Document B8vaKGK9kw5nYowZozeDzY0RL

U n cia ssifie d S E C U R IT Y C L A S S IF IC A T IO N O F T H IS P A G E (W hen D e ie E n te re d ) REPORT DOCUMENTATION PAGE R EAD INSTRUCTIONS B E F O R E CO M PLETIN G FORM 1. R E P O R T N U M BER 2. G O VT A C C ESSIO N NO. i . R E C IP IE N T 'S C A T A LO G N UM BER ARL 75-0110, Vol I 4. T I T L E (e n d S u b title ) Analytical Methodology for Herbicide Orange Vol. I . Determination of Chemical Composition 7. AU T H O R / a) B.M. Hughes, D.C. Fee, M.L. Taylor, T.O. Tiernan (ARL), C.E. H i l l , J r . , and R .L.C . Wu (SRL) S. T Y P E O F R E P O R T 8 P ER IO D C O V ER ED TECHNICAL - FINAL December 1972-December 1974 6. P ER FO R M IN G O RG. R E P O R T NUM BER i! 8 . C O N T R A C T O R G R A N T N U M B E R f.J F33615-73-C-4099 and in house ; 9. P ER FO R M IN G O R G A N IZA TIO N NAM E AND A O O RESS ARL (AFSC) & Systems Research Laboratories Chemistry Research Laboratory (LJ) Wright-Patterson AFB, OH 45433 11. C O N T R O LLIN G O F F IC E NAM E ANO A O O RESS ARL (LJ) Building 450, Area B Wright-Patterson AFB, OH 45433 14. M O N IT O R IN G A G E N C Y N A M E & A O D R E S S /f/ d ilte r e n t Iro m C o n tr o llin g O ffic e ) A ir Force Lo gistics Command (DS) Wright-Patterson A ir Force Base Ohio 45433 10. P R O G R A M E L E M E N T . P R O J E C T , T A S K A R E A 8 W ORK U N IT N U M BERS DOD Element 61102F 70230614 12. R E P O R T D A T E May 1975 I3 ^ ^ IM B E R O F PA G ES \ , 15. S E C U R IT Y C L A S S , ( o f th is re p o rt) UNCLASSIFIED : ; i 15. D EC LA S S IFIC A T IO N /D O W N G R A D IN G sc h ed u le 16. D IS T R IB U T IO N S T A T E M E N T /o/ R e p o rt) Approved for public release; distribution unlimited. ? 17. D IS T R IB U T IO N S T A T E M E N T (o 1 th e e b e tre c t e n te re d In B lo c k 20. I I d ilte r e n t Iro m R e p o rt) 18. S U P P L E M E N T A R Y N O T E S 19. K E Y W O RDS (C o n tin u e o n re v e rs e s id e I f n e c e s s a r y a n d id e n t if y b y b lo c k n u m b e r) Analysis Tetrachlorodibenzo-p-dioxin (TCDD) Chlorophenoxy-Type Herbicide Dioxin Gas Chromatograph-Mass Spectrometer Organochlorine Compounds Syi* Computerized Data Acquisition Herbicide Orange .f . 20. A B S T R A C T (C o n tin u e on re v e rs e s id e I f n e c e s s a ry and id e n tify b y b lo c k n um ber) &- This report describes research performed by ARL at the request of the A ir Force jf Lo g istics Command to develop and apply analytical methodology to characterize the USAF inventory of Herbicide Orange stocks. A computerized Gas ChromatographMass Spectrometer (GC-MS) system was developed which permitted determination of the 15 to 25 major and minor herbicide components which are ty p ica lly present in the stocks located at Gulfport, M ississip p i. For determination of tetrachlorodibenzo-p-dioxin (TCDD), a fu lly automated GC-Quadrupole MS was developed and used in conjunction with an improved column-chromatography DD s 1473 E D IT IO N O F I N O V 65 tS O B S O L E T E S E C U R IT Y C L A S S IF IC A T IO N O F T H IS P A G E (W h in Dm te E n te n d ) J U n cla ssifie d s e c u r i t y c l a s s i f i c a t i o n o f t h i s RAGEfHh.n o . i . Ef ii. i-./; Item 20 Continued sample-clean-up technique. The analytical methodology is described in detail I 8 4 ' B Unclassified S E C U R IT Y C L A S S IF IC A T IO N O F t h i s P A G E fH T i.n D . c E n ltrm d ) PREFACE The research and development described in this report were performed inhouse by the Gaseous Ionization and Excitation Processes Group!of the Chemistry Research Laboratory, Aerospace Research Laboratories1(AFSC), Wright Patterson AFB, Ohio. This work was funded by Air Force:Logistics Command, Assistant Deputy Chief of Staff/Distribution, Mr. Karl Merrill. Dr. Billy E. Welch, Special Assistant for Environmental Quality,: Office of the Secretary of the Air Force, had overall cognizance for this effort which was undertaken to provide analytical chemistry support of USAF efforts to dispose of excess herbicide stocks in accordance with Environmental Protection Agency guidelines. The in-house work force was augmented during these studies via Contract No. F33615-73-C-4099 with Systems Research Laboratories, Inc., Dayton, Ohio 45440. These studies were performed under Project 7023, Task 702306, Work Unit 70230614, "Advanced Mass Spectrometric Analytical and Diagnostic Techniques for Materials and Research Applications." The A!RL principal investigator in these studies was Dr. Thomas 0. Tieman, ARL (LJ), Wright Patterson AFB, Ohio 45433. l 1 I QC OO 4'!"i7 LIST OF ILLUSTRATIONS PAGE 1 D i s t r i b u t i o n of TCDD in Fraction of Column Eluate 24 la Schematic R e p r e s e n t a t i o n of A u t omated GC-QMS 28 Sys tem !( lb F r a g m e n t a t i o n Pathway A : j 45 2 Fragmentation Pathway B I ! 47 3 Fragmentation PathwayC 48 4 Fragmentation PathwayD .51 5 80 ppb Standard and Replicate Injections for Dow C h e m i c a l . (A S N -10) Sample ; 56 6 Dioxin D i s t r i b u t i o n in 43 Barrels of Hercules (ASN-14) 62 .. 7 Dioxin D i s t r i b u t i o n in 60 Barrels of Thompson 1 (ASN-5) 63 8 Dioxin D i s t r i b u t i o n in 80 Barrels of Dow Chemical (ASN-10) 64 9 Dioxin Dist r i b u t i o n in 61 Barrels Labeled Hercules (ASN-8) 65 vii SECTION I INTRODUCTION Luring the 1960's a herbicide formulation consisting mainly of the n-butyl esters of 2,4-dichlorophenoxvacetic acid (2,4-D) and 2,4,5-tric'nlorcphenoxyacetic acid (2,4,5-T) and designated Herbicide Orange was employed as a defoliant in Southeast Asia. Research performed at Bionetics Laboratories and reported i 'o ; : by Courtney et al early in 1970 implicated 2,4,5-T as a teratogenic agent. It was later reported"^ ^ that the 2,4,5-T formulation employed by Courtney et al contained 30 pg/g of 2,3,7,8-tetracnlorodibenzo-p-dioxin (2,3,7,8-TCDD)-- one H Cl HH 2,3,7,S-tetracnlorodibenzo-p-dioxin of the most toxic and and potent teratogenic substancgs-known. Subsequent to these findings, the Environmental Protection Agency promulgated more stringent rules regulating the domestic use of 2,4,5-T, and the Secretary of Defense ordered that use of these herbicide formulations in South Vietnam be discon- __ tinued. 'Tlfie abrupt ban on usage of 2,4,5-T defoliants left the Department of Def^ast?^the Department of the Air Force, in particular) with 2.3 million gal lons of such defoliants which are still stored in 55-gal. drums in Gulfport, Mississippi, and Johnston Island in the Pacific Ocean. Several methods for disposing of these herbicide stocks from the inventory are now under considera tion. In order to secure required data to support use of selected lots of the herbicide inventory, the Air Force Logistics Command requested the Gaseous Excitation and Ionization Processes Group of the Chemistry Research Laboratory at the Aerospace Research Laboratories (Air Force Systems Command) to undertake the development and application of analytical methods for characterizing Air Force herbicide stocks at Gulfport, Mississippi. Prior to the work at AEL 1 18849 some preliminary analyses had been performed by Dow Chemical Co, and the sample numbering system devised by Dow was retained throughout our studies. An "Analysis Sequence Number" was assigned to each herbicide Transpor tation Control Number (TCN). The pertinent TCN's, the manufacturer of each I1 batch, and the related Analysis Sequence Numbers are shown below: / Manufacturer TCN Thompson Company 94638155X012 Hercules Company 946481560001 Dow Chemical Company 94638155X052 Hercules Company 94648192001 " -------------- ------ ---- ---- Analysis Sequence N o . Calions on Hand as of 12 Jan 73 5 44,440 8 27,500 10 383,680 14 118,360 Total Gallons 5 7 3 ,9 8 0 . Approximate Market Value @ $40/gallon $22,959,200 Representative samples from each of the above TCN's were collected by personnel from Kelly AFB/EHL(K) on 10 July 1973. Individual samples were taken by suspending a 1- or 2-oz. glass bottle from a wire and inserting the bottle:~ 18 in. into the herbicide and swirling the bottle. The bottle was then removed and capped and the exterior was cleaned. Each drum was numbered and that number was scribed onto the glass bottle. Samples are precisely identified by listing the Analysis Sequence Number and barrel number. The convention adopted is shown here: 7 Hercules 8 * t * Barrel // Manufacturer Analysis Sequence Number This report describes the development and application of methodology de veloped for mass-spectrometric characterization of contaminants present in the herbicide samples at levels > 0.1%, including all volatile compounds and the chlorophenoxyacetic acids. The techniques for determining tetrachlorodibenzo-pdioxin in concentrations >0.02 ppm (0.02 yg/g) are also described, and the analytical results are summarized. 2 18850 J TABLE I (continued) t? !?' ___iliAi^p _ , r ^ . . , ^ , A I A second method for identification of small peaks which may be associated with an unknown compound is the mass chromatogram. After studying a normalized background-subtracted scan, very small peaks can be associated with the spec trum of interest by plotting the intensity of a certain mass as a function of chromatographic elution time and comparing the observed behavior either with a more intense peak that is known tc arise from the unknown compound or with the total ion chromatogram of the unknown in the mixture. An example of the use of this subroutine is given in Appendix D (see Figure D-ll and D-12). Here total-ion chromatograms, the Mass-196 chromatogram, and the Mass-206 chromatogram for Herbicide Sample i-264 are displayed as a function of chromatographic retention time. It is evident that Masses 196 and 206 origi nate not from the same compound but from two different compounds which elute at slightly different times. In this case, the relative amounts are such that this difference can actually be seen as a shoulder which appears at a longer time on the total-ion chromatogram. However, the compound, if present in smaller quantities, could not be observed visually in the total-ion chromatogram. It coulc be detected only if one of the masses which are associated with the lesser compound were displayed as a function of retention time. This technique greatly facilitates distinction of background mass-spectrometric peaks from small peaks arising from the unknown compound. This markedly simplifies identification of unknowns. Qualitative identification of unknown species can be made by first obtaining a listing of spectra at elution times corresponding to maxima or shoulders in the reconstructed total-ion chromatogram, and then searching for a molecularion identification using the mass-chromatogram displays to distinguish back ground from authentic peaks. Mass spectra of components are verified by comparison 'with stanaard mass-spectrometric tables. Appendix E is a compila tion of standard spectra taken in this laboratory for compounds that are of interest due to their suspected presence in the herbicide samples or due to their possible interference with lov?