Document Eqz12Ep5aB7K4JKxxjrjeaVN

) 1 M I C - D & P - R & D - St. Lo u i s INTERIM (TYPE OF REPORT] REPORT REPORT NO.: MSL-0104 JOB/PROJECT NO.: 03-000-760.11-7403237 DATE: February 7, 1978 TITLE: U.V. Degradation of Peatachlorophenol AUTHORS: J - A. Hinkebein PERSONNEL: J. A. Hinkebein, D. P. Roman ABSTRACT: Distilled and Technical grade Penta was exposed to both natural and artificial daylight. Dioxins, Furans and hexachlorobenzene were formed as degradation products. AUTHORS: J * A - Hinkebein TITLE: U.V. D e g ra d a c i n o f P e n t a c h l u r o p l i o n o l MEPT. NO.: MSL-0104 COPY NO.: C O 3266 0J702O4 PC0 COMPANY C O N F I D E N T F^Ar. L This docum ent is the properly of M onsanto C om pany and the recipient is responsib le for its safekeeping and d is p o s itio n . It contains CONFIDENTIAL IN F O R M A T IO N w h r h m u c r n n t ho r o n m r li ir o H rp w p a lp rf tn 11n a i rfh ri ri 7Prf g2^33EB5SZ3El COPY NUMBER 1. P. A.ierney, J.W. Cross - N Res 2. J. S. Metcalf - B2NC 3. A. T. Smith - G2WD h. R. G. Potter - B3SB 5. Tech. Reports Library - R2C 6. Tech. Reports Library - R2C 7. E. A. Matzner - N3A 8. G. J. McEwan - N3A 9. J. H. Payne - N3A 10. J. D. Wilson - N3A 11. J. A. Hinkebein - N2B 12. D. P. Roman - N2B 13-16 .D. Danna - E2NB 17. M. E. Blaylock - B2NA ' 18. B.* W. Eley - A2SC ABSTRACT ONLY Akron - 1070 R. W. Wise Dayton - 1250 E. E. Hardy Via D. Danna - E2NB 4 copies Melbourne, Australia Montreal, Canada Louva1n-la-Neuve Central Reports Library H. E. Hadden - R2C ABSTRACT ONLY M. E. Miller - B3SB C. F. Call is - B2SA J. W. Cross - N3A M. W. Farrar - R2E R. K. Flitcraft - 1250 E. J. Griffith - N3D W. C. Ha/rmann - T3A S. A. Heininger - G5EA W. R. Knox - R4C F. P. Laelle/H. M. McJCelvey - G2WD E. A. Hatzner - 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'- R4B C. Y. Shen - N2B C, C. Sis 1er - R2E A. J. Speziale H. W. Touchette - 1730 M. C. Throdahl - DID J. D. Wilson - N3A F. B. Zlenty - T3A ,,1.- "TM SUBJECT TO PROTEO IiVE OROER. C O M P A N Y i R C O N FI D E INITIAL- W hen no longer needed, or upon request, return this re p o rt to o (j 7 u PCP 1,r\ I. INTRODUCTION SUBJECT TO ~''i 'W Koppers Co. reported some work, on UV (Ultra-violet) degradation of Penta. They found that the higher chlorodioxins such as octachlorodibenzo-pdioxin (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. II. 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 (HCB) . 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. 4. 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. III. RECOMMENDATIONS No additional work is planned on this project because we are going out of the Penta business in the U.S. IV. REFERENCES 1. Notebook pages 306996, 307000, 1220604,5,6,9,22. 2. Koppers Progress Report No. II, Fate of Chlorodibenzodioxins in Outdoor Exposure of Penta-Treated Wood, M. A. Phillips and S.J. Ondrev, Oct., 1976. V . ACKNOWLEDGEMENTS The analyses were performed by P . R. Michael of J.P. Mieure's group ir. MIC Applied Sciences. The U.V. exposure work was performed by: J. K. Sears and G. G. Mahnken of N.W. Touchette's group in MIC Plastics R&D. JO 70 o o ?.P -T VI. DETAILS 1. Experimental _?