Document 3BJL9LYxN6B7zX8o69EN227D

REPORT NO. 2970 FINAL REPORT ON AROCLOR IN GASES Job No. 171-1089 File No. 141 March 15, 1954 H, B. Richards, Jr. RESEARCH DEPARTMENT Phosphate Division --S/-- Monsanto ansiisa-rtass OSW 147758 STLCOPCB4039368 Report No. 2970 FINAL REPORT ON AROCLOR IN GASES Job No, 171-1089 File No. 141 WfOI\ ' fftalpcwyi irork Started*. Hay 8, 1953 Work Completedl~lE^iO^JL2Sa Report Submitted: MarfihJ.9.S4 Prepared By: H. B. Richards. Jr. ChemistB: AaJ1*JPJLsi&^ ILJL j&charftg,. Jr,. copies were made of this report and distributed as follows: 1. File - St, Louis Library 2. A. M. Elleriburg 3. H. K. Nason 4. Duplicate File - St. Louis Library 5. Safe Deposit or C. F. - St. Louis 6. F, B. Zienty 7. C. A. Hochwalt 8. N.rt.T. Samaras 9. Research Library File - Anniston 10. P. 0. Benignus - St, L 11. it. E. Kelly - St. L 12. H. L. Hubbard - St. L 13. T. 6. Allen " 14. Extra for MCL (England) 15. Extra for MCL (England) 16. Extra 17. Extra 18. Extra DSW 147759 This is Copy No. /3 is report and the information contained herein is the property of MONSANTO CHEMICAL COMPANY STLCOPCB4039369 ( CONFIDENTIAL This report and the information contained herein is the property of Monsanto Chemical Company, and should be considered confidential. It should be retained by the recipient, and not copied or loaned to others. OSW 1%?760 STLCOPCB4039370 CONTENTS I. Introduction ..... Page 1 H. Summary .......... 1 m. References ....... 2 rv. Expe rimental Work 2 V. Discussion ....... 9 YI. Conclusions ........... 11 vu. Recommendations .. 11 Appendix Operating Procedure for Willson Products, ^Incorporated Chlorinated Hydrocarbon Sampling Apparatus ............................................. ............................. 13 Data Sheet - Aroolor Yapor Detection 17 Sampling Positions ..................................... 12 Diagrammatic Sketch ...................... 18 Photograph of Samples GSM 147761 STLCOPCB4039371 I. INTRODUCTION: Dow Chemical Company is interested in using Aroelor as a plasticiser in manufacture of their Saran (vinylidine chloride) plastics, but iB hesitant for fear that the Aroelor vapor might produce toxic affects upon the personnel'in their plant. At the request of the Sales Department this work was undertaken to deter mine the Aroelor vapor concentration in the Anniston plant under usual working conditions. This data would then be used in an attempt to con vince Dow that the use of Aroelor in their plant would be safe. An outgro>' jrth of the problem was the determination of the Aroelor vapor present ii a room which had beon painted with a styrene latex paint using Aroelor a a plasticizer. This work is of interest to the Plastics Division, and was undertaken with this project since the same apparatus and analyjt ical procedures are used as in the Aroelor vapor tests in the plant. II, SUMMARY: An Interlin Report, No. 2892, covers the work up to July, 1953. This report supplements the Interim Report. Air saaplf:ng was continued in the plant under all normal operating conditions. I ie chlorine concentration in the air varied greatly giving calculated A oclor concentrations ranging from about 0.35 mg. per cu. meter up to 5 t 8 mg. per cu. mater. The filtering and drumming operations present t lie most severe exposure to the Aroelor vapors. No definite average daily exposure was determined. A small room, 14* x 13' x 14', was painted on four walls and on the ceiling with Lustrex Latex Paint, Lot No. P-0938 containing Aroelor 1246. The room has only one door and a small 12" ventilating fan with no windows that can be open. Most of the time the room was closed, especially, during the early tesjting periods. A hood, 2* x 3 1/2" x 7f, was also painted on three walls. The exhaust fan on the hood was not operated during the test period. Two 1000 watt electric hot platejs were turned on in the hood to heat the air