-level tetrachlorodibenzo-p-dioxin analysis. In each table the origin of the stanaard compound is given, along with the retention time of the compound and the time of the background spectrum. 12 18852 v.? 1`ti In addition to comparison of unknown spectra with spectra obtained from the literature or with standard spectra obtained under different conditions, it is often necessary to identify an unknown compound by comparison with the standard spectrum of an analogous compound. This method of identification is exemplified in the identification of an impurity present in each of the four herbicide samples analyzed-- the butyl ester of monochlorophenoxyacetic acid (XII). As can be seen from a comparison of the mass spectra in Tables A-9 and A-10 (see Appendix A), similarities between the two spectra include large m/e 57, 41, and 29 peaks, indicating the presence of the C^H^ group. The heaviest mass found that is associated with the molecular ion is 34 amu lower in Spectrum A-9 than in Spectrum A-10. The spectrum of I (Table A-10) has been identified from standard spectra to be the butyl ester of dichlorophenoxyacetic acid and the difference in the molecular-ion mass of 34 units, along with intense butyl ion fragments, indicates that Spectrum H of Gulfport //7 is a butyl ester of monochlorophenoxyacetic acid. In addition, Spectra I and H both have very intense m/e 91, m/e 101, and m/e 114 peaks. These correspond to loss of C.H Cl, CO C 11 , and CHCO.C.H , respectively, from the molecular ion. ho z h y Similar analogies are necessary in cases where the exact compound of interest is not readily available. Two other identification techniques reported here greatly simplify the inter pretation of the spectra of unknowns found in the four Gulfport herbicide samples analyzed. These techniques are (1) identification of butyl fragments in the spectrum and (2) the use of the isotope distributions to determine the number of chlorine atoms present in a given fragment. The basis for the butylfragment approach is seen in Figure A-6 (Appendix A ) . It is evident that only those total-ion chromatographic peaks which exhibit Masses 57, 41, and 29 can be assucdated with a butyl compound. Since the major components of Herbicide Orange are butyl esters, these compounds along with impurities containing butyl groups gave rise to these masses. The second technique mentioned above-- the chlorine-isotope distribution-- was also quite useful in classifying unknown compounds. Since the natural-chlorine 35 37 isotope distribution of Cl: Cl is approximately 3:1, mass spectra of 13 widely recognized tobe the most toxic small molecule known (LD,-q = 0.6 yig/kg ;in guinea pigs); the threat to man must at this point be assumed to be equally great. Thus, analytical methods for determining TCDD have been sought which can be used to detect and quantify TCDD in such samples as food stuffs, water, -1"' and soil at extremely low levels-- on the order of 1 x 10 g TCDD/g or 80 1 part-per-trillion. Baughman and Meselson"'' have used such a method,and Rvan10 and Crummettl"1have reported somewhat similar methods. It should be noted at this point that several structural isomers can quite properly be referred to as tetrachlorodibenzc-p-dioxin; thus, it is possible to encounter not only 2,3,7,8-TCDD but also 1>- .3,d-TCDD, 2,3,6,8-TCDD, 2,3,6,9-TCDD, etc. Approximately twenty tetrachlorodibenzo-p-dioxins are pos sible. Any analytical method which does not involve a very sophisticated gcheme for separating highly similar compounds prior to mass-spectral deter mination or which utilizes solely the molecular-ion region of the mass spectrum cannot possibly be used to make a distinction between the respective tetrachlorodibenzo-p-dioxins which may be present in the sample. Furthermore, depending upon the resolution of the mass spectrometer being employed, such techniques cannot be used to differentiate tetrachlorodibenzo-p-dioxin from other tetrachlorinated hydrocarbons having nearly the same mass (or mass frag ments) as the TCDD. Specifically, it is not at all certain at this writing ----------------- 12 whether the TCDD levels in Gulfport Herbicides reported by Dow in 1971 and 13 1972 represent 2,3,7,8-TCDD or a mixture of TCDD's which may be composed, in part, of the 2,3,7,8-TCDD. At worst, the Dow values represent upper limits. The emphasis in the work reported herein was the characterization of herbicide stocks stored at Gulfport, Mississippi; in the case of TCDD, a method which could be used to detect reliably and quantify tetrachlorodibenzo-p-dioxin present in Herbicide Orange at levels greater than 0.1 ppm was needed. The 8-11 methods alluded to above were not suitable for our purposes since the levels of TCDD of concern were 10^ greater than TCDD levels detectable by the techniques referred to above. Rather than ultrasensitive methodology, we sought to develop an approach which has adequate sensitivity and specificity 19 18854 i SECTION III ; RESULTS AND DISCUSSION A. VOLATILE CONSTITUENTS IDENTIFIED IN HERBICIDE ORANGE Tables IV through vtt 'aro lists of the components we have determined p h p present in the four representative samples of Gulfport Herbicide_^ a n g e ^ / T h e actual mass-spectral and gas-cffromatographic data utTfained for each of the four herbicide specimens have been consoli dated and included in the report in Appendices A-D. In establishing the identity of components in each of the four herbicide samples, it was also helpful to compare the analytical data from the four samples; in fact, in a qualitative sense these four specimens were found to be very similar. Table VIII contains gas-chromatographic retention times obtained in "fingerprinting" the four Herbicide-Orange speci mens (this "fingerprinting" technique is described in detail in Vol. II of this r e p o r t ) ^ along with the identities of the chromatographic peaks assigned following our GC-HS studies. The similarities of the r 'ur samples are apparent in Table VIII. A detailed discussion of the rationale employed in interpreting the large volume of data contained in Appendices A-D is outlined below in two parts: (1) identification of volatile unknowns in Herbicide Orange based upon direct comparison of mass spectra of unknowns with standard mass spectra and (2) identification of volatile unknowns based solely upon mass spectral data obtained for the unknown without confirmation by direct comparison with a standard spectrum. 1. COMPOUNDS IDENTIFIED BY COMPARISON WITH STANDARDS Butyl Esters of Dichlorophenoxyacetic Acid (XIII) and Trichlorophenoxyacetic Acid (XIV) The gas chromatograms and total-ion chromatograms obtained for each of the four Herbicide-Orange samples (Figures A-l, A-2, B-l, B-2, C-l, C - 2 , D-l, and D-2) indicate that each of the four samples 31 m um sam a >1. y ^ e* TABLE VITI RETENTION TIM!-.;, (SEC) FOP SPECIF" IDENTIFIED IN HERBICIDE ORANGE SAMPLES COMPOUND b GULFPORT DRUM NUMBER 2 59 251 264 Butanol (I) 27 Toluene (II) 43 Xylenes (III), Ethylbenzene(XI) - Butyl Chloride (IV) 136 Dichlorophenol (V) 255 Peak D(//251) - Trichlorophencl (VI) 493 Trichloroanisole (IX) - Dichloro-Methoxvanisole (X) - Dichloro-Methoxyanisole (X) - Butoxydic.hlorophenol (VII) - Butoxytrichlorophenol (VIIE) - Butyl-monochlorophenoxyacetate (XII) 1052 Butyl-dicnloropnenoxyacetate (XIII) 1262 Butyl-dichlorophenoxvacetate (XIII) 1357 Butyl-tric'nlorophenoxyacetate (XIV) 1462 Butyl-trichlorophenoxvacetate (XIV) 1614 Butyl-methoxv-dichlorophenoxyacetate (XV) 1650 Octyl-dichlorophenoxyacetate(XVI) 1768 Octyl'-dichlorop'nenoxypropionate (XVII) 1869 Octyl-trichlorophenoxvacetate(XVIII) 1931 l,l-dibutoxy-2-trichlorophenoxyethane (XXII) - Octyl-methoxy-dichlorophenoxyacetate (XXIII) 1966 Butyl-bis-dichlorophenoxyacetate(XIX) 2691 27 43 132 261 506 1075 1373 1482 1620 1671 - - 2711 26 c 126 252 390 757 990 1054 1265 1390 1464 1618 1646 - 1974 - 2665 27 43 68,76 257 507 629 713 761 1062 1140,1205 1406 1470 1626 1657 '2663 See chro matograms in Figures A - l , B-l, C-l and D-l of the appendix . Chromatographic parameters are as follows: 8 ft X 1/8" O.D . glass column packed with 10% DC-200 on Gas Chrom Q. Column temperature programmed from 110 to 240 C at 4 C/min. Data acq uisition: Autolab System IV computing integrator and 1-mV str ip-chart recorder . Drum fl is one of 500 drums obtained from Here ules Company (TCN 946 4 8156 000), Drum #5 9 is one of 2152 drums obtained Hercules Chemical Company (TCN 9464 8192 001), Drum it 251 is one o 6976 dr urns obtained from Dow Chemical Company (TCN 946 8155 X05 2), Drum #264 is one of 808 drums obta ined from Thomp X012) . Denotes none detected at levels greater than 0.1% 40 asters of d i c h l o r o p h e n o x y a c e t i c acid, t r i c h l o r o p h e n o x y a c e t i c acid, aQd dichlorophenoxypropionic acid. These were identified'only in Gulj-Port #7 in quantities greater than 0.1% of the total volatile samples. Mass-spectral data in Tables A-ll through A-13 and figures A-12 through A-14 can be compared with standard spectra given in Tables E-l through E-18. 2. IDENTIF I C A T I O N OF UNKNOWNS WITHOUT COMPARISON WITH STANDARDS t In order to identify the remaining components in the four Gulfport ^.samples, analogies with existing spectra shown largely in A p p endix E, along with molecular ion and fragmentation patterns, were relied -upon heavily. All components present in quantities larger than 0.1% * in the p r e - b u t y l ester of d i c h l o r o p h e n o x y a c e t i c acid region and -larger than 0.3% in the post-butyl ester of trichlorophenoxyacetic .acid region * were i d e n t ified,except compounds D and J in Gulfport #251 However, the lack of success in making an unambiguous identification ;;of these two compounds is not due to lack of sensitivity of the strument, but inability to d e t ermine the m o lecular ion and ;mportant fragmentation that would unambiguously identify the .unknown. This will be d i s cussed in more detail in a later portion i.o f this s e c t i o n . Butyl Esters of M o n o c h l o r o p h e n o x y a c e t i c Acid and Metho x y dichlorophenoxyacetic Acid "wo large impurities that are present in all four her b i c i d e samples ave been i d entified as the butyl esters of m o n o c h l o r o p h e n o x y a c e t i c cid (XII) and m e t h o x y - d i c h l o r o p h e n o x y a c e t i c acid (XV). In Gulfport #7, these compounds appear as peaks H and M (see Table A-9); in Gulfport #59, Pre-butyl ester = components eluting from the chromatographic column p r i o r to this ester. Post-butyl e s t e r = components eluting from the chromatographic column after butyl trichlorophenoxyacetate. t'r.ey are J 2 nd 0 (see Table B-9 and Figure B-ll); in G u lfport if 251, thev are K and P (see Table C-13 and Figure C-18; Table C-19 and Figure C-24); and in Gulfport #264, they are K and Q (see Table D-10 and Figure D-14). A complete spectrum of the b utyl ester of methoxyd i c h l o r o p h e n o x y a c e t i c acid superimposed upon the ester of trichlorophenoxyacetic acid was obtained only from #251 (Table C-19), and the other three samples were concluded to have this same contaminant, based