Document jNVJD203dJzvpNokpEw4kM565

PX >loS - ; j ! 'r : MIC-D&P-R&D - St. Louis INTERIM (TYPE OF REPORT) REPORT REPORT NO.: MSL-0104 JOB/PROJECTNO.: 03-000-760.11-7403237 DATE: February 7, 1978 TITLE: u.V. Degradation of Pentachlorophenol AUTHORS: J. A. Hinkebein PERSONNEL: J. A. Hinkebein, D. P. Ronan ABSTRACT: Distilled and Technical grade Penta was exposed to both natural and artificial daylight. Dioxins, rurans and hexachlorobenzene were fonaed as degradation products. . AUTHORS: J * A * HlnkebeXn TITLE: U.V. Degradation of lu'ntaelilorciplienol HfcPT. NO.: MSi<-0104 COPY NO.: \ V S \)5JE.C . VP- s C03.266 COMPANY CONFIDENT L This document is the property of Monsanto Company and the recipient is responsible for its safekeeping and disposition, It contains CONFIDENTIAL INFORMATION which must not be reproduced, revealed to unauthorizec nersons Or sent outside the ('nmnanv. withm rr nrnner aurhon7atinn_ : Q I S T E R I B U T T O : N. COPY NUMBER 1. P. A.lerney, J.W. Cross - N Res. File - M3A 2. J. S. Metcalf - B2NC 3. A. T. Smith - G2WD 4. R. G. Potter - B3S3 5. Tech. Reports Library - R2C 6. Tech. Reports Library - R2C 7. E. A. Matzner - M3A 8. G. J. McEwan - N3A 9. J. H. Payne - N3A 10. J. D. Wilson - M3A 11. J. A. Hinkebein - M2B 12. D. P. Roman - M23 13-16,.D. Danna - E2MB 17. M. E. Blaylock - B2MA 18. B.' W. Eley - A2SC ABSTRACT ONLY Akron - 1010 R. W. Wise Dayton - 1250 E. E. Hardy Via D. Danna - E2NB 4 copies Melbourne, Australia Montreal, Canada Louvain-la-Neuve Central Reports Library H. E. Madden - R2C ABSTRACT ONLY M. E. Miller - B3SB C. F. Call is - B2SA J. W. Cross - N3A M. W. Farrar - R2E R. K. FI iteraft - 1250 E. J. Griffith - N3D W. C. Hamnann - T3A S. A. Heininger - G5EA W. R. Knox - R4C F. P. LaBelle/H. M. McKelvey - G2W[ E. A. Matzner - N3A D. W. McDonald - E3SH G. J. McEwan - N3A J. S. Metcalf - B2NK D. E. Munie - B3SB T. M. Patrick - T3B J. H, Payne - N3A W. R. Richard - R2E C. W. Roos - RIB R. J. Schatz - E3SA R. Schuler - R48 C. Y. Shen - N2B C, C.Sisler - R2E A. J.Speziale - N N. W. Touchette - 1730 M. C. Throdahl - DID J. D. Wilson - N3A F. B. Zienty - T3A ' ''M L TiVE 0 ?.0 R. C O M P A N Y C O N F I DENiTTAL. When no longer needed, or upon request, return this report to uU 7 u i> r^lr I II. III. IV. V. -1 INTRODUCTION -, / S U B J ;T% A ? -- .7. Koppers Co. reported some work, on UV (Ultra-violet) degradation of Penta. They found chat the higher chlorodioxins such as octachlorodibenzo-p- dioxin (OCDD) were formed in significant amounts. These dioxins also degraded but at a slower rate. This implies that the use of distilled Penta instead of technical Penta will not guarantee preventing the introduction of dioxins into the environment. It was felt that these findings should be confirmed. This report covers our work on U V degradation of Monsanto technical Penta and Dow's EC-7 distilled Penta. SUMMARY and CONCLUSIONS 1. Penta degrades in U V light with a increase in dioxins and furans. The amount of dioxins in distilled Penta were as high as those in technical Penta for some samples. -2. U V degradation also forms significant levels of hexachlorobenzene (HC3). 3. In long term tests, the distilled Penta appeared to degrade faster than technical Penta. This resulted in the dioxins/furans and HCB levees rising to a maximum which then decreased. The dioxins/furans remained approximately constant in the technical Penta. U. Penta degraded much faster in the presence of oil. The oil did not appear to increase the dioxin degradation rate. 5. Our results were generally in agreement with those reported by Koppers. RECOMMENDATIONS No additional work is planned on this project because we are going out of the Penta business in the U.S. REFERENCES 1. Notebook pages 306996, 307000, 1220604,5,6,9,22. 