beyond front edge of desk to simulate position of operator's bead vban writing at desk. At soales for dnaseing Arooler, 54" frea floor and 14" from Arcelor outlet. Opposite side of drum from operator. Blank determinations as described. ' Miscellaneous positions, as described. . iV713 DSW WATER PCB-SD0000054569