upon F.I.D. r e t e n t i o n time (see Table VIII). If the spectra of the two butyl esters are compared with those of the b utyl esters of dichlorophenoxyacetic acid and trichlorophenoxyacetic acid (Tables E-19 and A-2, r e s p e c t i v e l y ) , it is appar e n t that p r ominent peaks which correspond to the m o l ecular ion and to the mol e c u l a r ion minus C ^ H g , C^HgCl, C O ^ H g , H C C 0 9C 4H 9> and O C H 2 CC>2 C 4H 9 (Fragmentation Pathway A outlined, Figure lb) are present. Based upon these features of the mass spectra, the unknowns are shown to be butyl esters of chlorinated p h e n o x y a ce tic acids. The isot o p e d i s t r i b u t i o n of the mol e c u l a r ion and the corresponding fr a g m e n t s conf i r m that these compounds are the monochloro- and dichloro-substituted phenoxyacetic acids. Compounds D and J in Gulfport #251 Two compounds coulc e^Identified conclusively in Gulfport #251. Compound--!)' is 1.2% c and C o m p o u n d J is on the o_rder of 0.1%. Data in Tables C-6 and C-ll and Figures C-9 and C-17 indicate that these compounds are very similar. Both compounds give rise to large butyl fra g m e n t s along with m/e 31 (CHgO+ ) , m/e 61, and m/e 116, but the isot o p e distr i b u t i o n s of these major fragments do not indicate the p r e s e n c e of chlorine. These unknowns are p o s s i b l y some type of butyl ether or ester of an u n c h l o r i n a t e d acid, or alcohol. Any further ide n t i f i c a t i o n w ould be c ompletely s p e c u l a t i v e due to the lack of positive i d e n t i f i c a t i o n of a m o l e c u l a r ion in the mass spectra and the absence of reference spectra among the 12,000 standard mass spectra catalogued in the General Electric mass spectral Search Routine computer library. 44 I S c S i ? Octyl Ester of MethoxT-dichloroplienoxyacetl 2 Acl. and 1 ,l - D i b u t o x y - 2 - T r iclilorophenoxyethane (XXII?- X major impurity found in each of the four herbicj.de samples vas determined to be the butyl ester of m e t h o x y - d i c h l o r o p h e n o x y a c e t i c acid. Such a compound could arise if cne of the chlorines in t r i c h l o r o p h e n o x y a c e t i c acid is r e p laced by a meth o x y group. Such an impurity in the trichlorophenoxyacetic acid would, when the acids are esterified with butanol or octanol, be converted to the corresponding ester during the synthesis of the herbicide. In ' : :i I 1 1- I ;j Gulfport #7 -- in; addition to the octyl esters of the dichloro- and trichlorophenoxyacetic acids -- the octyl ester of methoxy- dichlorophenoxyace tic acid was identified as Compound Q but was not identified in any of the other samples. Table A-14 gives a complete spectrum,and Figure A-15 shows it to elute after the analogous trichlorophenoxyacetic acid ester. Mass s p e c t r o m e t r i c a l l y a very similar compound to the octyl ester of m e t h o x y - d i c h l o r o p h e n o x y a c e t i c acid is the 1,l-dibutoxy-2-trichloro- h e n o x y e t h a n e . This compound was identified as Compound R in Gulfport #251. Its identity is b ased upon the s p e ctrum shown in .Table C-18 and mass c h r o m a t o g r a m s d i s played in Figure C-23. The ^retention times for this compound and the octyl ester of m e t h o x y idichlorophenoxyacetic acid are very similar; the major differences fcare: oct y l - i o n f r a g m e n t a t i o n is p r e s e n t in the octyl ester but .absent in the d i b utoxy compound; only di- and mono chlorinated fragments are present in the octyl ester, but prominent trichloro- henol and m o l ecular ions indicating a Cl^ species are present in .the dibutoxy spectrum. The i d e n t i f i c a t i o n of these compounds is not ased upon a complete mass spectrum; however, their most probable entities are the octyl ester of m e t h o x y - d i c h l o r o p h e n o x y a c e t i c acid 1,1-dibutoxy-trichlorophenoxy-ethane, respectively. 49 li: But:vl Esters of B i s - (chlor c ohenoxy )a ce ti c A c i d s The H e r b i c i d e - O r a n g e samples were found to contain the butyl esters' of b i s - ( c h l o r o p n e n o x y ) a c e t i c acids. These compounds can be product' during the synthesis of the h e rbicide by r e a ction of the correspoi chlorinated phenol with possible impurities in the 2-chloroacetic acid such as 2,2-dichloracetic acid. The three impurities found were the butyl esters of bis - ( d i c h l o r o p h e n o x y ) a c e t i c acid, bis(t r i c h l o r o p h e n o x y )acetic acid, and m e t h o x y - d i c h l o r o p h e n o x y t r i c h l o r o p h e n o x y a c e t i c acid. The last product is due to the metho dichlorophenol impurity in the t r i c h l o r o p h e n o l , as discussed in the previous section. Each of the four h e r b i c i d e samples was shown to contain at least two of these b i s - c o m p o u n d s . In #7 and # all three products were present in levels greater than 0.1%. In a d d i t i o n to the b utyl fragments, fragments very similar to the dichlorophenoxy-, trichlorophenoxy-, and methoxy-dichlorophenoxys esters are seen. However, the lack of m o l e c u l a r ions correspondin to the m o n o - s u b s t i t u t e d chlorinated p h enoxyace tic acid esters and the o c currence of this mass less 1 show the likelihood of a bissubstituted chlorinated phenoxyacetic ester. In addition, (m-101)*' ions with proper chlorine distributions were identified for Specie in #7 (see Table A-15), for Species P in #59 (see Table B-14), for;; Species T in #251 (see Table C - 1 6 ) , and Species R in #264 (see Table D-14) . The loss of 100 mass units from the radi c a l ion (m/e 275 for the bis-dichl o rophenoxyacetic ester and m/e 309 for the b i s - t r i c h l o r o p h e n o x y a c e t i c ester) was also seen to involve a r e a r r a n g e m e n t to y ield C O 2 and C^Hg as ne u t r a l products Prob a b l e . F r a g m e n t a t i o n P a t h w a y D is illustrated in Figure 4. B. Q U ANTITIES OF D I C H L O R O P H E N O X Y A C E T I C ACID AND TRICHL0R0PHEN0XYACETIC ACID PRESENT IN HERBICIDE ORANGE U s i n g the p r o c e d u r e for analysis described previously, we determinedd'* l the amount of di- and trichlo r o p h e n o x y a c e t i c acids in the four Gulfpo, samples. For calibration of the gas chromatograph, chloroform s o l u t i o n s of E P A / F D A - p r i m a r y - s t a n d a r d methyl dichloro- and methyl 50 PERCENT co co PARTS PER MILLION Figure 8. DIOXIN DISTRIBUTION IN 8 0 BARRELS OF DOW CHEMICAL ( A S N - 10 ) CV3 CO Ou CD rH ON Ln PARTS PER MILLION Figure 9. DIOXIN DISTRIBUTION IN 61 BARRELS LABELED HERCULES(ASN-8) SECTION IV SUMMARY OF RESULTS Table XV summarizes the results of the qualitative and quantitative analysis of selected samples of Herbicide Orange. Volatile con s t i tuents (with boiling points below 300C at 1 atm) and the chloro- p h e n o x y a c e t i c acids are the m ain components in the H e r b i c i d e - O r a n g e samples. The absolute r e s ponse of the flame ioniz a t i o n detector (FID) was det e r m i n e d for the butyl ester of 2,4,-D and the butyl e ster of 2,4,5-T through use of the EPA standards. Assuming that all components of the herbicide mixture gave an equal response on the flame i o n ization detector, we detected an average cf 96 +10% of the total herbicide sample injected onto the gas chromatographic column by FID. Thus, the relative amounts of volatile components listed in Tables IV through VII (pp. 32-39) and s u mmarized in Table XV (p. 68 ) represent the absolute composition of the sample in percent by weight (within the limits of the a s s u m p t i o n of equal detector response). This report describes the in-depth GC-MS qualitative and quantitative analysis of r e p r e s e n t a t i v e samples from four separate drums in Gulfport, Mississippi, w h i c h were taken as r e p r e s e n t a t i v e samples of four lots of H e r b i c i d e Or a n g e identified on the basis of p reliminary Dow Chemi c a l Co. A n a lyses as "low dioxin herbic i d e . " In addition to the in-depth; GC-MS c h a r a c t e r i z a t i o n of the four represe n t a t i v e samples, a concurrent study'*'"' described in Vol. II of this report was u n d e r t a k e n ,in which the h o m o g e n e i t y of the major and minor co n stituents in the drums r e p r e s e n t i n g each of the four H e r b i c i d e Orange batches was examined by suing flame-ionization gas chromatog r a p h y (FID-GC). By correlating the retention times measured for the various components in the FID-GC study (see Vol. II) with those m e a s u r e d in the present detailed GC-MS i d e n t i f i c a t i o n study, it is p o s sible to derive q u a l i t a t i v e data for the components of the several barrels of each h e r b i c i d e :lot analyzed. These results are summarized in Tables p,O ^ o ib G G J TABLE XV SUMMARY OF COMPOSITION OF HERBICIDE ORANCt COMPOUND GULFPORT DRUM NUMBER 2 7 Butanol (I) 0 ,.81 Toluene (II) 1,.3 Xylenes (III), Ethylbenzene(XI) -- Butyl Chloride (IV) Dichlorophenol (V) 0 11 0 .19 Peak D(//251) - Trichlorophenol (VI) 0 .41 Trichloroanisole (IX) - Dichloro-Methoxyanisole (X) - Dichloro-Methoxyanisole (X) - Butoxydiehlorophenol (VII) - Butoxytrichlorophenol (VIII) - Butvl-monochlorophenoxyacetate (XII) 0 .49 Butyl-dichlorophenoxvacette (XIII) Butyl-dichlorophenoxyacetate (XIII) 0 .78 4pn .4 Butyl-trichlorophenoxyacetats (XIV) 0 .92 Butyl-trichlorop'nenoxyacetate (XIV) 19 .0 Butyl-metnoxy-dichlorophenoxyacette (XV) Octyl-dichlorophenoxyacetate(XVI) 6 .1 3 .2 Octyl-dichloropnenoxypropionate(XVII) Octy]-trichlorophenoxyacetate(XVIII) 0 .3 2 .0 1,i-dibutoxy-2-trichiorophenoxyethane (XXII) -- Octyl-methoxy-dichlorophenoxyacetate (XXIII) 0 .37 Butyl-bis-dichloropnenoxyacetate(XIX) 0 .41 Butyl ester of bis Trichlorophe noxyaceticacid (XX) Butyl ester of Trichlorophenoxy - 0 .95 0 .16 2,4-Dichlorophenoxyacetic acid (free 0 .78 acid) 2,4,5-Trichlorophenoxyacetic ac id (free acid) 0 .84 Tetrachlorodibenzo-p-dioxin (pg /g)C < 0..05 59 0 .75 2 .2 -- 0 .16 0 .26 -- 0 .67 -- -- -- -- -- 1. 16 -- 44 .2 0 .70 42 .1 5 .4 -- -- -- -- -- 0 .58 1. 8 25]L 0 .28 --b -0 .14 -- 1. 2 -- -- -- 0. 22 0 .31 2 t6 4 .2 43 .3 0 .96 44. 1 1. 9 -- -- -- 0. 36 -- 0 .47 0 .19 264 13 0 .51 2 .6 -0 .28 " 3 .6 0 .75 0 .IS 0. 31 -- -- 0 .78 20 44 .9 0 .44 40 .1 2 .5 -- -- -- ----0 .27 0 .,53 0 .21 0 .65 -- 0 .19 -- c .,66 0. 78 0. 13 0 ,. 