2. Koppers Progress Report No. II, rate of Chlorodibenzodioxins in Outdoor Exposure of Penta-Treated Wood, M. A. Phillips and S.J. Ondrev, Oct., 197 6. ACKNOWLEDGEMENTS The analyses were performed by P. R. Michael of J.P. Mieure's group in MIC Applied Sciences. The U.V. exposure work was performed by: J. K. Sears and G. G. Mahnken of N.N. Touchette's group in MIC Plastics R&D. J l 70 o o P^P A -TT VI. DETAILS 1. Experimental SUBJECT TO PROTEi !UL. O R D I R . Solutions containing 15 mg of Penta per ml were made up in benzene. Solutions were prepared with Monsanto technical Penta, Dow EC-7 distilled Penta and, for one series of tests, Baker purified Penta. These solutions were applied to 1-3/4 x 5 inch strips of Whatmans No. 42 filter paper in 1/2 ml aliquots. This gives a loading of 7.5 mg per strip. This loading was used by Koppers to simulate Penta treated wood. One group of samples were also impregnated with 142.5 mg of oil (Lion :71 solvent) to determine the effect of the oil base of penta solutions. After the strips were dried, they were mounted between two pyrex plates. The edges of the pyrex plates were then wrapped with teflon tape to hold the plates together and to retard evaporation of the penta. The samples which were exposed to artificial light were mounted in holders and placed in the Fade-ometer. The instrument was an Atlas Electric Devices Model FBA-R Fade-ometer. The light source is a carbon arc with filters to simulate daylight. The control samples were stored in the dark, during the period that the other samples were exposed. The samples exposed to natural sunlight were placed on the building roof. After exposure the samples were extracted with benzene and analyzed by GLC with an electron capture detector. 2. Results In the first series of tests the effects of natural sunlight versus the fade-ometer and oil versus no oil were compared. The data are shown in Table 1. The analysis of the unexposed samples are in agreement with what would be expected for the various penta samples. The dioxins/furans are quite low in both EC-7 and Baker Penta. The HC3 is high in the EC-7 sample which is typical for this material. The dioxin/furan and HCB level of the Monsanto technical penta is also typical. The low penta recoveries were apparently due to loss by evaporation since a fresh strip gave 100% recovery. The samples exposed to sunlight showed a large increase in both dioxins/furans and HCB. The Monsanto technical Penta was somewhat different from the other samples in that the OCDF decreased and the HCB showed a much larger increase. The penta recovery was also much lower. For all three samples, the dioxins and HC3 formation appeared to be much more favored than the furan formation. The samples which were exposed in the fade-ometer were run in duplicate. In general there was good agreement between the duplicate samples. The fade-ometer results were also in good general agreement with the sunlight'samples. 007 0 2o 7 PCP penta loss but little change in the dioxin/furan/HC3 levels. The only significant difference between these samples and the unexposed samples was the moderate increase in OCDD for the EC-7. In another series, the penta impregnated strips were exposed for three days, treated with oil, and then exposed another three days. The results from these samples are similar to the previous oil treated samples. This data implies that the dioxins/furans/HCB levels are not effected by the oil. Koppers was of the opinion that the oil accelerated the degradation of these materials. Table 2 gives the results of a longer term test. The fade-ometer was used as the U.V. source in these