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FINAL REPORT NO. 39.96 b. (Cont'd.) the flaking period. There is little change in other dioxins from start to finish of flaking. The hepta CDD and OCDD values are Inflated due to exposure to caustic during sample clean-up (See Section B. 2.). c. Distilled Penta - Dow VS Monsanto (OR 236326) A sample of Dow's commercially refined Penta was obtained in September, 1974. Comparative analyses to Monsanto lab distilled Penta is presented below. Dow-Lot 09214M Monsanto-Lot 214234 Appearance Chem. Assay HOI MOT Aik. Insole. GLC: Tetra Penta H.B. Dioxins i ^Hepta CDD Hepta CDD OCDD Slightly Off-White Prills White Powder 101.262 0.12 101.692 . 0.12 98.02 99.02 0.052 0.042 7.62 11.52 ' 91.92 ^0.52* 88.52 0.12 Duplicate Analyses 'interfering Low Boilers 1 2 .8 ppm 1.2 ppm, 0 . 6 ppm, 0.1 ppm 0 . 1 ppm 9.9 ppm 0.6 ppm, 1.2 ppm * Unknown which nearly co-elutea with tatrachlorophenol There are a numbef of similarities as well as differences. Chemical assay, M0I, MOT, and Alkali Insols are comparable. Differences are as follows: 1) Appearance color of Monsanto material is noticeably lighter (due to our RT 53A stabiliser). 2) Tetrachlorophenol/Fentachlorophenol ratio is lower in the Dow sample. 3) Thera are a number of GLC "strangers" in the Dow sample particularly low hollars. 4) Monsanto distilled material is lover in total dioxins. GLC analysis was by internal marker method (OR 211759). Dioxin analy sis was by Method No. 70-20. (Response factors described in previous section of this report.) Reproducibility of dioxin test is not parti cularly good as indicated by duplicate analysis on the Monsanto sample. The Dow EC-7 sample was also examined for metals. Aluminum was the major metal present along with the usual trace amounts of other metals. This indicated the Penta was initially made by the phenol chlorination route and that refining does not remove all the aluminum catalyst; FINAL REPORT NO. 3996 37. F. 3. c. (Cont'd.) (For detailed metal analysis, see Appendix E.2.) Dow's recent distillation Fat. No.US 3816266 refers to the use of amine stabilizers.^ We suspected the unknown compo nent, co-eluting with tetrachlorophenol might be such a compound. The Dow sample was Individually spiked with the following aiblnes which were mentioned In their patent. None matched the elution time of the unknown. Trlethylamine Diphenylamine Tetraethylenepentamine Aniline Trlphenylamlne No other efforts were made to identify the unknown. * The wood treating Industry has indicated there Is a very severe caking and dust problem with Dow's EC-7 material. They also indicate Fenta solvency compared to technical Penta in common wood .treating oils la lower. There was one Instance where the EC-7 material could not be used In their process because of low solvency. No other producer, foreign or domestic, Is commercially marketing a-reflned Penta. Vulcan.Materials Co. however was recently Issued a Patent (Reference No. 31) which describes batch distillation of Penta. We have not studied the adaptability of our refined Fenta In the wood treating Industry. If we were to begin market ing refined Penta In a prilled form tomorrow, our product would likely have the same disadvantage as Dow's EC-7. d. Santophen - 1 W.G.K. AR&D examined Santophen 1 for dioxins. None were found. MDL In their test was 0.1 to 0.5 ppm. Because of Interferences however, chlorodloxlns with less than 3 chlorine atoms could not be*determined by their procedure. Their work is presented in W.G.K. AR&D Report No. 2648, "Dept. 239 - Santophen 1 - Analyses for Presence of Chlorodibenzo-p-dloxins in Product", 4-18-74, H. L. Camp bell (Reference^ No. 44). (See more recent analyses pg. 67.) e. Competitive Penta The following Penta samples were received and analyzed for the various properties indicated. 38. ' FINAL REPORT NO. 3996 Relchhold Lot 27874 Brazilian Chlorogil B-27-74 , . Brazilian Chlorogil 10-4-74 Mexican Pentarin Lot 12731 WGK Typical Appearance M0I MOT Brown Prills 1.02 32.02 Pulverized Flakes 2.02 9 . Z Pulverized Flakes < 0 .1 1 34.5Z Pulverized Flakes 6.02 11.52 Tan Prills < 0.12 55.02 Chemical Assay GLC* Tetra Penta HB 98.3% 6.99X 85.692 7.322 98.3X 10.82 80.72 8.52 97.82 12.72 78.42 8.92 95.62 4.42 84.62 11.02 97.52 6.02 86.52 7.52 Dioxins: ^Hepta** Hepta Pre-OCDD*** OCDD TOTAL. 3360 ppm 1337 " 101 " 1272 M 6070 " 1108 ppm 675 " 74 " 1314 " 3171 " 1570 ppm 1448 " 161 " 1555 " 4734 " 1601 ppm 1632 " 1143 3036 " 7403 " 700 ppm 1 0 0 " 370 " 2700 " 4770 " * Internal MKR. CLC Method (OR 211759). ** GLC Method (OR 212188) - Modified Method No. 70-20. *** This compound is probably Octachlorodibenzofuran.^3 e. (Cont'd.) Metal analyses were also run on- the Mexican and Brazilian samples (See Appendix E. 2. for details). Dioxins were determined by Method 70-20. *** ^0 W.G.K. typical material is comparable or better quality compared to the competitive samples. There was no gross difference In dioxin content between any of the samples. Dioxin values (hepta CDD & OCDD) are Inflated on all samples due to exposure to caustic in sample preparation (See Section B. 2. for details). The Relchhold sample was later Included In CEF studies. (See Section F-7). f , Miscellaneous Samples The following miscellaneous samples were also analyzed for dioxins by Method 70-20. ^Hepta CDD Hepta CDD OCDD 1) Dept. 236 Cone Tank Alkali Insolubles (OR 212171) 0/942 0.592 0.992 2) Venturi Penta (OR 212192) 3.3 ppm 1.4 ppm 5.9 ppm FINAL REPORT NO. 3996 39. F. 3. f. (Cont'd.) ^ Hepta CDD Hepta CDD OCDD 3) Dept. 237 Chloro- (All detected - total approx. 10 ppm) phenol Fractions cut (OR 212191) A) Overchlorinated (Not determined - Sample 2.45X Plant Penta-Ba, Contained 4.65Z Allc. Insole) J-9 (OR 256342) 5) Alkali Insolubles 0.37X 0.31X 1.05Z from Spent Cen tral Fume Scrubber Liquor (OR 212171) Cone tank Insolubles are from Santobrlte solution prepared from a mixture of scrap Penta and Prill Fume Liquor. Ven turi Penta is Penta from prill fumes. Chlorophenol Fractions Is raw material chlorophenol for Penta (Dept. 236). The overchlorinated Penta is an end of batch chlorlnator sample from a batch which was accidentally overchlorinated on Oct. 10, 1974. (Over chlorination resulted from faulty X-Pt. reading at end of batch.) As of this writing, we have not analyzed the alkali lnsols (Samples 1 & 5) for those dioxins containing less than 7 chlorine atoms. We suspect though, copious amounts of the lower chlorinated dioxins, Including TCDD, are present. We believe they are being generated through alkaline catalyzed cycllzatlon of dioxin precursors. These lnsols, and the aqueous solutions associated with them, should be handled with extreme care. 4. Plant Demo - Low Temp. Chlorination Bloassay tests (1973) on low temperature lab prepared Penta indi cated a moderation of CEF activity. This encouraged us to try low temperature chlorination in the Plant. Early in 1974, Amendment "F" to Dept. 236 SMPD (Reference No. 45) was prepared and approved to allow the tests. The following parameters were evaluated: 1) reduced temperature from 1.400.to 1.600 sp. gr., 2) Increased catalyst level, and 3) reduced X-Pt/batch temperature spread dur ing "rate of rise". Due to cooling limitations of the heat ex changer, low X-Pt./temp. spread could not be achieved without re ducing the CI2 feed rate to a trickle. This extended chlorination time too much. Another amendment (Reference No. 46) was written to permit reduction of batch size to 50X of normal. This time the low spread was achieved without extending chlorination time. In summary, the tests were carried out In seven segments, one of which was at standard conditions. Two to five batches were made at each set of conditions. Composite samples were made of each segment 40. FINAL REPORT NO. 3996 F. 4. (Cont'd.) and analyzed for higher Chlorodioxins and other properties. Data from the tests are summarized on Table No. 1 (Page 41). Test re sults at this point Indicated the following: (1) Low temperature from 1.400 to 1.600 sp. gr. gave a significant reduction in non-phenolic HB's eluting prior to hepta CDD. The reduction was comparable to that achieved In low temperature lab batches (211535 & 211525). (2) Increased catalyst level gave slightly lower total dioxins (We had not observed this In lab low temperature batches. In addi tion, Method No. 70-20 was used for analyses, and all values are no doubt Inflated.) (3) HB's remained about the same level In all segments (Internal marker method OR 211759). (4) From an operating standpoint, low temperature had a negligible effect on total batch time. Low spread was also easily main tained when batch size was cut In half. (A second heat exchanger would therefore be expected to give the same result on standard size batches.) (5) .