8 0 0 .07 0 .38 0 .18 68 TABLE XV (continued) Drum //7 is one of 500 drums o b t a i n e d from Hercules Company (TCN 9464 8156 000)* Drum #59 is one of 2152 drums obtained from Hercules Chemical Company (TCN 9464 8192 001); Drum #251 is one of 6976 drums obtai n e d from Dow Chemical Company (TCN 9463 8155 X052) J Drum #264 is one of 808 drums obtsained from Thompson Company (TCN 9463 8155 X012). '> : f Denotes none detected at levels greater than 0.1%. Note well that the tetrachlorodibenzo-p-dioxin content listed in pg/g (ppm); all other values are listed as relative percent (calculation of relative percent: _____ p_e_a_k___a_r_e_a___o_f__c__o_mpr.o__n_e_n_t___ __ ____ __ x 10,,0). total area of all volatile components is XVI, XVII, XVIII, XIX and suggest that each lot is generally quite h o m o geneous. Furthermore, the feasibility of using the "f ingerprint" of m a j o r and minor constituents to ascertain the m a n u facturer of an unidentified specimen of Herbicide Orange was con clusively demonstrated. The h omogeneity of each of the four batches of H e rbicide Orange with respect to TCDD c o n c e n t r a t i o n is of utmost concern. Our data as shown in b a r - g r a p h form (Figures 6-9) lead one to the conclusion that only Thompson Co. ASN 5 (44,440 gallons in storage) and Hercules ASN 14 C_1 1 8 .36 0 gallons in storage) are sufficiently unifqxm^*in TCDD content and other~^rt>h&t-rtVen~t's"'T:'0'-b-e^onsidered homogeneous throughout. /Hercules ASN 8 (27,500 gallons in storage)-, /Is inhomogeneous in TCDD content--8% of the drums sampled were found to contain i n o r d i n a t e l y high levels of TCDD. It may well be chat these "high dioxin specimens" or the drums from which they were obtained are actually mislabeled. This can be determined by the m ethodology d e scribed in Vol. II of this report. The DON ASN 10 T"38`3t 6'80-- g a l l o n s in storage) batch a_pj3eixs-- q-ui"te heterogeneous. The data shown in the bar graph (Figure 8) suggest the presence of two or more s u b - g r o u p s ,each with average TCDD content of well over 0.1 y g / g . It should be noted that the d i s t r ibution of dioxin levels in Figure 7 is suff i c i e n t l y n a r r o w (95% of the values obtained were wi t h i n 20% of the mean .value of 0.125 ppm) that it is a measure not only of the actual d i o x i n - l e v e l d i s t r ibution but also of the precision of the a n a l y t i c a l m e t h o d o l o g y (as discussed in an earlier section, the overall p r e c i s i o n of the analysis is 12.5%). For the Dow ASN 10 samples, however, the dis t r i b u t i o n of dioxin levels is much broader and clearly is i n d i c a t i v e of the actual spread of values in the batch itself. Again, the Dow material is certainly very inhomogeneous. 70 TABLE XVI f COMPOSITION OF VARIOUS DRUMS OF HERBICIDE ORANGE IN THE LOT DESIGNATED ANALYSIS SEQUENCE NUMBER 8 (HERCULES CO.)+ Compound Butanol ____ Drum Number____ 2 1_ 11B (b) 0.71 Cc) 26 0.81 27 1.36 25 Toluene 1.47 43 1.32 43 1.75 41 Butyl Chloride 0.07 134 0.11 136 0.11 137 Dichlorophenol 0.25 265 0.19 255 0.26 256 Trichlorophenol 0.43 511 0.41 493 0.42 497 Butyl monochlorophenoxyacetate 0.59 1075 0.49 1052 0.58 1057 Butyl dichlorophenoxyacetate (d) 0.78 0.37 1262 1267 Butyl dichlorophenoxyacetate 42.8 1382 42.5 1357 39.8 1367 Butyl trichlorophenoxyace tate 0.90 1486 0.92 1462 0.85 1467 Butyl trichlorophenoxyacetate 39.3 1608 39.0 1583 38.6 1593 Butyl methoxydichlorophenoxyace tate 5.87 1673 5.40 1650 6.00 1656 Octyl dichlorophenoxyacetate 3.32 1793 3.21 1768 3.46 1777 Octyl dichlorophenoxypropionate 0.32 1894 0.32 1869 0.35 1878 Octyl trichlorophenoxyace tate 2.29 1957 2.05 1931 2.33 1941 Octyl methoxydichlorophenoxyacetate 0.38 2002 0.37 1986 0.37 1976 Average 0.96 26 1.51 42 0.10 136 0.23 259 0.42 500 0.55 1061 0.58 1265 41.7 1369 0.89 1472 38.9 1595 5.76 1660 3.33 1779 0.33 1880 2.22 1943 0.37 1988 71 CG U ttm \ TABLE XVI (continued) Compound Butyl (bis-dichlorophenoxy)acetate Drum Number 21 11B 0.34 2691 0.41 2700 0.38 2717 Butyl (bis-trichlorophenoxy) acetate (e) 1.8 (e) Butyl (methoxydichlorophenoxy) tri- chlorophenoxyacetate (e) 0.21 (e) Tetrachlorodibenzo-p-dioxin (y g/ g ) <0.05 <0.05 <0.05 Average (a) 0.38 2703 (f) <0.05 TThis lot obtained from Hercules Comp any (TCN 9464 8156 0001) contains 500 d r u m s . (a) Average relative percent and retention time or the respective compounds found in these samples. Table shows two values for each volatile compound. ^k^Relative amount (%) of the compound (c) Gas chromatographic retention time of the compound (sec.) ( d )'Present in chromatogram but no numerical value obtained. Quantity present appears to be similar to amount found in other samples. The average was determined by dividing the sum of the values obtained by the number of actual observations. ( 6 ) Analyses not perrormed. ^ ^ A d d i t i o n a l TCDD analyses are summarized in Figure 9 , p. 65 . a. 18068 72 ABLE XVII COMPOSITION OF VARIOUS DRUMS OF HERBICIDE ORANGE II! THE IDT DESIGNATED ANALYSIS SEQUENCE NUMBER (HERCULES C0MP.-.;r: rnmpound ____________ Drum Number____________ Ave rags 17. 27. 39 42 50 59 Butanol Toluene (b) 0.79 (c) 25 2.57 39 C .67 27 2.31 43 0.87 26 2.75 42 0.77 27 2 .nQ 43 0.82 31 ? 35 49 0.75 27 2.24 43 Butyl Chloride 0.17 0.17 0.17 0.15 0.14 0.16 122 129 126 130 147 132 Dichlorophenol 0.34 0.32 0.33 0.30 0.30 0.26 249 257 250 258 287 261 Trichlorophenol 0.75 0.55 0.77 0.71 0.76 0.67 492 487 498 501 543 506 Butyl monochlorophenoxyace tate 1.42 1.39 1.44 1.28 1.34 1.16 1063 1063 1051 1068 1125 1075 Butyl dichlorophenoxyacetata 1.03 1.09 0.79 0.92 0.65 1274 1273 1260 1278 1338 (d) Butyl dichlorophenoxyacetate 43.1 42.6 42.3 42.7 43.4 44.4 1380 1380 1361 1385 1434 1393 Butyl trichlorophenoxyacetate 2.51 2.02 1.82 1.79 1.65 0.70 1473 14 71 1461 1476 1538 1482 Butyl trichlorophenoxyace tate 40.6 41.2 40.3 41.1 40.4 42.1 1606 1607 1588 1612 1662 1620 Butyl methoxydichlorophenoxyacetate 5.62 5 .71 6.16 5 .70 6.69 5.44 1665 1662 1653 1666 17 31 1671 Butyl (bis-dichlorophenoxy)acetate 0.45 0.46 0.53 0.39 0 .38 0.58 2687 2706 2670 2704 2314 2711 Butyl (bis-trichlorophenoxy)acetate (e) (e) (e) (e) (e) 1.8 Butyl (methoxydichlorophenoxy)- (e) (e) (e) (e) (e) 0.21 trichlorophenoxyacetate Tetrachlorodibenzo-p-dioxin (hg/g) <0.05 <0.05 0.08 0.06 0.07 0.07 0.78 27 2.52 43 0.16 131 0.31 260 0.70 505 1.34 1074 0.90 1285 43.2 1389 1.75 1434 41.0 1616 5.89 16 75 0.4/' 2715 ^"ihis lot obtained from Hercules Company (TCN 9464 8192 001) contains 2152 drums. (3.) Average relative percent and retention time for the respective compounds found in these samples. Table shows two values for each volatile compound. F TABLE XVII (continued) (b) Relative amount (%) of the compound. (c) Gas c h r o m a t ographic retention time ( s e c ) . (d) Present in chromatogram but no numerical value obtained. Quantity pres ent appears to be similar to amount found in other samples. In this case the average value was calculated by dividing the sum of the values o b t ained by the number of actual observations. (e) Analyses not performed. (f) A d d i t i o n a l TCDD analyses are s u m m a r i z e d in Figure 6, p. 62. i i 74 S'S'?. TABLE XVIII COMPOSITION OF VARIOUS DRUMS OF HERBICIDE ORANGE IN THE LOT DESIGNATED ANALYSIS SEQUENCE NUMBER 10 (DOW CHEMICAL C0.)t Compound Butanol 2A9 (b) 0.29 ( c ) 27 250 0.30 27 251 0.28 26 252 0.25 27 Dr urn INumber 253 25 A 255 0.61 0.2A 0.25 27 26 27 256 0.23 26 257 0.30 26 258 0.35 27 275 0.30 27 AAverage (a) 276 0.23 0.30 27 27 Toluene 0.17 0.23 A 0.15 0.61 A A A A A A A 0.10 (d) A3 A2 A2 A2 A2 Xylenes, Ethylbenzene 0.08 0.0 A A A 0.08 A A A A A A A 0.03 77 75 75 76 Butyl Chloride A A 0.1A A A A A A A 0.17 0.1A A 0.05 126 128 128 127 Dichlorophenol 0.11 0.10 0.10 0.10 0.2 A 0.10 0.10 0.10 0.13 0.1A 0.10 0.10 0.12 261 255 252 261 257 257 252 25A 25 A 256 255 258 256 Peak D AA Trichlorphenol 0.23 A0 3 0.38 A92 0.28 392 0. A8 A92 1.2 A 0.23 390 A0A 0.15 0.39 A78 A92 0.22 0.33 398 397 0.2 A 0.12 A87 A86 0.33 389 0.12 A 77 0.33 393 0.12 A83 0.A0 392 0.17 A 81 1.52 389 0.21 A80 1.26 393 0.21 A82 0.33 398 0.11 A87 0.57 395 0.23 A85 Butoxydichlorobenzene 0.10 772 Butoxytrichlorobenzene 0.10 1029 0.13 760 0.13 101A 0.22 757 0. A0 1012 0.11 773 0.16 1030 0.0A 791 0.10 10 2A 0 .1A 768 0.09 1025 0.1A 756 0.08 1011 0.13 76 A 0.08 1021 0.1A 761 0.12 1015 0.28 753 0.20 1009 0.31 761 0.37 1017 0.13 768 0.07 1025 0.16 765 0.16 1019 f Butyl monochlorophenoxyacetate 1.08 1. A2 1.59 1.08 1.01 1.25 1.27 1.25 1.55 2.2 A 1.59 1.26 1.38 1069 105 A 105 A 1070 1062 1066 1052 1062 1056 10A 9 1060 1066 1060 Butyl dichlorophenoxyacetate 2.15 2.69 3.07 1.87 0.92 2.85 2 .79 2.70 A.26 A. 15 2.99 2.78 2.77 1282 1268 1265 1280 127A 1280 1266 1277 1270 1260 1272 1280 1273 T A III,li XV I IT (continued) Compound Butyl dichlorophenoxyacetate 249 43.2 1404 250 43.8 1358 251 43.3 1390 252 4 3.8 14 06 Drum Number 253 254 255 44.3 44.7 44.4 1370 1403 1389 256 45.5 1403 257 44.1 1363 258 42.2 1353 275 44.2 1398 Average (a) 276 45.7 44.1 1408 1387 Butyl trichlorophenoxyace tate 1.23 2.23 0.96 1.45 0.83 0.82 0.85 0.85 1.32 1.46 0.99 0.85 1.22 1482 1464 1464 14 84 14 71 1478 1464 1475 1465 1454 1470 1479 14 71 Butyl trichlorophenoxyacetate 43.2 40.9 44 .1 42.8 41.9 45.6 45.6 44.8 42.1 41.1 43.6 44.5 43.4 1632 1582 1618 16 35 1596 16 33 1619 1631 1589 1577 1625 1635 1614 Butyl me tlioxy d1cli1o ro- 3 .A8 3.70 1.97 1.80 3 .34 2.18 2.21 2.19 3.73 3.33 1.99 2.19 2.68 phenoxyacetate 1662 1642 16 46 166 3 16 52 1662 1648 1659 1646 1632 1654 1663 165 2 Octyl dichloro-AA phenoxyacetate ~-j O' Octyl trichlorophenoxyacetate** 0.40 17 26 1. 19 1826 0 .70 1708 * 0.25 1717 * 0.37 17 28 1 .40 18 30 0.27 0.15 17 23 1731 1.64 0.12 1822 1819 0.18 1717 0 .12 1804 0.19 17 28 0.15 1816 0.27 1718 0.18 1801 0.30 1706 A 0.21 1724 0.07 1812 0.18 1732 0.14 1819 0.29 1722 0.42 1817 l.l-dibutoxy-2-trichlorophenoxyethane 0.24 1990 * 0.36 0.27 0.65 0.29 0.29 0.29 0.40 0.46 0.36 0.29 0.33 19 74 .1995 1986 1990 1974 1987 1976 1966 1982 1990 1983 Butyl (bis-dichlorophenoxy)acetate 0.42 2682 * 0.47 0.44 0.85 0.29 0.40 0.29 0.55 0.56 0.33 0.39 0.42 266 5 2735 26 94 26 79 2652 2680 2682 2674 2677 2680 26 82 Tetrachlorodibenzo-p - dioxin (pg/g) 0.13 0.20 0.38 0.17 0.11 0.22 0.22 0.30 0.21 0.41 0.22 0.29 ^This lot obtained from Dow Chemical Go . (TON 946 3 815 5 X052) contains 6976 dr urns . (a )A.verage ret.ati,.ve percent an<1 retentl on time for the respect 1ve compounds found In these sum p1es . Table shows two values for eacli volatile compound ^k^xhe relative amount (%) of the compound. (c) Gas chromatographic retention time (sen). CO 00 -J. TABLE XVIII (continued) (d) In the cases where a compound was detected in only a few of the samples and not in others, the average was calculated by dividing the sum of the values by 12. (e) Additional TCDD analyses are summarized in Figure 8, p. 64. *None detected. Tentative identification based solely on gas chromatographic retention time. Drums 249, 250, 251, and 252 contain an unidentified component at an average retention time of 79G sec and average relative percent concentration of 0.14; Drums 251, 254, 255, 256, 257, 258, 275, and 276 contained another unidentified component with retention time of 888 sec and 0.07 retention time and average relative percent concentration. Also, Drum 253 exhibited an unidentified component at 291 sec, relative intensity, 0.13% and Drum 252 was found to contain a component with a retention time of 1502 sec and relative intensity of 1.78%. TABLE XIX COMPOSITION OF VARIOUS DRUMS OF HERBICIDE ORANGE IN THE LOT DESIGNATED ANALYSIS SEQUENCE NUMBER 5 (THOMPSON CO.)t Compound Dr urn Number 262 263 264 274 Butano1 (b) 2.1 1.6 1.1 1.8 (c) 26 27 27 27 Toluene 0.78 0.68 0.51 0.62 42 42 43 43 Xylenes, ethyl benzene 3.8 3.5 2.6 3.5 71 71 72 72 Butyl chloride 0.15 0.14 0.10 0.14 104 103 104 105 Dichlorophenol 0.38 0.35 0.28 0.36 257 254 257 259 Unknown 0.15 0.14 0.11 0.14 291 287 289 293 Trichlorophenol 4.7 4.3 3.6 4.3 506 501 507 510 Dichloromethoxy.anisole 0.17 0.16 0.13 0.16 599 594 601 603 Trichloroanisole 0.99 0.90 0.75 0.91 629 625 629 634 Dicnloromethoxyanisole 0.23 0.21 0.18 0.21 712 708 713 717 Di chi orome thoxyanisole 0.45 0.42 0.31 0.42 760 756 761 766 Butyl monochlorophenoxyacetate 1.1 0.96 0.78 0.97 1060 1057 1062 1066 Butyl dichlorophenoxyacetate 0.36 1148 0.29 1145 Butyl dichlorophenoxyacetate 0.28 0.16 1200 , 1205 1212 0.30 1209 , 1220 Unknown 0.11 0.40 1238 1236 0.39 1245 A*verage (a) 1.7 27 0.65 43 3.4 72 0.13 104 0.34 257 0.14 290 4. 