during the sampling operatiot Sampling lof the air in the room revealed that the Aroelor vapor concentration rapidly ijeached a maximum and then generally decreased to a relatively safe low level after three days. In the heated laboratory hood the concentration remained |in the 1.0 - 2.0 mg. per cu. meter range over a period of about one month. In a heated room it appears that the concentration of Aroelor 1248 vapors may remain high for a long period of time. DSW 147762 l ii STLCOPCB4039372 -2 < III. REFERENCES* Rpport No. 2892, Interim Report on Aroclor in Gases, June 17, 1953, H. B. Richards, Jr. IT. EXPERIHENTAL WORK: Tne apparatus and operating procedure are described in the Appendix to Report No. 2892. This description is supplemented in this rpport by a photograph of the test apparatus, Willson Product's Incorporated, Chlorinated Hydrocarbon Sampling Apparatus. The sampling positions in the plant are the same as described in the Interim Report No. 2892. Ajialytical Procedures Anniston Test No. 20-25-41, Nephelometric determination of Cl" ion. Ranges 5 - 120 micrograms in 20 ml. maximum volume. Apparatus* 1. Fisher Electrophotometer with blue 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. f Solutions* 1. 3N Nitric Acid - 190 ml. CP cone. HNG3 diluted to 1,000. 2. 0.3$ Silver Nitrate - 3 grams dissolved in 1,000 ml. dis tilled water. Store in dark bottle out of light, 3. 1$ Phenolphthalein. 1 gram solid in 100 ml. CP Methanol. Procedure* 1, Pipette required volume of water solution into 25 ml. volumetric graduate. Adjust sample size to obtain 10 120 micrograms of Cl in less than 22 ml. For testing scrubber solutions of Aroclor vapor tests use 10ml. ' 2, Add 1`drop Phenolphthalein and neutralize with 3 N nitric acid (or dilute caustic if sample is acjd). 3. Dilute to 22 ml. with dist-flled water. 4. Add 1 ml, HN03 and 1 ml. AgNO^ in this order. 5. Mix by inverting Only Once and set in complete darkness for 30 Min. 6. Balance Electrophotometer with distilled water in both tubes, using blue filter and 25 ml. cylindrical sample tubes. ( DSW 147763 STLCOPCB4039373 -37, Transfer sample to the Electrophotometer tube quickly with minimum exposure to light and read density or "A* scale, Read quickly without prolonged exposure of sample to the beam of blue light. 8, Compare the scale reading with a calibration chart made from identical determinations of standard chloride solutions, 9, Make 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 may be taken directly from the curve. However a new curve must be made when reagents change, 10, To calculate parts per million (ppm.) of chlorides, divide answer in micrograms by volume of sample. ppm. * Micrograms Cl Volume of Sample % * Micrograms Cl Volume X 10,000 DSw 147764 STLCOPCB4039374 4 TABLE I AROCLOR 1242 TAPOR CONCENTRATION IN THE PLANT Test No, 1 ositlon No. Concentration, Chlorine kk/cu.m. Aroclor Remarks 10 5 29 4 80 5 0.14 1.5 1.6 31 6-S 2.2 45 1 46 2 47 3 0.85 0.34 0.85 i 0.33 3.6 3.6 5.3 2.0 0.80 2.0 Still vented on top Still in 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 time of test. OSVi lib* STLCOPCB4039375 TABLE XI AROCLOR 1254 VAPOR CONCENTRATION IN THE PLANT Test Position Concentration, mg,cm. m. No. No. Chlorine Aroclor Remarks 24 10 25 5 27 5 32 6-S 33 6-N 34 3 35 4 36 4 37 5 38 5 39 IQ 40 7 42 6-N 43 6 44 8 0.68 1.4 0.41 0.50 0.76 0.92 1.45 1.04 0.75 2.68 1.93 1.39 0.51 0.37 0.94 0.68 1.30 1.98 2.40 3.66 0.40____________ 0.80 0.73 1.46 2.4 4.5 4.3 8.0 1.3 2.4 By steam recorder Still operating on 1254 Filtering 1254 at 110-115 C. Pumping 1254 from receiver to B. T. By steam recorder Filtering 1254 at 110 C, Drumming 1254 at 150 C.' NOTE: Th*} analytical procedure on samples 37-40 inclusive vas carried l/2 the normal sample size. I ! I DSW l^lbb STLCOPCB4039376 6 { TABLE IXX AROCLOR 1.260 VAPOR CONCENTRATION IN THE PUNT Test No. I osition