(6 ) Average chlorine efficiency was Increased about 4Z when catalyst charge was doubled. Normal quality characteristics remained essentially the same In all segments. Batch temperature In the tests was primarily controlled by varying the chlorine feed rate while maintaining the same amount of cooling. 5. BloAssay On Low Temp, Plant Penta & Penta Oil Solution a. CEF and Chloracne Response The composite samples (OR 212180) from low temperature plant chlorination tests (References 45 & 46) were submitted for CEF and chloracne tests. A sample of Venturi Penta In AD-73 oil (48X wt.) was also submitted along* with a sample of our current Penta additive mixture. The test results are summarized on Tables No. 2 & 3, (Pages 42 & 43). Some of the plant low temperature samples showed a moderation In CEF activity (negative at 500 ppm), but none matched the modera tion observed in low temperature lab Penta samples. The 48X Penta solution sample and the additive mixture were each void of CEF activity at the highest dietary level tested (1500 ppm). The chloracne responses on plant test samples were very confounding bast sample waa the control material? ? 1 DEPT. 236 TABLE HO. .1 AMENDMENTS f 4 H DATA SUMMARY - AVERAGES S. H. Vogel 5/13/74 a bc 1.400 1.600 d r.r. al sh . ci2 1.600 130C. Cat. Final Heat Fra- Total Chea. Total Assay Trap. Tenp. Cpnc. Spread History H.CDD R.CDD OCDD OCDD Dloxlna H B H01 MOT Assay Tims S i . A n ___ (C) (C) *PI) IPI) (pi) (PP) (pi) (X) (X) (X) <Z) w CONDITIONS OR 212180-1 CONTROLS (5) 94.75 94.8 106.9 0.073 7.0 16.3 713 1003 369 2716 4800 7.84 2.8 49.1 97.9 6,11H 81.9 CONTROL 01 212180-2 Segment 1 (5) 93.6 79.3 114.4 0.074 6.7 16.4 689 1303 468 2929 5391 7.45 2.8 39.0 97.6 6'7" 83.6 80C. OR 212180-3 Segment 2 (3) 95.8 64.7 104.5 0.075 6.5 . 15.2 409 1170 522 2526' 4627 7.09 1.7 37.0 98.3 7* 52" 82.1 65c. OR 212180-4 Segment 3 (5) 96.0 OR 212180-5 64.4 K'2.5 0.124 6.5 14.8 389 942 544 1944 3819 7.13 3.7 44.0 98.2 8*31" 86.8 65C 2xCAT. (Long r.rJlam) Segment 4 (3) 95.0 63.1 104.4 0.066 3.1 41.1 397 850 334 2836 4417 7.53 3.3 32.0 98.4 14*7" 81.2 65C Low Stremi OR 212160-6 l/2 Batch Segment 5 (4) 94.5 62.6 110.4 0.127 3.6 14.8 487 659 452 2696 4294 8.30 4.9 69.5 97.8 6'36" 65C. Low Spread 2x CAT OR 212180-7 Segncnt 6 (7) 94.0 V 64.4 110.1 0.093 2.8 18.0 332 559 314 2139 3344 7.50 4.0 66.8 98.2 6'58" -- 1/2 Batch 6SC.Low Spread KH-261 90-95 -- 95 -- 110 -- 0.073 .-- 7.0 - 1 7 793 1092 120 3775` .5780 -- 9.0 Plant Std. Lot 211535 211525 100 80 -- 110 0.073 -- 3.0 < io 321 523 < 30 3409 4303 7.45 100 80 ^ 1 1 0 0.073 < 1.0 4 10 337 504 291 3593 4725 7.22 Lab Reduced Trap. Lab High Level Ci 12938 100 '*'55 -- 70 -0.073 < 1.0 REICHH0LD (6/6/73)-- .-- -- -- -- 4 1.0 --- 209 190 369 < 1 0 647 < 10- 999 2196 1577 3033 5.30 8.28 Lab Kin.Temp. TOTAL PERICARDIAL FLUID (Survivors Only) Total Deaths a. Average batch tap. from 1.400 to 1.600 sp. gr. 70C. (degrees C) Spie. Fluid b. Average batch tap. fro* 1.600 sp. gr. to 130C. batch tap. 1 3.55 10 c. Lbs. Aluminum catalyst per lb. mol*-- 'phenol. 2 3.15 15 d. ( a ) 2 area, between R Pt. 4 batth tap. from 130C. batch tap. to end of batch 3 1.70 12 (from atrip -chart). * 2.15 12 e. NjCDD -- >Hepta CDD 5 1.25 7 f. Probably Octachlorodlbenzofuran - ace Reference No. 43. 6 7 COMMENTS 1.65 6 f. Total batch time from 1.400 sp. gr. to end of batch. 1.3* - 6_____________ J U l Determined by Cr* chenee of Scrubber Phenol. * n A i i v i u u i i u i u i l in n i a l i o n i a m o u a i j i c a -- n t i v r u j n o i 2. Lu e 5 entri are Includo! for ccmparlson purposea. ._ 3. - Por dctalls on compoaltlng - Set Notebook Page 212180. TABLE NO. 2 CHICK EDEMA FACTOR BIOASSAY WITH PLANT-PRODUCED PENTACHOLORPHENOL Project No. BTL-74- Lot No. 28 212180-1 29 212180-2 30 212180-3 31 212180-4 Low 32 Spread 212180-5 33 ii it 212180-6 34 M II 212180-7 Process Condition Standard ppm 0 150 500 . 1000 1500 Pericardial Fluid Volume (ml) 0 .1 0 0 .1 2 0.15* 1.34* 1 .20* ppm 0 150 500 1000 1500 Total Mortality per 12 checks Deaths 1 0 1 2 6 10 80C do 0.10 0.12 1.24* 0.52* do 2 2 2 8 15 65C do 0 .1 2 0.18* 1.06* 0.33* do 0 2 2 7 12 65C 2x Catalyst do 0.10 0.12 1.33* 0 .86* do 0 0 1 10 12 65C Blow CI2 rate 0.09 0.13 0 .20* ' 0.38* 0.33* 0 0 0 4 3 7 65C 2X catalyst reduced batch do 0.13 0.46* 0.39* 0.60* do 0 1 0 5 6 65C reduced batch do 0 .1 2 0.15* 0 .22* 0.69* do 0 0 0 6 6 35 212180-9 Recovered Venturi do --- 0.12 -- 0 .1 0 do -- 0 ----- 2 2 36 212180-8 Additive Mixture ** do 0.10 do 00 i * indicates positive check edema factor activity. I ** 15 ppm in diet equivalent to 1500 ppm pentachlorophenol addition. TABLE NO. 3 Rabbit Ear Chlorcne Bioassay with Plant-Produced Pentachlorophenol * Project No. CMU-74-41 Lot No. -- A 212180-1 B 212180-2 C i212180-3 0 212180-4 E 212180-5 F 212180-6 G 212180-7 Process Condition Ointment Control Standard Batch 80C. 65C. 65C 2x Catalyst 65C Slow Clj rate 65C 2x Catalyst reduced Batch 65C Reduced Batch Change In Ear Thickness (10-3 inch) 12.4 a 16.0 22.9 23.6 18.8 18.5 18.3 20.9 Visual Score 0.2 a 1.0 2.0 1.9 1.5 1.6 1.5 1.6 Microscopic Score 0.1 a 0.9 1.3 1.5 a 1.0 1.3 1.4 1.6 * Thirty applications of 0.5 g of an ointment containing 5X test material. a,Indicates values that were NOT statistically different from control; all unmarked values are statistically greater than the .control. 44 PINAL REPORT NO. 3996 F . 5. 6. b . Quantitative Evaluation of CEF Data We next tried to avaluatli the BloAssay date quantitatively to aee how d o m e va did cone to matching the Improvement: eean In the low temp, lab batches. This evaluation is found In Appen dix E (Item No. 3). In shorts the "low spread*' samples came within a few X of matching 211525 and 211535 material. The evaluation also predicts that If X-Pt/temp. spread is kept at 1C or less during "rate of rise11, we will match or surpass the CEF improvement obtained on the-lab low temp. Penta. In addition only three of 17 process parameters that..ware exam ined for relationship to CEF data gave confounding correlation to the predicted. Statistically, the low temperature from 1.400 to 1.600 Sp. Gr. was also quite Important in moderating CEF activity. Chlorination Studies a. CAT. Impurities, Al/S Catalyst, Cat. Swamping Effect, and Penta Sulfur Analyses. tf Additional chlorination studies were carried out in the 74-75 period. The studies were aimed at finding ways to suppress dioxin/HB formation. Areas studied were: (1) Alternate catalyst systems (2) Effect of catalyst Impurities (Fe & Mn) (3) Effect when swamping with highly soluble catalysts (SbCl3 & ZnCl2). Data from this work Is presented on Table No. 4 (Page 46), Only the Al/Te and Al/S alternate catalyst systems demonstrated a moderation in by-product formation. Chlorination selectivity va*s also enhanced as evidenced by higher than normal trl & tetrachlorophenol maxlmums. Reactivity was essentially unchange' ed as measured by chlorination time. One peculiarity of these systems Is- the obvious reductlon/ellmlnatlon of two non-phenollc components on the GC, believed to be hepta and octachlorodlbenzo- furan. (See Figure No. lt Page 45.) Similar benefits vara also observed over a large range of- Al/S catalyst ratios. This Implies ther* Is some miulaal amount of sulfur or tellurium re quired, and no benefit la gained when using quantities above the minimal amount. Other benefits are slightly Increased chemical assay, markedly reduced alkali Insolubles, 'and a significant re duction In < bapta CDD non-phenollcu7~ Recently examined Kelch- hold Penta also has these characteristics. We looked for sulfur In their material: (256347) 8ULFUR v- Avg. Relchhold Lot No. 6-6-73 10 ppa & 5 ppm 8 ppm16 Lab Prepared Al/S Cat. OR 256330 I" . s 16 ppa & 13 ppa 15 ppa v. 1OA c TM r*i-- /. . co* iPECnoKorTmethod ho.71-1 (houimo) 1 .0 CUM FOTTA IN 10 KL I I J f l I K l - CHXUHATOCUmED OVIK 4 0 KL A ljO . ( I I HjO DEACTIVATED), C0 7 0 1 ITT 100 M. i i k u i i i u X n . J . o 1 1 o r jo o o i d i u m cm in je c t e d . CC COWPITIOWI (Hr-1710 - NICKEL 41 D m Crt) 110C.