2 506 0.16 599 0.89 629 0.21 713 0.40 761 0.95 1061 0 . 1 6 (d) 1147 0.19 1209 0.23 1240 V ai. kw '* w;V 'f; v. "r $-XaL? J 1 ` 's5 *a if V' ' f > M S' J -s % i'. ,7\ "4 $ X' O TABLE XIX (continued) Drum Number 262 263 264 274 lutyl d i c h l o r o p h e n o x y a c e t a t e f ^utyl dichlorophenoxyacetate 0.21 0.54 0.53 0.52 1267 1264 1268 1276 42.1 41.2 44.9 41.3 1389 1387 1406 1397 ^Butyl trichlorophenoxyacetate 0.37 0.36 0.44 0.36 1465 1464 1470 1473 Butyl trichlorophenoxyacetate 41.1 38.4 40.1 38.3 1605 1605 1626 1619 e 4.6 2.5 4.6 1649 1657 1659 Unknown 0.33 2296 Unknown 0.12 23 79 Butyl-bis-dichlorophenoxyacetate 0.38 0.27 2689 2663 Tetrachlorodibenzo-p-dioxin (ug/g) (e) (e) 0.18 (e) Av erage (a) 0.45 1269 42.4 1395 0.38 1468 39.5 1614 2 . 9 (d) 1655 0.1 2296 0.03 2379 0.16 2676 (e) This lot obtained from Thompson Company (TCN 9463 8155 X012) contains 808 drums. (a) Average relative percent and retention time for the r e s p e c t i v e compounds found in these samples. Table shows two values for each volatile compound. (b) Relative am o u n t (%) of the compound. (c) Gas c h r o m a t o g r a p h i c ret e n t i o n time of the compound (sec). (d) In the case w h e r e a compound was detected in only a few of the samples and not in others, the average was calculated by d i v i d i n g the sum of the values by 4. (e) A d d i t i o n a l TCDD analyses are summarized in Figure 7, p. 63. 79 v* f .'J , / REFERENCES 1. K. D. Icurtney, E. K. Gaylor, M. D. Hogan, H. F. Falk, R. R. Bates, and I. Mitcnall, Science 16S, 864 (197C) . 2. K. D. Courtney and J. A. Moore, Toxicology and Applied Fharmacology 20. 396 (1971) . 3. J. L. Frierson, D. J. Thompson, C. G. Gerbig, and V. B. Robinson, Toxicology and Applied Pharmacology 17_, 317 (1970). 4. G. L. Sparscnu, F. L. Dunn, and V. K. Rowe, Food Cosmet. Toxicol. _9, 405 (1971). 5. B. A. Schwetz, J. M. Norris, G. L. Sparschu, V. K. Rowe, P. J. Gehring, J. L. Emerson, and C. C. Gerbig in Chlorodioxins-- Origin and Fate, American Chemical Society Advances in Chemistry Series 120 (E. H. Blair, ed} (Washington, D. C., American Chemical Society, 1974) , p. 55. 6. A. Poland and E. Glover in Environmental Health Perspectives Experimental Issue Nc. 5 (Washington, D. C., U. S. Department of Health, Education, and Welfare, September 1973), p. 245. 7. D. Firestone, ibid, p. 59. S. Fi. Baugr.mar. and M. Meselson in Chlorodioxins-- Origin and Fate, American Chemical Society Advances in Chemistry Series 120 (E. H. Blair, ed.) (Washington, D. C., American Chemical Society, 1974), p. 92. 9. R. Baughman and K. Meselson in Environmental Health Perspectives Experimental Issue No. 5 (Washington, D. C., U. S. Department of Health, Education, and Welfare, September 1973), p.27. 10. J. F. Ryan, F. J. Biros, and R. L. Harless, Paper C-2 presented at the 22nd Annual Conference on Mass Spectrometry and Allied Topics, 20 May 1974, Philadelphia, Pa. 11. W. B. Crummett and R. H. Ste'nl in Environmental Health Perspectives Experimental Issue No. 5 (Washington, D. C., U. S. Department of Health, Education, and Welfare, September 1973), p. 15 12. Dow Chemical Co. Report No. IAS-43 issued to SAAMA/PIMM, Kelly AFB, Texas, 7 September 1971. 13. Dow Chemical Co. Report No. IAS-246 issued to SAAMA/SFQT, Kelly AFB, Texas, 26 December 1972. 80 4 . W. C. Guenther, " T olarsnco Intervals for Univ a r i a t e D i s tributions", Naval R e s earch Logistics Quarterly IJ^, 309 (1972). 1 5 . D. C. Fee, B. M. Hughes, T, C. Tiernan, C. E. Hill, and M. L. Taylor, "Analytical M e t h o d o l o g y for Her b i c i d e Orange, l,e s p o w o e r c o m p a n y cc*. Mr. Paul Mayfield - Executive Mr. Charles Haddock - Legal Dr. Lemuel C. McGee - Medical Mr. P. J. Reno - Synthetics Mr. R. T. Yates - Synthetics -- Mr. C. L Dunn - Synthetics M r . J. M. Eagan - Synthetics -- Mr. H. E. Wilder - Jacksonville Mr. A. D. Sidvell - Jacksonville i-Mr. Ashworth Bur.js'ff~- \Advertising Vilmingtdh, Delaware March 26 j, 1965 / TO: Mr. John G. Copeland - Synthetics Department 7S0M: John ?. Fravley - Medical Department Report of Meeting with Ibv Chemical Company on the Toxicity of Trichloropher.ol Impurities __ _^v the^ "A't^oh of Mr^V.._JC--SoWe^-i Bioehemi Research Department, Dev Chemical Company, Mr. C. L. IXinn and the writer (along with representatives of other TCP producers-- see letter attached) met in Midland on March 2k, 1965 to discuss impurities in TCP. Mr. Rove and Dr. Holder of Dow reported that 60 to TO employes of D the past tvo years have developed chloracne froa-exposures to materials in their TCP operation. Chloracne is a'disfiguring disease-involving blockage and inflammation cf the sebaceous glands of tiiiTkinj~partlcularly of the face. It is believed to b- a ^syiitem^c disease and requires several years after exposure for the condition to di sapp^ar Dow has conducted considerable research to identify the cause of this ccr.iiticr. and has concluded that several impurities, sometimes present in TCP, are responsible. They have identified one of these impurities which they believe is the principal acnegen-- 2,3jTj8-tetrachlorodibenzo-p-dIoxin. They have developed (and supplied to all attendee*) a chemical method for the detection of this material vhich is sensitive/to 1 ppm (gas chromatography and flame ionisation). \y There was considerable'discussion of the clinical aspects of the disease a.td the toxicological research Dow has conducted. In brief, 2,3#T,8-TCD2D has teer. shown to produce the disease in rabbits at a concentration of Up ppm after or.e application of 0.1 ml to the ear, and at a concentration of O.h ppm after eight applications. Ho evidence of the disease has been produced by concentrations u? to 20 ppm for sl single application and up to 0.1 ppm for twenty-five applications to rabbit ears. The compound has also been demonstrated to be a potent liver toxicant by oral or skin exposure. As little as 0.017 mg/kg is lethal to & rabcits by the oral route. Dov has analyzed commercial samples of TCP of *Vl producers and has found up UQ GO 2,3,7,8-TCDED in some. In finished samples of 2,k,5*,T-eci4 they have -our.d up to 10 ppm. Ho Hercules sample-analyzed contained any significant aeneger.. Dov has reduced their TCP capacity aud is checking-all production to POW DER COMPANY Mr. Jchr. G. Copeland Page 2 March 26, 1 9 r.ot positive that burning vill completely destroy the acnegem. Dow's intention ir. requesting this meeting .was to inform all TCP producers of this information so that they car. take steps to control the quality of their TCP production. A sample of 2 , 3,7,3-TCDE3 for analytical control was supplied to each company* The-'Michigan State Departmeni^of Health has been consulted on this problem because of labor_-.r-e-iations -problems. Cow suspects that the Federal Government has k~ronT~aware-gf-^the--problem*. srfd-"C5at" Hercules take immediate steps to determine whether any acr.eger.'s are formed in our TCP process. Th^-tfiould'be determined by chemical analyses ar.d biological assays. If any sp6h materialsj are formed, we should dete-.cir.e the fate of these materials in four plant--whether they are chemically destroyed, burned, or discharged in the w^ate stream, etc. We should also conside: :e desirability of constant monitoring olVpur TCP or 2,U,5JT-acid production by chemical methods to protect against illegitimate claims of acne from users of our 2 y i,5 ~ ? products. L- , - a 1 18873 JL KtACVKJS . A' I H u h ly Tonic Im purit tn 2 , 4. >T ricMoroo>o*o) ip i w w * ACHMENT o Envircrr m ntal Protection Agency Pesticides Office Criteria end Evaluation Division Washington, D. C. 20250 Attention i Mr. Carroll w . Collier Chief Chemist Chemistry Branch Gentlemen* -A Re: Your letter of March 16, 1973 requesting information a* "dioxin" content Af Transvaal 2,4,5-T Butyl Ester E?A Reg* No. Uo87-31 and Transvaal 2,4,5-T Low \tolatile Eater EPA Reg* No. 116S7-33 The subject ester products are manufactured from the appropriate purciusod alcohols and 2,4,5-T acid of cur plant production. Tic 2,4,5-T acid is produced from the coupling of ntnochloro-acetic a d d and 2,4,5-Trichlorophenol produced in our plant. 1. Tlje "dioxin" with which we are concerned la 2,3,7,8-tetrachloro-ditienzO-p-dicodn, since It Is the most UJcely "dioxin" to be expected in 2,4,5-T acid. Accordingly, we examine our 2,4,5-T a d d production. ____ The level of 2,3,7,8-TCDO f o n d in our 2 ,4,5-T1acid ranges frcn aroints classed as undetected to a high of 2 ppm as determined in our laboratory. The average amouit found is below 1 b p s . ______ Since the operating conditions employed to manufacture our esters involves relatively lower temperatures than those which are nocess saxy for the generation of "dioxin" fran ortho-substituted chlcancphenols in alkaline madia, and employ an a d d catalyst, we do not routinely ex amine our esters fear dioxin content. Samples of esters which we have examined fran time to time hove yielded results wtiich range from "undetected to a high of 1.5 pftru 2. Ths analytical procedure which we use Is based upon that publicised by C. A. Elvidge (THE ANALYST, Oct. 1971, Vol. 96, pp. 721-727) for the analysis of asters, femulated products and free add. 18833 REQUIS..O N N O T E : R E Q U lS IT Ip M E R TO F I L L IN A R E A S WITH C O R N E R SIG N A LS IF A P P L IC A B L E TO T H IS O RDER ir 'X & a / / * ; V SUwCvCvEkS.T' bE Oi / own l a s t v. .Innwovonn Ti rf iTsnnovwn n L A S T . O . (tO, R EQ U ISITIO N NO. E N D O R s t! DO W C H E M I C A L U.S.A. I F tirm n o ti or P C t -n d s p T h y C t Q . c CNf Um jnc 7 0 d f~ O . Ac Jit//**' $ /ito ( P r f & v chs< . ~~ " 7?asyi ,,s f / s y FCrrrrrrrrrrr" 08227 923942 S T IC K P .O . N U M B ER H E R I r_ Y ^e q Ui s i t io n co i r 1,111 l|L V F N O N C " J F T C qT vhd l ougn N 8 ! / C - 'n ____ I C H E C K FO R E X T R A E X P E D IT IN G T h is means that the R e q u isitio n Approver A U T H O R IZ E S ad d itio n al charges (or Prem ium Fo llo w -u p , H igher p rice , Premium fre ig h t, ond /or any other s p e c ia l m ethods to m eet requested delivery date. S H IP P IN G IN FO R M A TIO N D A TES ' ft y\ y a d d it io n a l c o p ie s to d Q l \ 0 |Z . G >t r^ v V l L O S . V f Hl R TO PMONA H & ) \ - Z O cJZ | V H I q u I S 116n Ua T ^69 r V o a TE REQUIRIO .O. S. POiNl FPL ICMT T(AMb Tax code ORDEN DATE P C L 'S J x * L p o i o ] M I S D&-c C. r p " A & J / ' * M L \ J u ,a fm c r* M kJ PAYMENT TERMS / /o - x g - 7 7 1 FVA>RK ORDER V a u TH.NO. C. W SUFFIX \0 Q V r CCHAROC ACCOUNT 1 1T EM rV u . > . / c P R lC E /U N tT OF PURCHASE -- //fA "S %r OlSCOUN T Q U A N TITY Vr U N lT OF r DOW &P U R CH A S E CLASS CODE A) S ^ D ESC R IP TIO N fY l/ f i. -I-2-3>o o O L . c'7 2 -< ?f7 9 o t ~Tr?i C n u o n c ^CC-TlC I\c i C^ ( ' I S T / ) c /u ) ST 4s r~ - ro i /IsSPY. /Yijrl f-VbS&GL&niCiCi* } `5 `Z/JfAX//yiM Diax /aJ PPM /rfm ^TurZt? /o % r f / n t t m u / r t A .U / I/ / % xr* < A l 11 I I i >11T A I N I N (> N t C E S S A R Y D E P A R T M W M U A P I ' H ' i V A i I ' LJ T R E Q U I S I T I O N IN P L A N T M A I L . N O I'.NVI. I .i il 'l . H l Q u l R E O . 