tests. The dioxins analyses were completed on only the unexposed, 12 day, and 24 day samples because the project was deemphasized when we decided to get out of the penta business. A total of 46 days had elapsed between the _time that the_samples were prepared'rand:-the" "time- that"'they*were extracted"for analysisV" Th'is was primarily'due"to the' fade-ometer being shut'down over week ends. The penta recoveries show a uniform decrease with exposure.' In comparing Monsanto technical penta with EC-7, it appears that Monsanto technical penta is more volatile than EC-7 but EC-7 degrades faster.' The'dioxin/ furan levels in the unexposed samples appeared normal. The HCB levels were low indicating a loss by evaporation. The exposed Monsanto technical samples did not show much of a change in the dioxin/furan level. This may be due to these materials degrading at about the same rate as they were formed. The 12 day EC-7 sample shows high levels of dioxins/furans/ HC3 and shows that under certain conditions distilled penta can produce as much or more dioxins/furans/HC3 as technical penta. The 24 day EC-7 is showing a decrease in the dioxin/furan/HCB levels indicating that they are degrading faster than they are being formed since there is very little penta left to degrade. The general structures of the dioxins and furans are given below: 0 (n + n 1) - C h l o r o d i b e n z o - p - d i o x i n O n (n + n 1) - c h l o r o d i b a n z o f u r a n N and n 1 can have any v a l u e from 0 to 4 . 1)070^53 PC? n.iw H O 7 Puni a rueovu ry (%) OGDD (ppm) OCDF (ppm) hu pl.il GDDM'Dl'" (ppm ) hu x.i GDIM-GDI' (ppm) IIGH (ppm) Unexposed 70 0.9 0.4 <0.1* <0.1 101 Muns a nto Teclm (c a l Pont a recovery (X) OGDD ( pin) OGUK ( ppm) hep l a GDIM-CDG (ppm ) liu xa GDDbCUE (pi>m) IIGH (ppm) 62 1105 112 4 75 18 ` 26 linker P u rifie d Pun La re co v e ry (%) OGDD (p[>m) Of.DP (ppm) hup la CDDHIDK (ppm) liux.i CIJ1M GUI-' (ppm ) IIGH (ppm) 71 12 <0.1 1.7 <0.1 6.8 TADUS 1 U V DEGRADATION Ob' PENTA - 3 DAY Exposure Sunlight 3 days 3 days 71 45 785 522 11 35 406 199 126 32 886 1374 3 days 41 585 28 270 37 1136 16 1479 82 2192 986 6628 25 2335 329 1158 227 54 73 22 1673 125 606 36 3268 66 1108 1.6 481 1.34 1207 41 561 44 200 25 1244 37 390 12 112 917 1015 GDI) oi' CDK = c h I n r o d l h e n z o d l o x i n or fura n IIGH - liuxaeh l oruhenzene * d e t e c t i o n l i m i t ~ c o r r e s p o n d s to 1x10 -9 gram. i f EXPOSURE Fade-Quieter 3 days with o il 0,74 57 <0.1 2.7 <0.1 95 3 days w/0 o i l + 3 days w /o ll 0.71 568 41 270 42 1277 0.58 1114 98 514 45 38 0.79 8.7 <0.1 4.4 < 0.1 8.0 0.59 2412 383 1207 237 6109 cin- ! : ,r- - i 0.79 f * ; 1192 i- 95 413 G 53 - j 2082 - J -i n i} i ti-' O,,i Zj O ' i rn fO D.iyii Exposed * Muiisaul o l cell II II II II II II II II II II n" II II 0 3 6 9 12 15 18 21 2A Dow E C - 7 0 li II 3 II II 6 II II 9 II II 12 It II 13 1a II II 2 1 M II 24 TAI1I.K 2 U V DEGRADATION OK RENTA - 24 DAY EXPOSURE Pent a re c o v e ry (%) 24 20.80 17.07 8.17 4 .8 5.61 3.35 2.91 1.87 4 1 . 30 39.07 25.73 10.21 2.53 1 .2 2 0.43 0.38 0.19 IlC 8 (ppm) OCDD (ppm) 7 .1 1200 OCDK (ppm) 200 >. 'i 733 867 , 111 2187 34.7 2653 1053 0.4 2293 >/ ' 127 \' >t 2. L l I V 5 2 0 360 946.7 74.7 hep in CDIHCDE hexa CDDiCDK 507 2 6 .7 387 5 8 .7 467 2.3 oco C~ (i l_ r.. ) c) / "l 71.7 0.4 O J w1 o/ -/ , 160 /7 P/ o' 7 /,5V,. 7 ^ 73.3 k IJ V e x p o s u r e l i m e . 46 d a y s e l a p s e d b e t w e e n p r e p a r 1ng L lie s a m p l e s and e x t r a c t i n g w i t h b e n z e n e f o r a n a l y s i s / f -) APPROVAL PAGE: -6 - i f . A. Hinkabein, Author -n \ VLtT^v- D. ?. Roman, Group Leader Wilson, Manager R&D DATE 2 > -/f/-7 sr DATE /T-7 DATE _ S' W'' -, ^ ' & a 0 7 3 2 71 ?C?