* II. 1 1/4 I. GUI! COLIMI liant euul HELIUM 40 b I/b Ib . ru ici 110 bI / b Ib , INJECTION TEXT. 110C. OCTLCTO TEXT. HOC. ATTENUATION 14 1 LUCI 10 1 tuu i intekval IM 41 U-40, 10/100 CULON V HF I I I I 8 si *3. , 9 f - ~ S Ab Ck t-.K-.A-r.-oJs ,Ttu fi* . V /-/V -7C ATckr/iJ. 7J / * / f 03 73 7 <10S Q1/ 3 3JSC, A C.AT At/n* Al A . AlA * - CcOaMtC;. "T7V^.rr5fVAr3r v..ta;- b ___________ a /ftVw7..T7/WV3 74/1.7iV7 ff* <>l*OD //a /ZVo 7.77 J S J______ c _________________________________________________ pf* CJ>{L^ S/r HC /S f**. a<.or <IO /0<f PtM, QUto J/J/7AV7 4.99^9A..75#H<U C<sMMBajFsplfcjjvk J v;^ .9 *'7 7*fStStt3JA*Jt 4 3 79 17 0 *4Waaas5Sst1A*t,t33a337ia700o ti/sAidt *..V/Avrj*t oA lfa Ai.<*, *i/l% V.------ A/m* .h/ .i M-Mdl {*/. IC JL/xa, .i/v.t /Sat.a.aoa- ffK2SitZAr**S.ni2mI,d7r;/J.w..9V/Uw7f7 '<wM11 A? 3i 7ta/ /O f/ fVSi-77i vf 1 A? /fi* ///Va /fS ! *ii1 J37r ?/A S* /*oJf Mo* (^f'iJ*C^ K9A99jU.0>&41^Ai oto,X4Xfl^3O.<0Ka/i}/Mm^ooFTr'/*yCo/i.U.or^'/fc*TH' Uii*^f 3 9.7art3io 3 9S5S4L3Z7tViL ML AJL AX 333c i b i l i AJL 3 9s5t633137* aA m/ s 9a54JVV AS/S 1175SC6-333?0? Ai/s Al/S c.* ooc,,.5SVtV 1/0....0W775if" SY.S nmi ?9C.S9 J^73...t:4fni 7Vi /ASV id/*. o **i/.H* o.V// A/a- S.t V.V <7.S./V faoV ti.es Si.Ci Pi.CI n .u 7.if 7o* 4.v3r t3ot/r j *7 Col /ai/ J3A9*f m33 i*ti AIA 73//%Vt9As33CAaa/Aaf'.3*733/o^ f <<1*100 ./t? / . f / fS /o/.O <10 fe.A /vya ? J <10 Ja/,a e*ir/**e trek ARIOOOX1^1AiraiAtM^LoorftfATguAUz hmSZSJ//(AUCfT"V*AouJ^n <f.O <o.l <7o.(0I j/Pfn?yit*r.,..0Q*o iji'1Cr0JlVrli.i-4.rtAv<-,v*t5.iVS UiT^oiAr- X-iJ/nVAi. Kr. CvAtG4Lo/*;aAT*A--UJo^L I^T fOtl/TlJ 03,3as-ti7t asbi-tt AI/osh hifa# o.v/.3 <o.*.0* -*#-3.7/ y^^.75"50 1 / Jittcrotk^r/Vu^--^Poc/j'jvAirT&/ or^s*i37a _____ C o m iL V i'j W /. /MoLfia-FVa tu Pk** 1 / & * r c L A. H u l T - /V# 4 & r * T / * > J 3 . g 'c. AVoo -- /too />>*. 7 0 V, V. T .^4.i <Lk ^ . a 5"> Ryf+6Us /a /u * c (.. ft -iV* Xc.4, KdirLft. iwrtr4L A4u l o X *. qr*Ms 7 * 7 M + <2f *H L te -l Ma a k a jl o A ^ n -fS ? C, ktf*MLii.l Louj<4 J, UjCb //yr^ c j TTtA) tay/TV C->0 ,, OcTAC-kU^oX-'l x^X4^>AA/-xx^y' ^* i r.Y\ * pvr< O^- w*ie UkoJ /W77 /t-Tt-k 7a*<*. ^ '. FINAL REPORT NO. 3996 47. F. 6 . a. The analyses were carried out by P. Jeannot of Physical Sci ences Center. An oxyhydrogen combustion technique vaaused. (Notebook Page 772190) Although there is a vide variation In duplicate analyses, there is Indication that Reichhold may be using sulfur In their system. Average sulfur content In their material Is higher than our standard material. In addition, of the initial 94 ppm sulfur added to OR 256330, only 15 ppm re mained at the end of chlorination. The same thing may have happened to the Reichhold sample during manufacture. A major assumption Is made -- that being, the sulfur analyses are not grossly in error. All Al/S runs on TABLE 4 were made at low temperature front-end (60C. from 1.400 --- 1.600 gr.). Some additional Al/S batches were made at standard manufacturing temperatures. Data from these runs-are presented on TABLE No. 5. Only cursory dioxin analyses (Method 73-1) have been run on 'these samples to date. Compared to the control, non-phenolics in all Al/S runs are reduced about the same amount. We cannot explain the unusually high and variable HB content in the batches. Further evaluation might be done before Al/S system is tried In the plant. . Although ve have not tested Al/Selenium system, It should ex hibit the same affects as Al/Te or Al/S systems. Selenium Is an analogue of Te and S. Use of Te or Se at this time was ruled out due to their toxic and cost disadvantages. b. H?0 Content Before- Catalyst Addition Introduction of moisture to the chlorination mass via raw ma terials or other sources has traditionally been a concern. Presence of moisture after catalyst addition is known to moderate catalyst activity, or In severe cases, totally deactivate the catalyst. The detrimental effects of moisture In CI2 feed has been Illustrated in a 1972 study by Nell Thompson. ^ Chemical assay and other quality characteristics are significantly harmed. In lab chlorination studies, we have tried to minimize the mois ture (in raw material phenol) problem by chlorinating for 30 to 60 minutes prior to catalyst addition. By-product HCl strips the moisture out. This is Illustrated on Figure No. 2 (Moisture vs Level of Chlorination). Moisture content goes essentially to zero near the dichlor stage. Figure No. 2 also shows moisture profiles while chlorinating In the presence of sulfur as well as S02* The rate of H2O disappearance was essentially the Bame on all three profiles. We had hoped S or SO2 would facilitate ti tration of H20 to H2SO4 , analogous to K. 7. titration: so2 + h 2o h 2so3 + h 2o <-- > + *2 < h2so3 H2 SO4 + 2HI  < A-k IvL u /wivri'aoj M/s ATig V M - va 7% h L < L " O S ' . /-/V-7 C ^ .//. L Cj ^|xli.|,T ; 0 ^ * - L S a **. V ATi_k*S -- e x L S / r S r l . H*4 4 . % *f M A T w r / + S*Kotd C**'..*".J, /'`c. /,yo `--* S/'&i*) 4^ i O AT. *Tt-W NO. g a -t ; TerRAr ^EpjTA r t >4_*. H m xwio6. AtAi/ bF-itc. A U . M o r H*T C. Max M r >vc C oiWHffWtf a s 7 Wi /U o ./S 2n m S i.V H M l 0,03*0 'T.f i 3?,0 -<oJ 6f, JJ.S* <2a/7X*- a snoH *. 31O J S / o S s M 2MM ? , l 0,0 3? 77.0 3iC io,o 5*fl/5* /J,7 A S 7 0 <W a 57 o H 7 m / s o .i/'e y Akl G . s / f t 7 17.7.S7 S I.S 9/6 A ioaf y * S/,0 < J SV.a /a, 0 .10 t li( > / 2/ 0 i-- 3T 3 .. t ^V<Lw ^ / " V W t / (2)h W . G . K . `S T V o J 0 t / 7 X t / r C K T E u d A n t r i ' <2o4*i P;oi To Li* b c ^ A T c J w T) i/o K/J #C <3* -ffTO V f.) /l*Cwt>"J0'S H c * A c U l o * * b c w a w * *- u C t** s * J 2 .a * t& aT-n/tra o* di'ox/J bj M c r k ^ l AO ~ 7 3 - | CAff.Jc#) ( a 5 ^"?Vo) CO FINAL REPORT NO. 3996 49. F. 6 . b. (Coat'd.) The difference being, Cl2 would be the oxidizing agent instead of I2, Due to the high proton concentration in the Bass, ve b u b pect the equilibrium to sulfate was suppressed. This might be worth another try in the presence of barium ion which should force the equilibrium to the right by precipitating BaS03 and BaSCty. Aside froth catalyst deactivation effects, moisture no doubt plays another detrimental role, in that hypochlorous acid is formed. Cl2 + H20 > H0C1 + HC1 B0C1 Is a powerful oxidizing agent. Are dioxins generated when Penta is oxidized -by H0C1? Or more importantly, is H0C1 the principal reason for dioxin formation during chlorination? A few milligrams'of distilled Fenta were Introduced to a 2SC. basic solution of B0C1. Reaction was immediate. A yellow oil was first produced, which slowly became a tarry substance. Recovery of the oxidation products through hexane extraction + GC after phenollcs removal showed a host of products, but OCDD and hepta CDD were present in large concentrations. The ex periment was repeated in acidic H0C1 solution. The reaction again proceeded but not as fsBt as in KsOCl, (256757). We also tried Fenta oxidation with aqueous Na202 . No reaction occurred. (The oxidation potentials for NaOCl and Na202 are very similar.) This leads us to be more convinced that a cyclohexadlenone is involved in dioxin formation. H0C1 OH Cl Cl Cl + h 2o h22 + Cl No TGEnT 1-- cl*(Chlorine Radical) Cl i Intermediates (2-hydroxy ^ diphenyl ether) Dioxins >'rrl. I(IKK r.n {VTP *< At 50. FINAL REPORT NO. 3996 F. 6. b. (Cont'd.) The overall detrimental effects of moisture in the chlor ination, both before and after-catalyst addition, are not clearly known. We don't know for example, at what level of chlorination a positive CEF on the mass first becomes apparent, and if it's related to moisture content. 