1> * s *.s . , , > i n u M * W t J ^.pp.o.io*. O l i i fioo s r - t d ij 0 0 90 N h HAS SUN CHIUID AND lAIIIS APPIOViD STANDARDS IOI: I. RAD IATIO N SO U R C ES 2 NOISE C O N TRO L 4. I N D U S T R I A L HYflMlf ('HN Tf' TRANSVAAL, INC. Information Regarding Products Manufactured The phenoxy h e r b i c i d e s , 2,4 -D , 2 , 4 , 5 - T , 2,4-D P, s i l v e x ( 2 ,4 ,5 - T P ) , and r e la te d s a l t s and e s t e r s , are c a ll e d s e l e c t i v e h e rb ic id e s which are w idely used in crop production and in the c a r e f u l management of f o r e s t , rangeland and i n d u s t r i a l ,_..uri)h_and a q u a tic s i t e s . They e ach ki l Implants by causing m alfunctions in p la n t growth p ro cesses.' Broad-leaved p lan ts are g e n e r a l i y s'us'cepfTlfl'e~to`'the" ptieTioxy-- .......' h e r b ic id e s . Most g r a s s e s , co n ifero u s t re e s and c e r t a i n legumes are r e la t iv e ly r e s is ta n t to t h e ir actio n. The phenoxy h e r b ic id e s , w h ile predominantly t o x ic to green p la n t s , are much le s s t o x ic to b i r d s , f i s h , i n s e c t s , mammals, r e p t i l e s , s h e l l f i s h , worms, fu n g i, and b a c t e r i a . When properly used, they do not occur in s o i l s and water a t l e v e l s which would harm anin.als and micro-organisms, they do not concentrate, in.ftwd-xhajjns^jand -- do not p e r s i s t from y e a r t o ' y e a r in cropland s. They are detected only r a r e l y in food and, when so found, ere present only in i n s i g n i f i c a n t amounts. ____________________ "A'lTTghly poisonous substance, a kind of d io xin c a ll e d TCDD (sh o rt fo r the compound 2 , 3 , 7 ,8 - t e t r a c h l o r o d i b e n z o - p - d io x i n ) , i s an unavoidable contaminant o f commercial s u p p lie s of 2 ,4 ,5 - T and s i l v e x ( 2 ,4 ,5 - T P ) . The amount present in c u r r e n t l y produced form ulations of 2 ,4 ,5 - T and s i l v e x , l e s s than 0.1 p a rt per m illio n ., i s not enough to a l t e r the t o x ic o lo g ic a l p r o p e rtie s of ch'ese~pre- parations nor to a ffe c t plants or animals in the environment or to endanger human l i f e . ------------------ --- \ I / J The phenoxy h e rb ic id e s are w id e ly used because they a re more e f f i c i e n t and u s u a lly l e s s hazardous and l e s s i n ju r io u s to the environment tnan a lt e r n a t iv e methods. The use of such chemicals is a f a c t o r ; i n re ducing the co st of a g r i c u l t u r a l crops and t h e i r use in f o r e s t , rangeJLand-and non-crop s itu a tio n s provides_additional savings. Dalapon, the name fo r t e c h n ic a l 2 , 2 - d i ch lo ro p ro p io n ic a c i d , i s as the sodium s a l t in water s o l u t i o n 'f o r thereon t roT~o~f~-annual p eren n ial...g ra sses. fI t k i l l s g ra sse s by absorption through roots and leaves causing m alfunctions of growth. While i t i s not r e a d ily degraded in p l a n t s , i t leaches into s o i l and i s r a p i d l y and completely broken down bv m icrobial a c t io n . ? n Hr. Jarrs>*' scutna Di ree tor,i'.Air Division State of Ar:<ansas Deoar cment of Pollution 3001 Nati ona I Dri ve Littl e Rock, AR ynn-nc Dear Mr. Scut ,na;;; enclosed wi t.n C.1"!Z atta ' sra 3a`/z ' c a'ecas a~ inform raw materials arc a-- j Z Z 'tnUT act_rai" \; 'ansvaa; , - "ne Rather tn.an at*7--I1CZ Z ' Z c tace ':. wnic.o mi gn someth'ng , r z z o :-- ;1---t aaar to ha-'a;; copy some puoi' c z nif :raa:i on The retort ant~ ~ z ri '"he Pher.cxv Hera-:cides" r 3c2PI"t]v mv'. Council for Acri cu ;"ur31 Sc'enee ano 7eennoi cav ;A3IA pJ r o v e e s a general d is c u s s io n . These cages are supo!amentad by mater i al an in d iv id u a l pnencxy h eroic* css taxer -nom 'He roi cio Handbook of che Weed Scien ce S o c ie ty of -nee c a . " h ir e Eoi c io n . 1974. Information on the various cnemioa's usee in the manuraccura c - produces at t h i s p la n t i s reproduced from "Dangerous P ro p e rtie s of Inc us t r i a l M a t e r ia l s 1' by N. Ir v i n e S a x . Fcurcn E d i t i o n . 1973 'Van Mcscrane Reinhold Company'. Also in c lu d e c *s ; cooy a f our method ~a~ are :eterm*nation of TCDC in 2 .4 ,5 - T a c id . Ui fi> A fte r you have had an ooccrcur.icv ca ac aver th is n a t a r i a l , ana esoeci i f more inform ation i s desi reo, we wou 3a aporeci aca K anv or of i t with you a t veur ccnvenienca. With re sp e ct to 2 ,4 ..5 -7 . a report ,-tooerc Hasnes; :nc. and seme inform ation from Weeos : ocav ana -arm unem*ca: s snou: be ar interese. 18806 Mr. J a r r e l l Southall Department of P o llu t io n Control and Ecology March 15, 1976 Page 2 Irf my opinion much "scare -head" informatiorv-has.,been extant about TCD-- ^ and the use._of, .2 ,4 , 5 -T. ''A report from the National Academy of Sciences states in conclusion that: "The Committee could fin d no co n clu sive evidence of a s s o c ia t io n between exposure to h e rb ic id e s and b irth d e fe cts in humans. A v a ila b le records of two major Saigon h o s p ita ls and ev alu a tio n of records in a t h i r d , as f a r as they go, showed no c o n s is te n t pattern of a s s o c ia t io n between r a t e s of congenital malformations and annual amounts of h e rb ic id e s sprayed. The Committee recognizes however that the material is not adequate for d e fin ite conclusions." I t i s of i n t e r e s t to note in t h is regard that there were no reports of chloracne from persons interviewed by the Committee, although q u a lif ie d medical p a th o lo g ists who have studied TCDD and chloracne b e lie v e that the f i r s t symptoms r e s u l t i n g from exposure to TCDD by humans is the m anifestation of chloracne on exposed portions of the body. Sincerely, TRANSVAAL, INC. AES:ew Enclosures (6) A. E. Si dwell' ' Director of Research, Emeritus 18807 TO: ALL VERTAC EMPLOYEES 0000103 d a t e : ( December 12, 1984 FROM: c . P. Boraar, Jr. CC: SU8JECT: Year End Summary The same excellent momentum and effort which allowed us to meet our Profit Plan for 1983 set the stage for Vertac's continued success in 1984. We have made hard fought but sustained progress throughout.the year, and I want to outline for you some of the obstacles and opportunities which we have faced together and some of the accomplishments which we have made. PlUKQjaSS-- ----------- -ertac's 1983 acquisition of Dow Chemical Company's formulated phenoxy_ usiness gave us the o_pportuni ty to capture" a" dointhant-- phenoxy"market share in 1984, although other companies seeking to capture the same market share created lower than hoped for prices. When Dow failed to furnish sufficient technical phenoxies to supply our customers, we reacted immediately by supplying the necessary funds to rehabilitate and restart the Jacksonville plant and bring it up to full capacity. In fact, within three months after this effort began, we were setting new production records. The exceptional efforts and teamwork at Jacksonville helped us to avert a major marketing disaster and maintain Vertac's credibility as a principal supplier of 2,4-D products in the United States. POTASSIUM NITRATE We have had an almost unprecedented opportunity to excel in the area of potassium nitrate and chlorine. Both of these products have been sold out since the beginning of the year, and we have been able to increase prices to very attractive levels. The potassium nitrate complex has made an excellent contribution this year; and if we had been able to produce at past production levels, we could have substantially exceeded our Profit Plan for this year. Unfortunately, production for the first half of the year was only average; and we have lost a month's production in the second half due to plant problems, creating difficulties for many of our customers. We hope that we have solved the problems associated with this unit and look forward to taking advantage of this unique opportunity in future: months. I PROPANIL AND CUSTOM MANUFACTURING Many of you are aware of our 1981 litigation which allowed Vertac to benefit from the Rohm and Haas propanil patent. This patent was overturned by the; Courts in 1984, resulting in a significant drop in propanil pricing s W V? \S and reducing our profit margin by a third. Fortunately., this loss in profits has hr-on offset by the addition of other important contract manufacturing projects at West Helena and Vicksburg, and we expect to add several new custom projects in the next few months. KVJb -JJ2 2 -P K J-? JL Another major .item for Vertac was the EPA litigation over Jacksonville. Vertac has spent millions of dollars and several years of effort to correct past problems at the site and, in 1984, set forth a proposed final remedial plan based on the last two years of studies. Although El'A had earlier approved this plan in principle, a change in the bureaucratic structure caused a reversal of KPA's position. This was not because our plan was inadequate scientifically, but simply boause they felt it to be politically desirable to see us spend mo..e money. Vertac challenged EPA in Court and, after a very major battle, won the Court's approval to proceed with our remedial plan. While on the one hand this was a great victory for Vertac, the implementation of.the'remedial'plan -is. a very costly process which will continue .into '1985. Fin/?ICTI!G ,, - We were-succesful in increasing Vertac's bank credit line from $14 million to^.$20 million while reducing our interest rates. This, additional N\ ^borrowing power has allowed us to continue to expand our business base and to handle a severe overrun in capital spending at Jacksonville and \ Vicksburg. The ability to obtain this financing is an example of the j renewed confidence in Vertac as a result of our more recent performance. Tilth lave been nrhaj-^Hir-rrirF^nt- achievements -too numerous to mmvtio detail here, including major new advancements inemployee safety. While we cannot be certain what our final year-end,results will be, we are confident that with good production and continued strong sales in December, we can meet or exceed our 1984 Profit Plan. As I am sure you know by now, there is a direct relationship between profitability and the income and benefits afforded to each of us at Vertac. Accordingly, I am pleased to announce that, effective December 3, we are increasing wages for our hourly employees by six per cent. Further,.