No. Concentration, mg/ou. m. Chlorine Aroclor 11 5 0.32 13 4 14 5 0.55 0,52 15 6-S 1.5 16 6-N 1.2 18 5 0.22 19 4 0,91 20 4 0.75 0.53 0.92 0.87 2.5 2.0 0.36 1.5 1.2 21 4 28 8 22 7 0.53 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 Drumming 1260 at 15 By operator's desk assuming 50$ Cl. DS ^llbl STLCOPCB4039377 7 { TABLE IT AR.OCI.OR 3-248 VAPOR FROM UJSTBEX LATEX PAINT. LOT P-0938 Test No. Date Concentration, mg./cu. m. Chlorine Aroelor Remarks Temp, At sample Intake 53 7/20 0.32 0.67 Center, east. 30 min. after 32 C. painting 54 20 1.28 2.68 Center, 1 1/2 hrs. after 32 painting 55 21 0.93 1.93 Center, south 31 56 21 0.92 1.93 Center 31 57 21 0.53 1.11 North east corner 32 58 21 0.98 2.0 46 59 21 0.52 1.1 In laboratory hood 45 60 22 0.57 1.2 50 61 22 0.30 0.62 Comer 33 62 22 0.55 1.1 Center 3? 63 23 0.12 0.25 Corner 40 64 23 0.14 .29 Center 33 66 24 0.11 0.23 Comer 33 i 67 24 68 28 4.9 1.14 9.6 Center} 34 2.4 Comer / Anomolous deviation , 33 69 28 2.5 5.2 Center} probably air contain-- 34 . ination. 70 8/12 0.34 0.71 Comer 38 71 12 0.21 0.44 Center 35 72 3.8 1.3 2.7 In laboratory hood at 60* C > 73 18 0.52 1.1 Comer,fan off 4 hrs. after 37 ventilating. 74 18 0.57 1.2 Center 41 76 9/10 0.23 0.48 Center 37 78 3.0 0 0 Corner 35 79 10/5 0.18 0.37 Center 35 80 5 0.43 0.89 Comer 34 DSW 1%7768 STLCOPCB4039378 Test No. 12 26 41 52 65 77 17 23 48 49 50 51 75 81 -8- . TABLE V BUNK AND MISCELLANEOUS DETERMINATIONS otal CT E* Concentration. mg./cu, ib. Chlorine Aroclor Remarks 0.006 0.007 0 0.007 0 0.006 MWW t,1|t1n ann > mr ----- - < -- m 0.21 0.32 0.32 0.89 0 0.64 0.10 0 ---- *Mi**n ---- 0.42 0.64 --- MWMM Reagent blanks. Total Cl in reagents to be subtracted from vapor determinations. atii, blanks on 5-19 and 5-20, on aroclor tank at North end of building. Assuming 50$ Cl. Blanks on air in instrument room before painting. Tests made on July 17. Air blanks in instrument room No heat on combustion tube. Tests made on 9-10, and 10-5, respectively. 1`.1769 STLCOPCB4039379 -9 V. DisC9SSI0N* The conditions of the tests and the limitations 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 detected by this apparatus can be attributed to three sources* 1. Chlorinated hydrocarbons in the air (Arodors, or any other chlorinated hydrocarbon). 2. Chlorine in the air as free Cl2 or as HC1. 3. Chlorine ion present in the absorption solution and wash wa+er. me No. 3 can be eliminated by use of Cl free reagents, or by making blank determlnations on the reagents used and subtracting the Cl from this source from the total,. The latter method was used throughout these tests. The chlorine from source No. 2 listed above insofar as these tests are concerned is indistinguishable from the chlorine from the aroclors. Furthermore, the concentration of Cl2 and HC1 in the plant area varies so greatly and rapidly that the establishment of a satisfactory "blank" to (compensate for this source is impossible without a statistical evalu ation. It was felt that the amount of work involved for such an evalu ation would not be justified. For this reason the results from all the vapsr tests include chlorine from Sources 1 and 2. Under normal plant conditions, however, chlorine from Source 2 should be relatively low and "the results are therefore assumed as chlorine from Arodor, In somje instances this assumption might produce gross error in the reported resjults, and must therefore be kept in mind in any discussion or evalu ation of the reported results. Another assumption was made in the method of converting the chlorine concentration in the air to Aroclor concentration. The Aroclor vapor was assumed to contain the same percent of chlorine as the aroclor from which it was vaporized. For example, Aroclor 1242 vapor was assjumed to contain 42# chlorine. This assumption is probably not true sinpo the vapor would more likely be richer in the more volatile, lower chlorinated