7. Bioassay - CEF on paraclilorophenol, 2, 4-dichlorophenol, Lab Fenta Al/S and Al/Te catalyst, Reichhold Penta, and benzene chlorodioxln solutions of hexa--CDD and TCDD. In December 1974, another series of chlorophenol samples were submitted for CEF evaluation. BTL REPORT NO. IDENTIFICATION DIETARY LEVELS BTL-74-104 BTL-74-105 BTL-74-106 BTL-74-107 BTLr-74-108 BTL-74-109 BTL-74-120 BTL-74-87 BTL-74-88 BTL-74-89 BTL-74-90 p-chlorophenol-S till Residue 150,1500 ppa Fractions phenol - 236- Feed 1500 ppm Refined p-chlorophenol (PCP) 1500 ppm Refined 2, 4-DCP 1500 ppm Hexa CDD benzene solution 0.5,2,10,50,250 ppb TCDD benzene solution 0.005,0.02,0.1,0.5,2.5 ppb Reichhold Penta-256386 0,150,500,1000,1500 ppm Lab Fenta - 211535 (Low Temp.) M Lab Penta - Al/Te-256304 II Lab Penta - Al/S -256330 II Lab Fenta - Al/S - 256338 II Results of the tests are presented in TABLE No. 6. page 52. In summary, the following was Indicated; (1) CEF activity was not observed in PCP Btlll residue, frac tlons phenol, refined para, or refined 2, 4-DCP - at the highest level tested (1500 ppm). (2) Reichhold's Penta exhibited positive CEF activity - but not as severely as our conmerclal material. (Certain nonphenollc components (dlbenzofurans?) are reduced or ab sent In the Reichhold sample; these same components are reduced or absent in our Al/S and Al/Te batches.) Reich hold has also indicated CEF activity on their Fenta was negative on tests run at Hilltop Laboratories. REC studies were not made on this series of samples. Hence, we cannot say if REC toxicity is Improved by the Al/S system or on Reichhold's sample.3 (3) Al/Te and Al/S prepared material shows negative or reduced CEF activity: Al/Te-256304 - negative at 1500 ppm level A l / S -256330 - " " 500 ppm level Al/S- 256338 - " "If 1000 ppm level FINAL REPORT NO. 3996 51. F. 7. (Coat'd.) (4) Low Temp. Lab Pehta 211535 had negative CEF response at 1500 ppm level. This sample, when previously tested (BTL-73-28B), was positive at 1500 ppm level, but negative at 500 ppm level. (5) From the CEF data on HCDD and TCDD solutions, ve could expect a positive CEF response with Pentachlorophenol containing at least 0.5 ppm TCDD or between 50 and 250 ppm HCDD. 8 . Low Level Dioxin Analyses - Plant 6 Lab Penta In early 1975, Applied Science's new sensitive gas chromatograph/mass spectrometry system became operational. Analyses of 5 selected Penta samples were carried out with the new system. All of the samples had previously been studied for CEF activity. SAMPLE IDENTIFICATION TCDD ppm Dioxins Penta CDD HexaCDD HeptaCDD OCDD 212180-1-Plant Std.Cond. 212180-7-Plant Low Temp. 211535-Lab Low Temp. KH-261-Plant Std. Cond. 256338-Lab Al/S Catalyst < 0.01 * < 0.01 < 0.01 0 . 0 1 < 0.01 0.01 0.01 0.02 0.04 0.03 8 8 8 15 !5 160 1060 170 1090 130 995 290 1980 110 870 None of the samples contained TCDD (M.D.L. 10 ppb). Concentration levels for other chlorodloxlns are below the level of toxicological significance as Indicated In BloTest studies on TCDD and hexaCDD solu tions (BTL 74-108 & 109). There are Insufficient dioxins 'present to account for the degrees of CEF activity observed. This suggests other "unknown" compounds are contributing to CEF activity. These samples were not exposed to caustic In analytical preparation. Chlorophenols were removed by alumina treatment (Applied Science method 73-1). This series of samples represents our first "accurate" dioxin analyses of Penta. 9. ' Dioxin Precursors a) Base Catalyzed Ring Closure to Dioxins As just discussed In the preceedlng section, dioxins alone do not account for the total CEF activity observed in technical Penta. It Is apparent the activity Is due to a combination of dioxins and other Impurities In Penta. (Pure Penta does not elicit CEF activity.^7) Besides dioxins, there are four other major classes "of Impurities In Penta: Chlorobenzenes Chlorodlphenylethers Chlorohydroxy diphenyl ethers Chlorodibenzofurans TABU. .<0. 6 CHICK EDEMA FACTOR BIOASSAY WITH CHLOROPHENOLS Project No. BTL-74 Lot No. OR- . PROCESS CONDITION (Identification) Relchhold commercial 120 256386 Pentachlorophenol 89 211535 75 Lab Batch (73-28B) * 211535 75C. Lab Batch 88 256304 60C., Al, Te Catalyat 89 256330 60C., Al, S Catalyst 90 256338 60C., Al, S Catalyat 104 256315-1 Chlorophenol Stili Realdue 105 256325-2 Pentachlorophenol Feed Stock PPM 0 150 500 1000 1500 Pericardial Fluid Volume (mi) 0.05 0.08 0.10 0.08 0.08 -- 0.10 .-- 0.33* 0.11 0.10 0.10 0.62* 0.13 -- 0,12 0.66* 0.12 0.48* 0.10 do -- 0.13 . 0.60* 0.67* do -- 0.10 0.05 0.06 -- 0.10 0.19* o.io if* cE e do -- -- -- 0.08 106 107 73-280 256315-4 256315-6 CP 1327 CP 3394 KM-261 do -- do -- 0.10 -- -- -- -- -- ;_ -- 0.04 ; 0.08 -- 1.842 74-28 Plant Penta OR 212180-1 ' 0.10 -- -- -- 1,675 * 108 CP 76171 PPB 0 2 10 50 250 0.05 0.11 0.08 o . i v 2.20* PPM 0 150 500 1000 Mortality per 12 chicks 1500 001 5 11 0- 0 6 10 1 0 1 .. - 1 0 - 1 - 12 do - 1 5 8 do 1 4 6 00 do do do - - 02 -- -- --- -- PPB 10 50 0 o' i : ' I J{ j 250 000 0 9 0 0.02 0.1 o.s; 2.5 0 0.02 0.1 0.5 2.5 109 CP 76172 0.05 0.08 0.09 0,20* 0.84* 000 0 7 CP 1309 CP 1327 CP 3394 CP 76171 Pentachlorophenol para-Chlorophenol 2, 4-dichlorophenol Hexachlorodibeozo-p-dloxin * IndicaCea positive chick edema factor activity. FINAL REPORT KO. 3996 53. F. 9. a) (Cont'd.) Chlorobenzenes end chlorodiphenylethers are not knovn to be chlor- acnegenic, nor are they known to produce CEF activity. This leaves chlorodlbenxofurans (DBF), end chlorohydroxy dlphenylethere (HDFK) as the nost.llkaly suspects contributing to CEF activity. DBF's are known to be chloracnagqnlc. CEF activity for DBF's la not known, but is estl&ated to be about 1 / 1 0 that of correspond ing dioxins. This estliaate Is based on comparative acute toxicity responses between DBF's and dioxins. ^ In ald-1975, we had no way of quantitating DBF's. (Method develop ment for DBF analyses Is currently going on at Applied Science at G.O.) Our Interest then turned to EDPE's. Two types of HDPE's are found In Fenta, " chlorinated 2-HDPE, and chlorinated 4-HDPE. 2-HDPE's are dioxin precursors, and are sometimes referred to as predloxlns. ------ Cl---------- 1 --------------=--------- 61---- :---- 61---------- Bonachloro-2-bydroxy dlphenylether (2-HDPE) OCDD By loss of a molecule of &C1, the precursor Is converted to a dioxin. Literature had Indicated as much as 5Z (wt)*'EDPE's are present In technical grade chlorophenol. The literature and our work had also lndlpated four conditions In which these pre cursors cydlze to dioxins: 1) Pyrolysis of sodium chlorophenata 52 2) Pyrolysis of HDPE under GC conditions 53 3) Photolysis ^4 A) Chlorine radical Initiation 22 While analyzing Catomance Penta-esters In 1973, ve had observed dioxins (heps. CDD & OCDD) Increased dramatically when Fenta samples were exposed to morpholine. This was our first Indication the 2-HDPE*s would also cycllze to dioxins under quite mild basic conditions (See Section E-7) Cl' Cl - Morpholine ^ Morpholine.HC1 + OCDD (Morpholine Is a highly) basic amine FINAL REPORT.NO. 3996 (Cont'd.) This phenomenon raised Che question as to whether NaOH would also cause cydlzatlon. This was Indeed found to be true when a caustic solution of technical Fenta was report edly extracted with hexane. Dioxins were generated in the tine Intervals between extractions, and were repeatedly found In each hexane extract. Bexa CDD, hepta CDD, and OCDD were being formed. (OR 256751) The base catalyzed cydlzatlon reaction was .also shown to be selective In that no additional precursors are generated during base exposure. Cooking distilled Fenta In NaOH so lution or in morpholine did not cause dioxins to Increase (OR 256754). The Increase In dioxins in "base exposed" technical Penta la due solely to cydlzatlon of the precur sors present In the Fenta prior to base treatment. Significance of Precursor Cydlzatlon Due to the ease of cycllzatlqn In the presence of bases, cydlzatlon In biological systems may also be possible. Bases, such as amides In protein, may be basic enough to cause 2-HDFE's to be converted to dioxins. Thus, Ingestion of 2-HDFE's may produce the same pathogenic effects as in gestion of dioxins themsdves. Further, the concentration of 2-HDFE's plus dioxins in Fenta Is high enough to account for the degree of CEF activity observed on technical Fenta. Attempts to cause cydlzatlon with egg albumin were Incon clusive. Accurate measurement of dioxins after exposure could not be made due to Interferences from other compounds (OR 256763). The second point of significance regarding the cydlzatlon Is that all dioxin analyses which had utilized a preliminary caustic clean-up step, no doubt gave erroneously high dioxin values. More dioxins were generated In the caustic clean-up step. All dioxin analyses which were run from 1970 up to April 1975, utilized a caustic clean-up and are therefore all erroneously high. Thirdly, It seems somewhat unlikely that the concentration of hexa CDD found in "toxic fat" H by Cantrell could have arisen solely from original hexa-CDD in the technical Penta, which had contaminated the fat. A more likely source of this concentration hexa-CDD, was probably heptachloro-2- HDPE in the Penta. Fatty amines catalyzed cydlzatlon of this precursor to hexa CDD. (This precursor is present in concentrations as high as 320 ppm In technical Fenta - See Page 57 - FIKAL REPORT NO. 3996 53. F. 9. b. (Cont'd.) It Is also apparent, even In the most recent literature on dioxins, that others have not recognised the near facile cyellzatlon phenom enon. Dioxin analyses are still utilising a caustic clean-up atap.