`during the next month we will review the individual performance of our salaried employees (exempt and non-exempt) with the goal of making appropriate merit increases in the three to: seven percent range in January. In this action we will be returning almost a fourth of Vertac's 1984. profits to our employees through increased wages and benefits in 1985. As a member of the Vertac team, I hope you feel pride in the progress which we have made and confidence in our potential for the future. We are constantly seeking out new ventures which will strengthen our present position and further expand our future opportunities. I look forward to informing you as these new ventures are finalized. Meanwhile, please accept our sincerest appreciation for your continued contribution to the success of Vertac and our very best wishes for a Happy Holiday Season and a mutually Prosperous New Year. CPB:ap ft' \ TO: ALL VERTAC EMPLOYEES 0000103 o a t e : ( December 12, 1984 from : c. P. Botnar, Jr. CC: SUBJECT: Year End Summary The same excellent momentum and effort which allowed us to meet our Profit Plan for 1983 set the stage for Vertac's continued success in 1984. We have made hard fought but: sustained progress throughout, the year, and I want to outline for you some of the obstacles and opportunities which we have faced together and some of the accomplishments which we have made. Pl^jjPXIES rtac's 1983 acquisition of Dow Chemical Company's formulated phenoxy usiness gave us the opportunity toic^tnre A dominant phenoxy market share in 1984, although other companies seeking to capture the same market share created lower than hoped for prices. When Dow failed to furnish sufficient technical phenoxies to supply our customers, we reacted immediately by supplying the necessary funds to rehabilitate and restart the Jacksonville plant and bring it up to full capacity. In fact, within three months after this effort began, we were setting new production records. The exceptional efforts and teamwork at Jacksonville helped us to avert a major marketing disaster and maintain Vertac's credibility as a principal supplier of 2,4-D products in the United States. POTASSIUM NITRATE We have had an almost unprecedented opportunity to excel in the area of potassium nitrate and chlorine. Both of these products have been sold out since the beginning of the year, and we have been able to increase prices to very attractive levels. The potassium nitrate complex has made an excellent contribution this year; and if we had been able to produce at past production levels, we could have substantially exceeded our Profit Plan for this year. Unfortunately, production for the first half of the year was only average; and we have lost a month's production in the second half due to plant problems, creating difficulties for many of our customers. We hope that we have solved the problems associated with this unit and look forward to taking advantage of this unique opportunity in future months. PROPANIL AND CUSTOM MANUFACTURING Many of you are aware of our 1981 litigation which allowed Vertac to benefit from the Rohm and Haas propanil patent. This patent was overturned by the Courts in 1984, resulting in a significant drop in propanil pricing 18890 and reducing our profit margin by a third. Fortunately, this loss in profits lias br-vn offset by the addition of other important contract manufacturing projects at West Helena and Vicksburg, and wa expect to add several new custom projects in the next few months. KPAJj/jJdVi/flOW Another major item for Vertac was the EPA litigation over Jacksonville. Vertac 1ms spent millions of dollars and several years of effort to correct past problems at the site and, in 1984, set forth a proposed final remedial plan based on the last two years of studies. Although EPA had earlier approved this plan in principle, a change in the bureaucratic structure caused a reversal of KPA's position. This was not because our plan was inadequate scientifically, but simply bcause they felt it to be politically desirable to see us spend w-. e money. Vertac challenged EPA in Court and, after a very major battle, won the Court's approval to proceed with our remedial plan. While on the one hand this was a great victory for Vertac, the implementation o--fetra'l'emedial plan-- very costly process which will continue intcT'1985. FIIa*I'CTlIG ,, We were-succesful in increasing Vertac's bank credit line from $14 m" lion to .$20 million while reducing our interest rates. This additional iorrowing power has allowed us to continue to expand our business base aril to handle a severe overrun in capital spending at Jacksonville and Vicksburg. The ability to obtain this financing is an example of the renewed confidence in Vertac as a result of our more recent performance. There-- have be^n m-hftx-wirffffFanr achievements -too numerous to imj. detail here, including major new advancements in employee safety. in While we cannot be certain what our final year-end, results will be, we are confident that with good production and continued strong sales in December, we can meet or exceed our 1984 Profit Plan. As I am sure you know by now, there is a direct;relationship between profitability and the income and benefits afforded to each of us at Vertac. Accordingly, I am pleased to announce that, effective December 3 we are increasing wages for our hourly employees by six per cent. Further, during the next month we will review the individual performance of our salaried;employees (exempt and non-exempt) with the goal of making appropriate merit increases in the three to seven percent range in January. In this action we will be returning almost a fourth of Vertac's 1984. profits to our employees through increased wages and benefits in 1985. As a member of the Vertac team, I hope you feel pride in the progress which we have made and confidence in our potential for the future. We are constantly seeking out new ventures which will strengthen our present position and further expand our future opportunities. I look forward to informing you as these new ventures are finalized. Meanwhile, please accept our sincerest appreciation for your continued contribution to the success of Vertac and our very best wishes for a Happy Holiday Season and a mutually Prosperous New Year. CPB.-ap i i i n r i f m i * i r n 'V * '- iif . rn*nr**r.r<# * M l f f U T f H C O t U AUT '> n / \ i!n \ ( I ' i M i i u j i ' 11? > 'r.Hi 'iM nit r.K-.v v.^y. lir i-ml-er 17, 19^/* .'I. . .',. 1W"'*l.il . ti i>>*r "!. I'- F ! pri. r i r wer 1.>urn1 ft3 i on r i<*r ` cto n , ;J. <. omit r . r . T 'e e d a le : You a re -/ell aware that thei a i s in c re a sin g in te r e s t i.-i toi^ y over th use of p e s tic id e s and h e rb ic id e s . Kany In q u ir ie s on t h is su b je ct cone to the Deuartaent o f H e a lth , and In view of our lack of inform ation your help and advice i s needed. Th o ; in I n t e r o f H e a lt h , The H on . fJe o o V 'fl h. D um ont, . . j . , h j:; <.*:.'! rn* in arrange meeting in fre d e ric to n so t in t the I on ir i tMeta und O rganizations usin^ p e s tic id e s and h e rb ic id e s . >'i i v i t ; so"!*- j iris-J Ic tio n over t h e ir use, .-.ay be tro iii'h t lo - j- \ ' - r ii r- 'M .-ii otm. r i t Is f e l t that your 0r *ani2at ion .'"i ! i fi/iv*' i v il'M i N* co n trib u tio n to make to the d is c u s s io n s , the if t .-) laoee nf t* ; ese nt a 1 1vi: would be ;'r * a t ly a . ,.rec 1ated. r i 1(> w> i p - not bound by a n y S p e c i f i c t e r n s o f r>- F**r-nr- , ./on i d l i k t * I n a r r i v e at. rHCOfv.i.'>ndat Io n u r on i c r . -- i i~- rr,-.\ j I-.. r:/| |. . i n nrder t. > expi-.l It e tt.e v - :n r n f ' i. r r - . i ! i , n it*'t O'li lit ii' of y mr iut i flit in * :. .-u lie c t i : r ,*ies', e-.t f o r i i s r u s r .in n ,/m ,ii)? P 5 in c o n ^ i t t e e . I! 'll iJ-: lift- r.D ;ir<aifii u,n nt thin tir-, .v . I .i --f-1 to h p ir fron y'>u /m s-vin as p o s sib le , sn tr.a t our i !.- r-in I 1** s c h e d u le d J ' t r i n r t h e f i r s t week o f J jn u r y . Vourr: very t r u ly , '7 . V ( u U `{' i 1 .lwyn J . Cameron, '. l'.--. j i * i-t.or <i H try '..'v i n**Min>: j i v i i i o n 18892 VERTAC CHEMICAL. CORPORATION 24th Floor 5100 Poplar Memphis, T N 38137 901-767-6851 MEMORANDUM TELEX 53927 To: All Jacksonville Plant Employees Subject: Shift in Production Emphasis August llf 1983 Effective September 1, 1983/ we will shift our emphasis at Jacksonville from the operation of the primary 2,4-D process ing unit to the full-scale utilization of the 2,4-D waste recovery unit. This will necessitate a shutdown of certain production facilities associated with the primary processing unit. Since we are uncertain as to when these facilities will come back into full utilization, some reduction in personnel cannot be avoided. We will utilize as many employees as possible in the operation of the recovery unit and in the research projects which are being transferred to the Jackson ville laboratories. We will give principal consideration to senority and acquired skills in filling these positions. In the interim, all hourly employees affected will receive at at least two week's notice plus accumulated vacation pay and the following severance pay upon completion of their duties throughout the notice period: Date of Employement Amount of Severance After January 1, 1983 After January 1, 1978, but prior to January 1, 1983 Prior to January 1, 1978 1 week's pay 2 w e e k 's pay 3 w e e k 's pay Salaried employees affected will receive severance pay based on age and tenure in accordance with Company policy. Again, in accordance with Company policy, all affected personnel will be asked to an take an.exit physical. If your position is to be changed or you are to be affected b this layoff, you will be notified by August 15, 1983. As you are aware, this plant has come under unwarranted pressure as a result of newspaper sensationalism-and distortions---which lave frightenedjnany-- Gi-fei-z-ens-i-- I-t-- is our sincere hope that over the next several months we caji--convince the residents "of-rJacJcson- ville that V e r t a c 1s present tnd future -operations pose no threat to the unity s o"t H ^ t yo u can continue To those employees whose layoff cannot be avoided, you have our Sincere regrets. We will attempt in every way possible to assist you in locating new employment. When circumstances permit us to increase production levels, we hope that you will^want to return to Vertac, R A G :ap V< p o V INTERNAL CORRESPONDENCE TO: ALL VERTAC EMPLOYEES d a t e : December 12, 1984 FROM: C. P. Bomar, Jr. CC: SUBJECT: Year End Summary The same excellent momentum and effort which allowed us to meet our Profit Plan for 1983 set the stage for Vertac's continued success in 1984. We have made hard fought but sustained progress throughout the year, and I want to outline for you some of the obstacles and opportunities which we have faced together and some of the accomplishments which we have made. pire?:oxiES Vertac's 1983 acquisition of Dow Chemical Company's formulated phenoxy business gave us the opportunity to capture a dominant phenoxy market share in 