material. Use of this assumption therefore minimizes the concentration of chlorinated hydrocarbon (Aroclor) calculated from any given chlorine concentration found in the air. Tables I, U, and HI are tabulations of all of the tests in the Aroclor plant. The calculated Aroclor vapor concentration was in the 0.5-1 mg. per cu. meter range during the still operation and with the sampling intake close to the still except for the tests during Aroclor OSH l4*7?7Q STLCOPCB4039380 10 - 1242 operations which gave comparatively high results. The average of the concentrations of Aroclor 1242 vapors tested by the stiflls (Positions 1, 2, 4, & 5) was 2.1 mg. per cu. a., which is about 2.3 times as much as the average of 0.89 mg. per cu. m. for the tests of Aroclor 1260 vapors in the same positions. The most severe concentrations were encountered during filtering and drumming operations ranging from about 2 to 5 mg. per cu. meter usually, with one test going up as high as 8 mg. per cu, meter during drumming. No doubt the drumming operation results is the longest continuous exposure of an operator to high Aroclor vapor concentration in the plant, but this exposure only takes place intermittantly 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. This operation requires 20-30 min. work in a heavy Aroclor vapor concen tration. Formerly, this operation was necessary an average of one to two times per shift if both stills were producing liquid Aroclors. One of the filter presses was replaced by a Sparkler closed leaf filter about July 1, however, reducing the necessity of dressing a hot filter press to tin average of probably less than once per shift. An average daily exposure of the operator was not determined. As may be seen in Tables I, II, & HI the A roclor vapor concentration varies quite widely. Several variable factors such as location, temperature of jfcroclor, operation being carried out, boiling point of the Aroclor under test, and direction and intensity of drafts through the still room a3.1 affect the aroclor vapor concentration. Furthermore, the time spent by the operator in any one operation or location varies greatly from day to day. This situation makes establishment of an average daily exposure practically impossible. However, from general observations in the plant It appears that the operator spends no more than 4 to 6 hours a day actually in the Aroclor still room, and of thijs time probably no more than half is spent in localities of severe aroclor vapor concentration. Table IV is a complete tabulation of tests on the Lustrex Latex Paint, Lot[P-0938, from Springfield. The same limitations and assumptions apply to these tests as to the plant tests. The Aroclor vapor concen tration in the room rose rapidly to a maximum and then decreased. This trend is best presented graphicly as in Fig. I. Two sampling positions verje employed in the room, one in the approximate center of the room, and the other with the intake close to the wall in the northeast corner of the room. These positions are noted in Table IV. The Aroclor con centration in the heated laboratory hood remained in the 1-2 mg, per cu. meter at 45-80& C. throughout the test. Table V is a tabulation of the various blank determinations which were made. The value used for the reagent blank in all of these tests was 0.006 mg. Cl'*. 0SVi STLCOPCB4039381 - 11 - VI, COK ELUSIONS: 1* No absolute determinations of Aroclor vapor concentration can be made by the method used, due to presence of unknown quan tities of Cl2 and HC1 in the air. The assumptions made permit simplified evaluation of the data. .2 The apparent Aroclor concentration in the plant varies greatly from 0.5 to 1 mg. per cu. meter under mild conditions up to 5 to 6 mg. per cu. meter tinder the most severe conditions. 3* The filtering and drumming operations present the most severe exposure. 