^0* Dioxins are probably being generated In all Santobrlte solutions In Dept. 227. The alkali insolubles associated with these solutions are no doubt extremely high in dioxin content. Production personnel have been alerted to handle these, materials with caution. c. Morpholine Treatment as Method of Analysis Dioxin precursors In Penta can be measured Indirectly by converting them to dioxins which can then be quantitated. The procedure Is as follows: Add 5 grams of Fenta to a 250 ml flask and reflux In 50 ml mor pholine (Fisher M-263) for two hours (extended period may be required - see Page 58 ) Cool and quantitatively transfer to a 100 ml volumetric flask. Rinse flask and dilute to volume with aqueous IN NaOH. Cool to 25C. and readjust volume if necessary. Acidify a 20 ml representative aliquot, with 25 ml of 1:1 aqueous HC1. Cool, then extract twice with 10 ml por tions of nanograde benzene. Combine the benzene extracts and wash twice with 25 ml portions in aqueous NaOH followed by 325 ml water washes. Prepare appropriate dilution In benzene and chromatograph on ECGC by conditions given in Method 7&-20. Only Hepta CDD and OCDD can be quantitated. Hexa-CDD and lower chlorinated dioxins are masked by Interfering compounds. The following Penta samples were analyzed by the procedure. By subtracting original dioxins (before), hepta and octa CDD pre cursor concentrations are determined. Original dioxins determined by Method 73-1 (See Reference No. 42). SAMPLES ppm Hepta CDD hepta __PP Octa-CDD -^octa Before After Precursors Before After Precursors OR-212180^1 Plant Penta-Std.Cond. 160 2624 2464 1060 6237 5177 OR-212180-7 " " -Low Temp. 170 2847 2677 1090 6660 5570 OR-211535 Lab Penta -Low Tasp. 130 2658 - 2528 995 8222 7227 KM-261 Plant Penta - Std.Cond. 290 2934 2644 1980 8648 6668 0R-256338 Lab Penta-Al/S Cat. 0R-256754 Lab Distilled Penta 110 2151 0 . 1 N.D. 2041 N.D. 870 5164 1.3 0 .6 4294 N.D. OR-256754 Lab Distilled Penta IN NaOH in place of Morpholine 0 .1 N.D.*1 n .d : 1.3 0.3 N.D. OR-256386 Relchhold Penta 2081* 4422* OR-256304 Lab Penta- Al/Te Cat. 1884* 5080* *Includes original dioxins. Except for the distilled Penta samples, these were the same samples Just analyzed by Applied Sciences. (See Section F-8) All of the samples had also been previously studied for CEF activity. 56. FINAL REPORT NO. 3996 F. 9. c (Cont*d.) Large amounts of cydlsable hepta and octa CDD precursors are Indicated In all the technical grade samples. Lab Penta, prepared with Al/S or Al/Te catalyst, and the Relchhold sample all contain somewhat reduced amounts of these precursors. Dioxins were not generated In the distilled Penta samples in either the caustic or morpholine treatment. Dioxins generated In the technical grade samples therefore came about solely from cycllzstlon of the respective precursors. The final benzene extracts from preparation of the samples were submitted to Applied Science for dioxin analyses 'by GC/mass spectroscopy In hopes of quantitating hexa-CDD and lover chlorinated dioxins. Their results were as follows SMPLE 0R-212180-1-Plant Penta-Std. Cond. 0R-212180-7 " " -Low Temp. OR-211535 Lab Penta -Low temp. KM-261 Plant Penta,Std. Cond. 0R-256338- Lab Penta Al/S. Cat. Applied Science - Special Study S-75 - SS-17 Unknown Chloro Aromatic Penta CDD 0 . 2 ppm 0.09 ppm 0.3 0 .1 0 4. 0.38 0.3 0.36 2 . 0 1.47 * Hexa CDD Hepta CDD 112 ppm 1940 ppm 102 1630 68 1270 35 1210 175 1490 The amount of Individual dioxins present In the samples before morpholine has been subtracted from the listed values. Thus, the dioxin levels reported here represent original precursor concentrations. No dlchlor or trl CDD was found In any of these samples with a detection limit of 0.1 ppm. The unknown chloro aromatic had a different GC retention time and mass spectrum from 2,3,7,8-tetra CDD. Its spectrum did contain 322 and 259 Ions which would be expected.from TCDD. The full mass spectrum however, con tains Ions foreign to TCDD. Because the spectrum was very weak, the possibility that this component Is a tetra CDD, but not the 2,3,7,8 lBomer, cannot be ruled out. Fenta-CDD, hexa-CDD, and hepta-CDD were found In concentra tions roughly ten times that of the original .levels before morpholine treatment. Hepta-CDD values were s I b o , on the average, about 1000 ppm less than vhat our analyses had indicated (1500 vs 2500 ppm). Our higher hepta-CDD could be due to the inclusion of unresolved hepta dlbenzofurana. An alternative method for precursor determination, which permits quantitation of Penta-CDD through OCDD precursors without the diphenyl ether and furan interferences is as FINAL REPORT NO. 3996 57. F. 9. c. (Coat'd.) A one grim Penta sample Is dissolved la 10 ml nanograde benzene and chromatographed as described in Applied Science Method 73-1 (Ref. No. 42) with 200 ml nanograde benzene. All phenolic type compounds, which include dioxin precursors, are retained on the alumina. These are released and collected from the alumina by eluting 200 ml methan ol over the alumina. The methanol eluent is collected in a 250 ml round bottom flask. 25 ml of morpholine is added. Equip the flaBk with a Snyder column and place in a steam bath. Methanol is boiled out, while morpholine causes dioxin precursors to cydlze to dioxins (extended cook period may be required to assure complete cydlzetion See Page 58 ). The mixture is then cooled and acidified to pH ^2.0 by addition of 1:1 aqueous HC1. After cooling, the mixture is extracted twice with 10 ml portions of nanograde benzene. The ben zene extracts are combined, washed twice with 25 ml portions in aqueous NaOH, followed by three 25 ml water washes. Appropriate di lutions in benzene are prepared and ECGC'd. Alternatively, the ben zene extract is concentrated by evaporation to 5 ml. A 1/2 ml ali quot is then chromatographed over 1 gram of AI2O3 , (W- 2 0 0 basic activity grade super 1 - from ICN Pharmaceuticals - 3440 Eschwege Vest Germany) contained in a 1 ml disposable plpet with 10 ml of ZX CH2Cl2:98Z Hexane solution. This removes minute interferences re maining in the TCDD area. A second 10 ml fraction consisting of 50Z (vol.) CH2CI2 in hexane is collected. This fraction contains only the dioxins. An appropriate dilution is made and ECGC'd. The chromatograms are free of Interferences in the Penta CDD and TCDD region allowing quantitation to 0.1 ppm and lower if desired. (The final chromatographing clean-np technique was developed by H. R. Buser of Switzerland. *) Hexa CDD precursor content was determined in the following samples utilizing the method just described (without the final AI2O3 treat ment). . Hexa-CDD Precursors in Penta SAMPLE "'i-' Hexa CDD OR 212180-1 OR 212180-7 OR 211535 KM-261 OR 256338 t OR 256304 OR 256386 OR 214234 Plant Penta - Std. Cond. n ii - Low Temp. Lab Penta - Low Temp. Plant Penta - Std. Cond. Lab Penta - Al/S Cat. Lab Penta - Al/Te Cat. Reichhold Penta Lab Distilled Penta 316 320 186 112 150 175 161 ^ 0.1 Plant Batch - Sampled @ 130C. during rate of rise > 2 0 0 *This sample also contained >50 ppm of what was suspected to be Penta - CDD. 58. FINAL