_ c e ' """;... a1 SUBJECT TO PROTECTIVE ORDER. Solutions containing 15 tig 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 NTo. 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 rag of oil (Lion :7l 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 10071 recovery. The samples exposed to sunlight showed a large increase in both dioxins/furans and H C 3 . 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 HCB 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. 00 70 2o 7 PLP penta loss but little change in the dioxin/furan/HCB levels. The only significant difference between these samples and the unexposed samples was Che 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 tern 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*%nd' T;hEr time'that'`they were extracted'"for analysis'.' Th'is was primarily 'due'iid 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/rurans/ HCB and shows that under certain conditions distilled penca can produce as much or more dioxins/furans/HCB 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: O Cl n (n+n ') - C h l o r o d i b e n z o - o - d i o x i n n (n + n ') - c h l o r o d i b e n z o f u r a n N and n' can have any value from 0 to 4. PC? TA Lli 1 U V DECUADATION OK PENTA - 3 DAY >iw I X - 7 ' e m a r e c o v e r y (%) OCM) (ppm) OCM' ( p [in) i e p t .1 CDIHCDF (ppin) icx.i CMHCDF (ppm) ICI! (ppm) Unexposed 70 0.9 0.4 <0.1* <0.1 101 Itins.iuto Techn l ca 1 l'enta r e c o v e ry ( Z) OCDI) (ppm) OCUF (ppm) l i e p t a CDIHCDF (ppin) liexa CDIHCDF (ppm) IICH (ppm) ` 62 1 105 112 475 18 26 laker P u rifie d l'enta recovery (Z) OCM) (ppm) OCDK (ppm) l i e p ta CDIHCDF (ppm) liexa CDIHCDF (ppm) IICIl ( ppm) 71 12 <0.1 1. 7 <0.1 6.8 Exposure Sun 1lgl\L 3 days 3 days 71 45 785 522 11 35 406 199 126 32 886 1374 16 14 79 82 2192 986 6628 25 2335 329 1158 227 54 73 66 1108 1.6 481 134 1207 41 561 44 200 25 1244 3 days 41 585 28 270 37 1136 22 1673 125 606 36 3268 37 390 12 112 917 101 5 !DD u r CDF = cli 1o r o d l b e n z o d i o x i n o r f u r a n u;u - hexaelt l o rohenzene * le i ci: Li on l i m i t - c o r re s p o n d s to 1x10 - 9 gram. / ( KXI'OSUKE K;nic-oinc ter_____ 3 days with oil 0.74 57 <0.1 2.7 < 0.1 95 3 Jays w/0 oil + 3 days w / o T 1 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 in c~ Cj 0.79 ;L : 1192 95 413 ^ 2082 -o :j O * r/ O, J U f/T .> Days Exposed * Monsanto tech 11t l H1 1 M tl 1 r 11 MM 111 1 H Tl II 11 0 3 6 9 12 15 J8 21 24 Dow EC-7 0 n 11 3 ti II 6 it II 9 11 11 12 11 11 15 n M 18 11 11 21 11 n 24 TABUS 2 , U V DEGRADATION OF I*ENTA - 24 DAY EXPOSURE Penta recovery (/i) llCll (ppm) x- CD 24 20.80 1 7.1 17.07 8.17 733 5.61 3.35 2.91 1.87 2187 OGDD (ppm) 1200 867 1053 OCDF (ppm) 200 111 !I- : 127 41.30 39.07 25.73 10.21 2.53 1.22 0.43 0.38 0.19 34.7 2653 360 0.4 2.1 2293 ,520 9/16.7 76.7 hepta CDIH-CDF 507 hexa CDD+CDF 26.7 387 5B.7 o467 71.7 ? i g 'l 2.3 O 7 3 0.4 ~0 o'} 1333 (J3 ' 7i Z! ) 160 3I 9I ov 6$. 7^ 73.3 011 * U V e x p o s u r e Lime. 46 d a y s e l a p s e d b e t w e e n preparing the samples and extracting with benzene for analysis. / f 1 AFPROVAL PAGE: -6- A. Hinkebein, Author \ ' v Uc r ^ s} D. P. Roman, Group Leader p^-/?-7r DATE DATE u O 702 ?L - PCP