4. No average daily exposure may be developed from these data. 5. The Aroclor vapor concentration in the room painted with Lustrex Latex Paint was sufficiently high {greater than 1,0 mg, per cu. meter) to make the room tmusabl.e for about 3 days. After this the odor and concentration of Aroclor 1248 diminished to a safe limit. VII. RECOMMENDATIONSl J Any1 recommendations on the lack of toxic effects of Aroclor in the concentrations found will have to come from the Medical Department. However, based on the present MAC of 1 mg./ cu. meter, it appears advisable to wear a mask or respirator if concentrations of Aroclor are high enough to be irritable to the nasal membrane. Sipco the room painted with Lustrex Latex Paint containing Aroclor 124:8 definitely has an odor of Aroclor for several days after painting, caution should be exercised in recommending Aroclor for this use. f\,B, H. B. RICHARDS cm March 23, 1954 OS* STLCOPCB4039382 SAMPLING POSITIONS Description_______ No. 1 still, simulating position of operator's head during charging operations. 64" from floor on west side of still about 18" from charging hole. No. 1 receiver, at sight glass, simulating position of operator's head. 54" from floor and 12" west of sight glass. No. 1 filter press? N- northside, S- southside. 54" from floor and 15" from edge of press when on south side.or 9" from edge of.press when on north side. Northside location simulates operator's head position when redressing the filter press. . No. 2 still, same as position 1 above. No. 2 receiver, same as position 2 above. No, 2 filter press, same as position 3 above. At operator's desk, 54" from floor and 8" beyond front edge of desk to simulate position of operator's head when writing at desk. At scales for drumming Aroclor, 54" from floor and 14" from Aroclor outlet. Opposite side of drum from operator. Blank determinations as described. Miscellaneous positions, as described. 1.7773 OSVi STLCOPCB4039383 - 13 - OPERATING- PROCEDURE FOR WILLSON PRODUCTS INCORPORATED. ^ chlorinaIed HYDROCARBON SAliPLm^APPmftjr The following outline of operating procedure for this apparatus has been found quite Satisfactory, and is considerably more detailed than the operating instructions supplied with the apparatus: 1. Mount the absorption apparatus on the tripod and start heating the furnace so that it reaches a bright red heat (850*0.) within 15-20 minutes. A rheostat setting of 40 was found to be about right on the instrument used here. This same setting is maintained throughout the runJ 2. Connect |the suction pump to the apparatus. A needle valve for bleeding in air to regulate the rate of flow through the apparatus affords much better control than does the bleeder cock on the pump alone. The base of an ordinary laboratory gas burner containing a needle valve is satisfactory. 3. Prepare the absorption column as follows: a. Close all outlets and fin with distilled water, drain and repeat to >ash the column. b'. Pipette 1 cc of the absorption solution into the column and allow to drain thoroughly. Add another 1 cc of absorption solution and drain. This prevents the absorption solution*s being diluted by residual water from the washing operation. Close the stopcock and attach suction tube to top f column. 4. When the combustion tube reaches the proper temperature start the pump before opening the stopcock to prevent the absorption solution from draining into the tube connecting the absorption tube to the combustion tube. !'urn the stopcock to the operating position, and simultaneously start the stop watch. 