REPORT NO. 3996 9. c. (Coat'd.) Some of the samples are those which were analyzed for hexa-CDD by Applied Science as Just discussed. Agree ment between labs is not good. Most values reported here are higher. The precision, recoveries, etc. re garding tha method have not been determined. There Is some question about the completeness of cydlzatlon of cycllzable precursors (see following section) d. Cydlzatlon In NaOE VS Morpholine Initially we observed no difference in the amount of hepta and OCDD generated between 1 and 2 hour refluxing .In morpholine. We therefore concluded that cydlzatlon was complete within the two hour period. This may not have been true however, as Indicated in the following comparison of cydlzatlon In NaOH VS morpholine at am bient temperatures (OR 256753). Dioxin.values given be low include original dioxins present In addition to those generated in cydlzatlon. Moles Base/gram Penta Hepta CDD OCDD 1.0 gram Penta, Lot KM-509 50 ml IN NaOH, Stirred 18 hours Q 256C. 0.050 5057 ppm 15,800 ppm 1.0 gram Penta, Lot KM-509 50 ml' Morpholine, Stirred 18 hours @ 25C. 0.574 5865 ppm 17,100 ppm 5.0 gram Penta KM-261 reflux in 50 ml Morpholine for 2 hours 0.115 2934 ppm 8,648 ppm No firm conclusions can be made from the data. There is indication however, NaOH may be more effective when com pared to equimolar amounts of morpholine. In addition, OCDD values are nearly double In the ambient runs com pared to that on KM-261 in refluxed morpholine. . The dif ference could be real; but more likely, KM-261 cyclizatlon was probably Incomplete. e. Cydlzatlon rate of Irgasan DP-300 VS dioxin precursors In Technical Penta Irgasan DP-300 (2,4,A,-trichloro-2'-hydroxydlphenylether) is a commercial antimicrobial agent manufactured by CIBAGEIGY. This compound also has the structure of a dioxin precursor: FINAL REPORT NO. 3996 F, 9. e. (Cont'd.) 59. Cl O OH Cl' O Cl Cl -HCl . L O IRGASN DP-300 2 ,8-dichlorodibenzo dioxin The rate of cydizatlon was observed In the following tests by monitoring HC1 generation (AgNO^ titration of Cl"). ppm HC1 Generated______ 96 hrs. 168 hrs. 456 hrs. 5.0 gram IRGASAN DP-300 50 ml Cl" free Morpholine Cook @ 55C. with stirring. 25.7 95.4 353.0 5.0 gram IRGASAN DP-300 50 ml Cl" free xylene Cook @ 55C. with stirring 25.7 25.7 39.0 The percent conversion to dioxin In the morpholine sample after 456 hrs. was only 0.27Z. Cydizatlon Is extremely slow. No conversion was apparent In the xylene solution which is not a basic solvent. (Confirmation of di-CDD by GC analyses not at tempted.) Since dioxins are generated very rapidly when Tech. Penta Is cooked In morpholine, we can only conclude that position and number of chlorines in the precursor significantly affect the rate of cydizatlon to dioxins. The most likely explanation is that the precursor must have chlorines in each position ortho to the ether linkage before cydizatlon proceeds with ease: 1 -chlorodibenzodioxin 60. F. 9. e. (Cont'd.) FINAL REPORT NO. 3996 Base --------- > HC1 + Very, Very Slow 2-(2'-monochlorophenoxy) Phenol dlbenzodloxln In the first reaction,chlorine atoms occupy both the 2* and 6 ' positions. Either chlorine can be lost in cycllzatlon. On the other hand, In the second reaction, there is only one chlorine available (position 2 1) to be lost In cycllzatlon - apparently, this difference greatly effects cycllzatlon rate. f. Speculative Toxicity of Various Dioxin Precursors The structural differences of the precursors also allows one to speculate as to what dioxin precursors might be toxic, and those that are not, based on their predicted ease of cycllzatlon In a biological system. For example: crX s X o 2,3,7,8 TCDD Precursor )ver^ lyery s iw TCDD This precursor may not be very toxic due to Its slow cycllzatlon rate. Its slow cycllzatlon rate may also ex plain, in part, why TCDD is not found in Tech. Penta (<0.01 ppm). The following dioxin precursor might be considered very toxic based on Its predicted ease of cycllzatlon to dioxin. Cl FINAL REPORT NO. 3996 61. F. 9. f. (Cont'd.) Two Isomers of Penta-CDD ere generated depending on which chlorine atom Is lost In the cydization. The 1,2,3,7,8 Iso mer would be expected to be highly toxic based on Poland & Glover's toxicity studies on chlorodibenzodioxins. *7 A recent toxicity study on one dioxin precursor substantiates our prediction. Dr. McConnell (NIEHS), at the March 1976 Meet ing of the Society of Toxicology, presented toxicological data (Paper No. 130) on 4,5,6-trichloro-2(2,4-dichloro-phenoxy) phenol. No deaths occurred among rats dosed with as high as 100 mg/kg body weight. Thus, this precursor did not produce demonstrable effects even at 50,000 times the LD50-30 of 2,3,7, 8-TCDD. This precursor Is not the type that would be expected to cycllze easily. Therefore little or negligible cycllzatlon would occur In the biological system. Consequently the precursor is not toxic because no dioxin forms In the biological system. g. CEF Relation to Precursor Concentrations in Penta * t. Our data at this point shows no clear relationship between CEF activity and precursor concentration (See TABLE No. 6 , Pg. 61 a) 10. Hexachlorobenzene In Penta The presence of hexachlorobenzene (HCB) In technical Penta came to light in the 1973-75 period. Method of analysis developed by Applied Science and by Monsanto Australia R&D 58 was adapted to our ECGC (OR 256740). A.few selected samples were analyzed yielding the following results. SAMPLE HEXACHLOROBENZENE ' IDENTIFICATION OR 2121B0-1 OR 212180-7 OR 211535 KM-261 OR 256338 OR 214234-Reflned Reichhold Lot No.72874 Dow EC-7 Lot No. 09214M Monsanto AustraliaBa.No.73346026 OR 256399 OR 256304 39.7 ppm 31.5 " 27.7 56.4 13.0 53.4 28.8 106. 15.3 999.6 30.6 Plant Penta-Std. Conditions Plant Penta-Amended Cond. Lab Penta - Low Temp. Plant Penta - Std. Cond. Lab Penta-Al+Sulfur Cat. Plant Penta-Lab Distilled Reichhold1s Improved Mat. Dow's Refined Material Lab-overchlorinated batch Lab, Al/Te Cat. ! TABLE HO. 6 TECHNICAL PENTA CEF RESPONSE VS DIOXIN PRECURSOR CONTENT SAMPLE & DESCRIPTION TOTAL* PENTA CDD <**HEXA CDD ~ H E P T A CDD --OCTA CDD TOTAL PERICARDIAL TOTAL* PRECURSORS PRECURSORS PRECURSORS ,PRECURSORS PRECURSORS FLUID DEATt OR-212180-1 Plant Penta - Std. Cond.. 0.09 ppm 316. ppm 2464 ppm 5177 ppm 7957.ppm 3.55 ml 10 OR-212180-7 " " - Low Temp. 0 .1 0 320. 2677 5570 8567. 1.34 6 OR-211535 Lab " --H II 0.38 KM-261 Plant " - Std. Cond . 0.36 OR-256338 Lab Penta - Al/S Cat. 1.47 186. 112. 150 2528 2644 2041 7227 6668 4294 9941.9424. 6487. 1.09 3.60 0.39 3 10 11 OR-256386 Reichhold Penta -- 161 1800 4000 5961. 1.74 16 NOTE: Precision of these values Is not known. The precursors were converted to dioxins by exposure to basic conditions, then dioxin concentrations were determined. Recoveries, and degree of conversion have not been determined, therefore these values may be erroneously low. The method of analysis Is des- crlbed on page ^ of this report ( *See Appendix E, Item 3. ' S. H. Vogel 6 la FINAL REPORT NO. 3996 10. (Cont'd.) Mechanism of formation of hexachlorobenzene is speculated to arise from BC1 cleavage of polychlorodiphenylethera. Lower chlorinated benzenes are also reported to be present. 56 There is some evidence the Al/S or the Al/Te catalyst system suppresses HCB formation to a moderate extent. The principal concern for hexachlorobenzene is its slow de gradation rate In the environment. CHLORINATED DIBENZODIOXINS: COMPARATIVE TOXICOLOGY 9 10 1 Dlbenzo-p-dioxln (DD) To show appreciable toxicity: 57 1. At least three of the 2,3,7,8 positions must be halogenated, AND 2. At least one of the eight carbons must be unsubstituted. THUS, DD, 2-CDD, 2,3-DCDD, 2,7-DCDD, 1,2,3,4-TCDD, and OCDD (Octa-) show little biological activity at levels tested. 2,3,7,8-TCDD is one of the most toxic substances known, as LD^q male guinea pig is 0 . 6 micrograms kg* body weight; LD^q for rabbit is 0.115 mg/kg. It is a potent acnegen, is positive cause of chick edema at l/4 g/kg/day feed, is teratogenic and it is mutagenic to certain bacteria. HCDD (Hexachloro, mixed Isomers) is active in chick edema and acnegeniclty testing at about ten times the level of 2,3,7,8-TCDD. It is far less lethal. Data on Penta-CDD and Hepta-CDD are not available except that HeptaCDD impurity in OCDD at 15Z level appears to have no adverse effects. PENTA TREATED WOOD - DIOXIN ANALYSES Wood borings supplied to Monsanto by Koppers Inc., were analyzed for hepta CDD and OCDD content by Applied Science of G.O. (Ref. No. 58) in March 1975. Fentachlorophenol and hepta- and octa-chlorodibenzodioxins were found in each of three treated woods examined. The lower chlorinated dibenzodloxlns could not be determined due to interferences. The data are shown in the following table. 64. FINAL REPORT NO. 3996 I. BIOASSAY - CEF & REC DATA SUMMARY (Cont'd.) BTL, NO. 73-20A 73- 28B 74- 87 73-28C DESCRIPTION Lab Paata - Solvant chlorination Lab Penta - Low Temp. 0R211535 Repeat of 73-28B Lab Fenta-hlgh level chlorination CEF RESPONSE Negative 8 1500 ppm Slight 8 1500, Neg. 8 500 Neg. 8 1500, Neg. 8 500 Slight 8 1500, Neg. 8 500 74-35 74-88 74-90 48X Penta in AD-73 Oil Prill fumes Lab Penta - Al/Te Cat. Lab Penta Al/S Cat. Negative 8 1500 Negative 8 1500 Slight 8 1500, Neg. @ 500 Low temperature chlorination, paralleling OR 211535. condition, was plants trialed (BTL-74-28 through 74-34). Although CEF improvement was indicated, the Improvement did not match OR 211535. Note however that all the "low spread" samples showed the most improvement. A semiquantitative assessment of this data is found in Appendix E-3. This assessment predicts a negative CEF response if spread is 1C or less. This might be accomplished in the plant by better heat removal during rate of rise. Lowest spread achieved during the low temperature plant runs was about 3C. CEF response of WGK Penta VS Reichhold is essentially equivalent (7249 vs 74-120). Prill fume Penta (74-35) did not elicit CEF activity indicating its purity. It is essentially sublimed Penta. The use of low temperature - low spread chlorination, coupled with a catalyst change to Al/Sulfur or Al/Tellerium presents the best oppor tunity for a lower by-product Penta. Further evaluation in the.lab of the Al/S catalyst system may be necessary before plant trial. (See Section F. 6-a for further discussion regarding Al/S Cat. System.) All chlorophenol process streams in para-chlorophenol and 2, 4-dlchloro phenol manufacture gave negative CEF responses at the 1500 ppm level (74-104 through 74-107). No firm conclusions can be made regarding the CMU chloracne data. A detailed description of CMU's method is found in their reports accom panying the test results on each sample. Solution containing the test material is applied to a rabbit's ear and skin irritation'is observed over a certain period of time. The test results on all samples were confusing, to say the least. A copy of their report No. CMU-74-41A through G is found in Appendix E-4. Ml 7 c k L g f o A . ^ __ DdVTvv__ - g k ffwAy *(. cCiLie d m& foe.raACeriv ffrMxrftmyfa/n*)!C*rAiirrn g/M c J \ U*c/*e. (kc<-) flY/alftA* *rtw **.7/-/ .(*.4 f*- A'*VI Kf. VL tf*. 7 1 -V f T a - | i f e L i *** XM - a t / J > A J C X 1 P T i*0j3 6 C rv 'w tJ .ri ** -- Pu> H t L a - r C**rA - . S r i. C 4 /*w j e /Y r Lt*L (ft* T*T%L ft* ts* * * f <7* .ll O.JO ./J .// Y Il . i f .Y * / r f iY 7 J - a PA 7 J - 1 8 7 i -a fe 7J - * f D 7J 7 i - ir a r - a / o A*ftX a R - f t / / AU o R - i/f a f R - p //j *y V i - a y /S' y V - jA 'jjy C U 4n W / * J iJ fl** k l*n a M y * e * M f #.*7 JO L a lf*> e - L+jTHf. cJlU n'^r.vJ ./* *I0 .ro 14b k m * Kj^X L 4 * l 1 . f t a ./t .// ft.K-7.C f -/L * -r- fw n t // *.rV D a rf A.A-7 *. U t A > i / t 4 ,/l ./a .at * - la t iiV > 'lk 4 .I I .*T - . if ft. Il / 7 /rtf4 f If r 3 V /* a a* 7Y- * / TV- M 7Y - J 7Y- 7! 7v - ja 7Y- JJ 7y - iv 7 Y- JV 7y- u o i- J //* - / a * . j u t * -a o A - A y ly /a -J A * . J/3vr> - Y /- */)y / y ft. ay a // * 6 ft - a/A/P 7 0A .//!// ! 7 V - /a 7Y- r r tv- w 7 V - *T 7r - * 7Y -fY 7 Y -/0 * IV- /(. 7*f-fa~t .a /ffjr .a rtJ a V aA -ftT L 320 oft. Jicur ft* a r c f t / T - f ft-jv tJ /r-a eft.art ar-Y a. act Jyr-<. f t r . f l * * -STft. Cm 4. JO f -- M if* - - - < i*t ./a - - - U * , LX CAT. / * -< * ' . ' ' . I M 4 ft - * I , - - --Ji IxeV a f - - t * t . - - - K fcA a cot Y tft *t fWa A a a I U i 4 40>ll O/L . 1 A U r/r* f f / K - f f l- a TPF, ftTO^ .t ./a C f / A f t / /ft* *.# a n A ft/ X x l * ./* t / P Afti" t j / ./ft ./A AJJ * * ' / ft . a *sl a 1 *Af cY ft e l f ./ft / *.a .1 ./ / ^ a U iiJ (iT, 7 t i 7 y Lab f a n LmJ 7 2 *y . cUu. - - Aj I / 7 1 *a*. - - y U /S car. . ... - A * / r . c a r. ^clh^la'X ftv/ft patii*- 'AanVi /^y/*i I'.JibftfU'H, ** a,v- *- : ur ftC a f aft ft At t,r a *t .o r .> a CA C i/ a/J ./a i# //A Aft ./I .4? ctr e./ ./ /f / *.*f Y a#f /* /r /A /A r A IT / /f // o o P A 'l 4nlU c C ff ") C ftu M . K*txl C e r t / K * r r ________ ft^ ia p M i. a* a.aV /? 7 f- .L T t.V a.a7 .iY T / -A7ft / x y 1.71 A V I 7J -AT# *Y I f . l* / . I f a r t r f tf o 7 f 9 aaCC T `t M < a . f(Y e gftC C^rfTV.l 4 * * A** A L M i. /ft V A ' I l i a T ula < * m | ffp 7ft -A7C 7ft .1 7 1 7J 7 * 7 f -*I f 7Y -Y I n. /.Y l /.a r ft/. A A a l A f t * aaV / . f t *7 a.fV /.ft f.Vfi M f /ft.Y e l * f /r Iff / m a a tt TU < . 1 ^ rt a r a fy m a " * -- Jpftc C x > .t 7 V - VI A I k * /.a I T V - V I 8 a a .t ft.a A l 7 Y -V IC i.fc M f . r / /A* M i a f i i f T t-o# 7 V -V /X ) 7 V -< / T V-V/ ft* '7Y-YI /W /.ft y/.r A t f / . i /.S' a . 7 A# /.a /.V 1.6 f 17 / f t * / a c t T L o p 4M * -ffcM C l ^ L ft-Z A U . * U*y * r /fta w lia* TL*a < e a l / r r t t eoi a" // 17* ite f l M <0.|irt4 7v-/r 7Y~t9f kjLjiAca# A -tty y. K + + , TXrvacPi o #. #a t. / -* .{ *4t .*(1*.*P a * J.a ft. .// o.fy .r x-a a .l/ at ft/t dL/AT-Ay a^aA * cr. \, 66. FINAL REPORT NO. 3996 J. "ACCURATE11 DIOXIN AND DIBENZOFURAN ANALYSES - Data Summary Table No. 8, page 67, summarizes all of our "accurate" dioxin/furan analyses on chlorophenols generated in the paBt few months. Sample preparation for all analyses listed utilized an alumina clean-up step. Thus problems of precursor cycllzatlon to dioxins due to caustic ex posure is avoided. Previous analyses had utilized a caustic clean-up step. Typical levels of dioxin and furan found In Penta are as follows: Dibenzodloxlns Dlbenzofurane Tetrachloro Penta " hexa " hepta n < 0 . 1 ppm 0.1 5-20 200 - 300 400 - 1000 .<0.1 ppm <0.5 30 - 90 250 - 450 150-- 600 Trace amounts of these impurities, but lover chlorinated, are also found in parachlorophenol, 2, 4-dichlorophenol, and Santophen 1. The presence of the highly toxic 2,3,7,8 TCDD has not been confirmed In N any WGK produced chlorophenols. (One parachlorophenol sample showed a TCDD level of 0.1 ppm, but is a questionable value due to interfer ences.) Relchhold Penta has somewhat lower amounts of furans and dioxins com pared to typical WGK Penta. Monsanto distilled, as well as Dow's EC 7 refined Penta, contain only trace amounts of dioxins. Furans in refined Penta have not been de termined . Alkali insolubles associated with Santobrlte solutions (cone tank mud) contain gross levels of dioxins. TCDD (0*10 ppm) was also detected In 301 aqueous Santobrlte solution. Production of this material (5PS-30) has been discontinued. Use of a weaker solution (21Z) as feed to Penta/oil solution Is continuing. Method 73-1, coupled with mass spectroscopy, was used for all dioxin analyses presented on TABLE 8. K. AR&D SPECIAL STUDY - PLANT PENTA DIOXINS & "COOKED" ALKALI INSOLUBLES ANALYSES In April 1976, WGK AR&D group analyzed a Beries of plant produced Penta samples for dioxins and alkali Insolubles by a modified proce dure supplied by PPT group. Method No. 73-1 clean-up procedure, fol lowed by simple ECGC, was used for dioxin analyses. The "cooked" alkali Insolubles method (OR 257048) Is essentially the same as our routine-Method No. 10,017 except-for the following changes: -- *-- SAMPLE DESCRIPTION TABLE BO. 8 1976 - "ACCURATE" CHLOROPKZNOL DIOXIH 6 DIBEHjfoFURAH AHALTSES F l i n t Fto ccsi Technology 3. H. Vogel 7/15/76 DATA SUMMARY (OR 257051) Method 73-1 Applied Science Analyses blXtn___(PP0______ DIBENZOFTJRANS (PI*) Cl Cl2 ci3 CI4 Cl5 Clfi Cl7 Cl8 ci4 ci5 Cl6 Cl; <*8 COttfENTS Santopben-1, RE-08-41 Santophen-1, RE-03-15 . H.D. H.D. 9.1 * 0.9 <0.03 1 J26.2 26.2 <0.9 p-Chlorophenol RE-10-5069' p-Chlorophenol RE-01-5003 0.8 <0.04 <0.02 <0.01 17.3* 6.5* 2.1* 0.1* 2,4-DlchlorophaDol, KE-06-1009 2,4- " " , Tk. 2, 1-15-74 2,4- " " , 931 (257059) 0.8 <0.02 <0.04 <0.01 0.3 <0.02 <0.03 <0.01 .0.18 0.23 0.3 <0.09 PenCo-60 KD-4 Penta-60 RD-2 <0.01 <0.2 9 <0.01 <0.25 11 90 130 100 150 Santobrlte SPS-30 (257051) Santobrita SPS-21 (Penta Sol'n.Feed ) 0.11 0.06 1.3 2.3 0.5 1.3 17 12 11 7.5 Cone Tank Alkali Insolublas <.13 <177 <352 1 . 