5. Adjust -:he rate of flow by manipulation of the bleeder valves to a rate of one J;o two liters per minute as indicated by the flow meter. The flow me-;er must be previously calibrated for use tinder the conditions of operation. This may be done by operating the apparatus with a calibrated gas meter (such as a wet-test meter) attached to the intake of the com bustion tube. It take? 3 to 5 minutes for the pump to reach a constant rate and the bleeder valves must be adjusted frequently during this time to maintain the proer sampling rate. The adjustment of the sampling rate must always be done with the furnace for the combustion tube on and the furnace must then rema:in on during the entire run. Since the furnace draws current from the same source as the pump any large changes in the load on the line DSW 147774 STLCOPCB4039384 14 - affect ths speed of the pump. 6. Continue the run for the desired period, 30 to 40 minutes for concen trations below 10 mg. of chlorinated material per cubic meter of air. 7. Close the stopcock, stop the pump, and turn off the current to the furnace. 8. Wash the absorption column by filling with distilled water to just above the beads. The beads are washed in this manner just twice and the washings containing the chloride are collected in a clean, 2-oz. bottle. The chloride in the washings is then determined by Anniston Analytieajl Methods, The concentration in the air may then be calculated. It is conlyenient to remove the apparatus from the tripod and to place it at a lower level to carry out the washing operations, but it may be done in place by using a step ladder if desired. 9. Repeat steps 1 through 8 as the normal operating cycle. Reagent BfLank - Although the reagents used in the absorption solution are specified as chlorine free, it is advisable to run a blank deter mination on the reagents. This blank is run by preparing the absorp tion column as in step 3 for a regular run. Then without drawing air through the apparatus the column is washed and the sample taken as in step 8. The chloride is then determined in the usual manner. Absorption Solution: Recrystallize sodium carbonate twice from dis tilled waiter in order to obtain chloride-free sodium carbonate. With this sodium carbonate make a saturated water solution (saturated at 25C.). To 80 cc. of the sodium carbonate solution add 20 cc. dis tilled water. Add one gram chloride-free arsenic trioxide to the 100 cc. carbonate solution. Chloride^free water may be obtained by distillation from sodium hy droxide} and chloride-free arsenic trioxide, by sublimation. . Sample Calculations: 1. MgCli HgC:k ppm, gm. Pi"V. * ffW^sMngs 103 milligrams Cl in washings, * Cl"* concentration in washings, wt. of washings in grams. OSV4 STLCOPCB4039385 15 - 2. MgCl/cu. m MgClp x 10 liters of sample milligrams of Cl per cubic meter in the sample* HgtV MgCl" in washings minus MgCl in reagent blank. Example No. 1: Patat Sate of sampling, 1pm. Dpration of sampling, min. Total vol. of sample, liters Npt wt. of washings, gm, Tptal Cl in blank, mg. %\ Cl in vapor being sampled Concentration of CT" in washings, ppm. 1.5 30 45 15.25 0.00S 54 6.3 Calculat ons: HgClj = 6.3 x 15.25 103 - 0.096 HgCl2 0.096 - 0.006 - 0.090 , MgCl/cu. n * 0.090 x 10 45 Cilorinated hydrocarbon concentration would then be: 2.0 0.54 3.7 mg./ cu. m. DSW STLCOPCB4039386 ( Example No, !? 16 ( ( OSW 147777 ( Sun No* - 17 - DATA SHEET - ABOCLOR VAPOR DETECTION Date: Bar. Press., rang. Hg.: Location of intake: Sate of sampling, 1pm.: Ambient temp, nt intake, *C.: General Remark* t Duration of sampling, min.: Total vol. of sample, liters: Analysis: Net vt. of washings, gnu: Cl cone, in washings, pjxn.J Total Cl in sample, mg.: Total Cl" in blank, mg.: Cl cone, in air, mg./cu. m.J Aroclor cone, in air, mg./cu. m.t ( QSW STLCOPCB4039388 - 18 - Diagrammatic. Sketch. Atodot SI ill Room 60* $liiiSi thvrttr Shift NoB /?ce<V4r o> O s /ftCcfrcr- Tank -HHB-- Ah.B pc'/itr Pr*ss Ptcdetr M.1 Bh*4 Tank A/*. 1 Filter Prext <Z> lSL Stunn Rttonkr. ^n-l <S> ArocUr Sienijte- Tank Denotes Sampling Post'-h'on ' N r Scale' */33**l,mO" H.B.R. - 6-22-55 DSW 1 4 7 7 7 9 STLCOPCB4039389 OSW 1 4 7 7 8 0 7Hour's STLCOPCB4039390 STLCOPCB4039391