12X Pentachlorophenol RE 06-56 " " " RE 07-74 " " " RE 08-84 " " " R E 08-89 "" RE ID-111 " " " R E 11-135 " " " RE 12-147 * " " RE 12-157 " n n OR 212180-1 " " " O R 212180-1 " " " OR 212180-7 " " " O R 212180-7 Relchhold Penta (OR 256386) Date of analysis May, 1975 April , 1976 May., 1975 April , 1976 <0.01 <0.01 <0.03 <0.01 <0.01 <0.02 <0.01 <0.01 <0.01 <0.01 <0.01 <0.02 <0.01 <0.05 <0.17 <0.08 <0.03 <0.12 <0.07 <0.17 <0.07 11 12.6 9.6 18 10.2 10 15.5 9.9 <0.01 <0.07 <0.01 <0.11 8 9.6 8 6.8 50.05 13 220 440 306 761 220 521 270 800 256 717 333 921 538 1983 305 826 160 1060 181 170 1090 160 123 3B0 - > Ha Penta beala (Dry beala) 0.6 .36 49 276 0.08 0.26 87 445 <0.01 <0.02 32 230 <*0.4 <1.7 37 90 Valuea nay be Inflated due to Interferences. *Poaalble Interference. Scrap + Frill Fuses Scrap + Prill Fuses. Santobrlte Mid 172 140 Very dark material. Plant Standard Condition. 610 ft Ff It " Low Temperature MH 11 57 Lot 72874 Dow Refined Fenta-09214W-EC7 Monaanto - Lab Refined (OR 214234) Lab Penta - OR 211535 i n _ n m " " - OR 256338 W W _H ff May, 1975 April , 1976 May, 1975 April , 1976 <0.01 <0.01 <0.01 <0.01 <0.01 <0.03 <0.02 zo:o2 0.3 0.2 <0.02 0 : 0 1 0.06 0.05 0.02 5 <0.03 <4:0 0.03 5 <0.09 <3.4 130 995 93 110 870 90 ' CoMerclal Plant Penta-Lab Refined. Low Temperature t 11 Al/S Catalyst 68. FINAL REPORT NO. 3996 K. AR&D SPECIAL STUDY - PLANT PENTA DIOXINS & "COOKED" ALKALI INSOLUBLES ANALYSES (Cont'd.)_________________________ I_____________ Cook with stirring at 80C. for 2-1/2 hours. Add] 10 ml of NaCl saturated H2O. Adjust pH to 9.0 - 9.5 vhllej still warn with 1:1 HC1. Cool and filter in normal manner. (The cooking procedure causes cycllzatlon of dioxin precursors to dioxins.) ! I A summary of the results is found in Appendix E-5. Conclusions from asthe study, were follows: i 1. There is no dioxin build-up during the first 4 hours of molten hold period prior to prilling. Our additives areiapparently stabilizing the material. 2. There le no clear relation between total dioxin level and cook ed alk-lneol. content. Additives also Interfere in the cooked alkall-insol. test causing Inflated values. "Cooked" alk-lnsol values on the average are about double compared to the routine method. One aampla (Chlor. Batch C-22) was also analysed byApplied Science at C.O. Agreement between labs was good. L. APPLIED SCIENCEDIOXINMETHODS OFANALYSES 1970 - 1976 A copy of each dioxinmethod of analysis developed by Applied Science from 1970 to 1976 la found inAppendix E-6 and E-7. M. PENTA BIODEGRADATION STUDY -PURDUE UNIVERSITY Fenta industry sponsored biodegradation studies were carried out by E. J. Kirsch et al at Purdue University in the period 1972 through 1975. Their studies are published in Reference No. 59. One major finding was that refined Fenta degrades more easily than technical grade Penta. DESCRIPTION OF RECOMMENDED PROCESS Process for Engineering Design, Report No. P-1729, describes a distillation process for Penta refining. (See Reference No. 38.) Amendments F and H to Dept. 236 SMPD were also Issued for plant trial of low temperature chlorination. (See References No. 45 and 46.) ANALYTICAL PROCEDURES Analytical procedures associated with the work detailed in this report are described or referenced throughout the "Results and Discussion" section. The dioxin GLC methods developed by Applied Science and PPT are also found in Appendix E-6 and E-7. I PINAL REPORT NO. 3996 69. TOXICITY. AND HAZARDS Chlorodibenzodioxins and chloro-dibenzofurans are known to be extremely toxic substances. Caution should be exercised when handling Penta Impuri ties, as veil as dloxin/furan analytical standards. ATMOSPHERIC AND STREAM POLLUTION The alkali Insolubles associated with Santobrlte solutions are current ly severed. Since they contain high levels of dioxins, another means of disposal should be found. Incineration Is recommended. Processes for the disposition of Venturi and Central fume scrubber vastes are described In another report (Reference No. 34). The Importance of good housekeeping and adequate ventlllatlon In chlorophenol production departments to minimize worker exposure to toxic Impurities, as well as to chlorophenols themselves, cannot be over emphasized. ACKNOWLEDGEMENTS Dioxin methods of analyses and related special studies were carried out by J. P. Mieure, M. W. Dietrich, G. W. Mappes, 0. E. Klnast, 0. Hicks, and others In the Applied Science section at G.O. Distillation studies and subsequent PED Report No. P-1729 for. Penta refin ing were the efforts of D. R. Cova and J. E. White of MIC Engineering Spe cialties . Process cost estimates on various approaches to Penta refining vere made by D. A. Novae of CED. Coordination of bloassay testing was handled by F. L. Wright, Dept, of Medicine and Environmental Health at G.O. Successful demonstration of lov temperature chlorination In the plant vere the efforts of R. R. Sorrell, J. Starzyk, and the chlorlnator operators R. Steele, F. Falconer, K. Wilcox, and C. Robinson. Acknowledgement Is also given to WGK control lab Section I personnel for providing numerous dioxin related analyses In support of plant and lab chlorination studies as veil as routine monitoring of competitive Penta and Santobrlte. Special thanks is also given to R. D. McEntire and B. Soehnlln for their ex cellent work In providing non-routine analyses associated with plant lov temperature chlorination studies. 7 14> X U - INTRODUCTION A special Safety Audit Committee was established by D. E . Munic to make a comprehensive safety audit of the DCA/PCA manufacturing facilities at Luling and the Chlorophenols manufacturing facilities at U. G. Krummric The committee' completed the safety audit of the DCA/PCA facility and the findings and recommendations were issued in a report issued February 24, 1977. The committee(l) for the safety audit of the-Chlorophenols manufacturing facility consists of the following: B. W. Eley, Senior Industrial Hygienist G. F. Fort, Manager Environmental Affairs, MIC D. J. Metherd, Operating Superintendent - D. P. Roman, Research Group Leader, R & D , MIC D&P W. W. Russell, Principal Safety Specialist, S&PP R. L. L i s s , Manager R&D, MIC D&P (Chairman) This committee carried out its Safety Audit, of the Chloroohenols m a n u facturing facility at the W. G. Krummrich plant primarily to determine if anv function, practice or condition of the entire process and products could have a significant impact on the safety or the oersonnl . property, or environment. A signiricant impact is aeiinea as a potentt,.i incident which might lead to a) major disabling injury or loss of life of personnel; b) an impact on the environment or the community which could lead to company liability or adverse publicity in maintaining our role as good citizens; c) major loss of property or market. FINDINGS 1. Overchlorination of pentachlorophenol provides a potential for major process accidents and formation of highly toxic materials. An earlier major incident at WGK and a very recent incident at NUFARM in Australia from ov.erchlorination results in unstable product subject to exothermic decomposition and eruption. 2. Since 1975 approximately 40% of the personnel who work continuously in Pentachlorophenol (Dept. 236) show visible evidence of chloracne with one to seven people requiring medical treatment semi-annually. The observed chloracne has been comedones or blackheads on the face, primarily around the eyes and on the cheekbones and tem.D les. 3. Monitoring of Pentachlorophenol (in air) conducted by the olant environmental control grouo indicates that at times , exposure i i ______________ . * ____________j . . _ _ i - c2 _ t. r f- i *i i limits established bv the American Conference of Governmental Industrial Hygienists (ACGIF) . (1) d . D . Lunn, Industrial Hygicnist, assisted in' one phase of the program