1984, although other companies seeking to capture the same market share created lower than hoped for prices. When Dow failed to furnish sufficient technical phenoxies to supply our custorrers, we reacted immediately by supplying the necessary funds to rehabilitate and restart the Jacksonville plant and bring it up to full capacity. In fact, within three months after this effort began, we were setting new production records. The exceptional efforts and teamwork at Jacksonville helped us to avert a major marketing disaster and maintain Vertac's credibility as a principal supplier of 2,4-D products in the United States. POTASSIUM NITRATE We have had an almost unprecedented opportunity to excel in the area of potassium nitrate and chlorine. Both of these products have been sold out since the beginning of the year, and we have been able to increase prices to very attractive levels. The potassium nitrate complex has made an excellent contribution this year; and if we had been able to produce at past production levels, we could have substantially exceeded our Profit Plan for this year. Unfortunately, production for the first half of the year was only average; and we have lost a month's production in the second half due to plant problems, creating difficulties for many of our customers. We hope that we have solved the problems associated with this unit and look forward to taking advantage of this unique opportunity in future months. PROPANIL AMD CUSTOM MANUFACTURING Many of you are aware of our 1981 litigation which allowed Vertac to benefit from the Rohm and Haas propanil patent. This patent was overturned by the Courts in 1984, resulting in a significant drop in propanil pricing fc 'h .id reducing our pi.of it maigin by a third. Fortunately, this loss in profits has bt-en offset by tbe audition of other ir.por 1ant contract r'.luf-jCturing projects at Vest Hilor.a and Vicksburg, ad re e'-.'-jct to arid several new custom projects in the next few months. E?A L ITIGATION V/ Another major item for Vertac was the EPA litigation over Jacksonville. Vertac has spent millions of dollars and several years of effort to correct past problems at the site and, in 1984, set forth a proposed final remedial plan based on the last two years of studies. Although EPA had earlier a^pievc-d this plan in principle, a change in the bureaucratic structure caused a reversal of EPA's position. This was not because our plan was inadequate scientifically, but simply because they felt it to be politically desi.'. ible to see us spend more money. Vertac challenged EPA in Court and, after a very major battle, won the Court's approval to proceed with our remedial plan. While on the one hand this was a great victory for Vertac, the implementation of the remedial plan is a very costly process which will continue into 1985. FINANCING We were succesful in increasing Vejrtac's bank credit line from $14 million to $20 million while reducing our interest rates. This additional borrowing power has allowed us to continue to expand our business base and to handle a severe overrun in capital spending at Jacksonville and Vicksburg. The ability to obtain this financing is an example of the renewed confidence in Vertac as a result of our more recent performance. There have been other important achievements too numerous to mention in detail here, including major new advancements in employee safety. While we cannot be certain what our final year-end results will be, we are confident that with good production and continued strong sales in December, we can meet or exceed our 1984 Profit Plan. As I am sure you know by now, there is a direct relationship between profitability and the income and benefits afforded to each of us at Vertac. Accordingly, I am pleased to announce that, effective December 3, we are increasing wages for our hourly employees by six per cent. Further, during the next month we will review the individual performance of our salaried employees (exempt and non-exempt) with the goal of making appropriate merit increases ir the three to seven percent range in January. In this action we will be returning almost a fourth of Vertac's 1984 profits to our employees through increased wages and benefits in 1985. As a member of the Vertac team, I hope you feel pride in the progress which we have made and confidence in our potential for the future. We are constantly seeking out new ventures which will strengthen our present position and further expand our future opportunities. I look forward to informing you as these new ventures are finalized. Meanwhile, please accept our sincerest appreciation for your continued contribution to the success of Vertac and our very best wishes for a Happy Holiday Season and a mutually Prosperous New Year. CPB:ap 18895 i 1 <I i 1 i ;f . . fZ -2 -U ' -. attachment y Sapt*br h / l M J \ . ' w b W i * { . . l" 9 Calaael t. C. Sba4 {SAO) t i r K o n u a f A ir Fore* A c m p ic i Faal* ' ! Kelly Air Farce U i t , T o u 74241 1 S u r Calaoal SAaarft V k m WtB i M c kU a tSa algn, n n r t i ni aparada* r ( a 1,000,000 sa lla f ( j u r Orante" plae a t he Oovarnaaat abanica1 plaat a t Vallen S erlas, SlasM iri. . v ' 4 141 ic t lafana w chic w kav W vli y . C. K r m , C t la u l, I Cerp* f la tin e a n la t e m C ity, JUaceuri', tkat va 4a aat iatan | ta k il aa thalr l a l l t l u t i n Ae. W A A M M -C O aj, tfateJ Saptoafcar 7 1947. . r f t k u U raaaaa far aur M i i i n 1 Sua aa e r it f c a l foctars M t li s e l V. 4ala: . * ,s "J4e tina ll a t t e l far auAsieair-a a f 4 li , i , 1947 ta ,, **r Octavar 12, 1947, 1 aat e ; '. t i r f k U i an a prejact f tU i aapiicuia. * i H* preacatatina e f slca ra a tlec u l & i a t loaatle*# ather. tban Cal4 Serias w r t preclulel k K a u t a f tkc .tiac llevo* far preparativa a f a reapenaiva k li la arv*r ta y*r e v lic lt a t ln a . *V v ou ll lik e te aua i th is f la t , a* fellows* ilw r roa** far a a t f t n n t l t j a 414 a t 1 . Sha V allas Seriar s it * . a;J i t la Aa U a iv en ity a f fSiaaea'l E^perlavaal Fara ar>4 tka A|uat Ituth t * M m , ) r n a t i ta Buck f a U u n i ta the plant U fa la s4ec at, in ee*e a f aa accidental ralaata a f product /roa tkc Orante F iant.2 2 . 14 raqvlramnt a f 13 aatkt tart p and f u l l apara tien la I t ontke un the W lim Sprint a lte appear* alaoat iap ciiik l to w at vitiwvt a teu iv e w a m m .j 3 . 14a la4or cltw atiea is tW S t. Lauta arca wmU praacatj ORANGE - 8 Million Gallons/Year (Basis: 6.0 million gallons/year estimte doted March 17, 1967) 27.600.000 #/yr. 21, 000,000 V y r. 20.200.000 V y r. 26.400.000 V y r. 27.600.000 V y r. 64.500.000 V y r. 2.300.000 Vmo. 1.750.000 */mo. 1.685.000 Vmo. 2.200.000 Vmo. 2.300.000 Vmo. 5.370.000 Vmo. , (2,000 gal.) (2,000 gal.) ( 750 gal.) (3,000 gol.> (3,000 gal.)/ (4,000 gal.) 17.000 M tch 20.000 #/batch 2,000 VkatcH 4.600 Vkatetr 4.600 ^/tatcHy 16,500 ^/tatch :ors for 8 million gallons Orange: Basis: Government Specifications - by volume 4 million gals. Bu-D @ 1.245 s p .g r . = 10.35Vgal. 4 million gals. Bu-T @ 1.325 sp. gr. = 11.02Vga! D * 1.245 x 8.33 x 4,000,000= 41,500,000 Vyear Butyl "D" Ester T= 1.325 x 8.33 x 4,000,000 = 44,200,000 V year Butyl "T" Ester 85,700,000 Vyear Total Mixed Ester Ester "D " Acid "T" Acid 6MM 8MM 64,500,000 # mixed x 1.328 85,700,000 ^ mixed 26,400,000 # (2.44) = 85,700,000 = 35,100,000 V y r . 2.44 j 27,600,000 9 (2.34) = 85,700,000 = 36,600,000 V y r . 2.34 54,000,000T 71,700,000 V y r. Total "0" and "T" Acid Ester Acid D T 85.700.000 Vyear mixed 50/50 by weight. 71.700.000 Vyear mixed "D"and "T". '35,100,000 Vyear 36.600.000 Vyear TCP = 20,200,000 # x 36,600,000 * T @ 8 M? 27,600,000 # T @ 6 M2 26,700,000 V year TCP DCP = 21,200,000 # x 35,100,000 * D @ 8 M? 26,400,000 * D @ 6 M2 \ MCA = 27,600,000 # x 71,700,000 # Total Acid (8M2) = 54,000,000 * Total (6MZ) -3 - 28.200.000 Vvear DCP 36,600,000 Vyear MCA . f Oronge ~ MCA ?6 ,6 00,000 9/yr. = 3,050,000 '/m o. = 102,000 '/day = 4,250 '/H r. 3,050,000 'MCA/mo. 17,000 * MCA/batch 720 hrs ./mo. 65 hrs./batch/unit 180 Batches/month 11 BatchesAlnit/Month Chlorinators: @ 2,000 gallons ( @ 4,000 gallons 180 Batches/Month 11 Batch/Unit/Month 16.4 Unite on MCA 8 Unite?) 2 - Rows of 8-2,000 gallon glass-lined, jacketed agitated reactors. 7 - Chlorinating each bank - 1 prechlorinating. 2 - Weigh tanks - acetic acid with plate coils, glass-lined. 16 - Primary condensers. 16 - Secondary condensers. 2 - Weigh tanks - phosphorous trichloride - stainless. 2 - Chillers - one for each chlorinator bank. 8 - Pumps - 1 for each 2 chlorinators. 2 - Absorbers - 1 for each 8 chlorinator tow. -4 . Orange - PCP . 28,200,000 */yr. * 2,350,000 % o . = 78,200 #/d ay = 3,260 #/Vir. 2,350,000 > DCP/mo. 20,000 * DCP/batcfT 117 Batches/month. 720 Hrs./mo. 60 Hrs./Batch/Unit 12 Batches/Unit/Month 117 Botches/Month = 12 Batches/Unit/Month 9#8 -- Say 10 Units on DCP @ 2,000 gai. 2 - Rows of 5-2,000 gal. glass-lined, jacketed, agitated reactors. 2 - Absorbers - 1 for each bank of 5 chlorinatcrs with temperature controls on makeup water. 5 %Pumps - 1 for each 2 chlorinators. 2 - Chillers - for chilled tempered jacket water, 1 for each 5 units. Also chilled tempered water on absorber condensers (2) 2 - Weigh tanks - 2,000 gals, glass-lined with plate coil vent tied into absorbers. Oronge - Chlorination - Qjtsde Tanks Chlorine; 58,500,000 *C l9/yr. = 4,880,000 #/mo. = 162,000 */day / ' '' /, 162,000 ~ 81 tons/day = 8 1 = 1.5 cars/day (55 tons/car) 2,000 55 Use railcars to store chlorine Vaporizors: 8 - 2 for each of 4 chlorinafor banks Phenol: 1,500,000 ^/mo. = 17.3 cars/mo. @ 10,000 gal. each 4 - 12,500 gal.-glass Chemstor storage tanks - (50,000 gal.) Acetic: 1,700,000 to 2,000,000 ^/mo. = 25.3 cars/mo. @ 10,000 gal. each ; (Mix) 6 - 12,500 g a l . - (75,000 gal.) / 5- 1 J '^.f DCP: 28,200,000 #/yr. = 2,350,000 */mo. = 78,200 */day = 3,260 #/W . (l 1,6^/gal. 2,430,000 gal./yr. = 202,500 gal./mo. = 6,750 gal./day = 280 gal ./hr. 4 - 12,500 gal .-glass lined tanks (50,000 gal. = 7.4 days) 1 MCA: 36,600,000 #/yr. = 3,050,000 #/m>. = 102,000 */day = 4,250 #/hr. T m #/ g l.) 3,180,000 g al./yr. = 265,000 gal ./mo. = 8,800 gal ./day = 366 gal./W . 4 - 12,500 gal.-glass lined tanks (50,000 gal. = 5 .7 days) j' ! HCI: 20 (32%) - Average from MCA " " DCP = 122,000 ^/day = 105,000 #/day _________ 227,000 */day r-. 227,000 = 23,500 gal./day containing phenolics, etc. 240.000 gal. (6 - 40,000 gal) Rubber Lined Tanks 125.000 gal. (10 - 12,500 gal.) Glass Lined Tanks 32% HCI purchased = 415,000 gals./yr. = 415 T/C's = l.lT / C p e r d a y Acetic Anhydride:*2 Phosphorus Trichloride: Brine: For Secondary MCA condensers 2 - 4,000 gal. wood (1 - for each chiller) Orange ~ Chlorinotion - Outside Tanks (Confrcf,) Tempered water: For phenol condensers 2 - 4,000 gal. wood (1 - for each tempered system) Unloading Stations - Chlorination 3 - Chlorine Tank car 1 - Acetic Tank car 1 - Phenol Tank car 1 - HCI Tank Car 1 - Acetic anhydride tank truck -7 - Oronge ~ TCP 26/700, QOQf/yr. = 2,250,000*/mo. = 74,500*/day = 3,100^/hr. 2,250,000^/mo. = 1,110 Botches/month = 37.2 botchcs/doy 2,000^/batch 720 Hrs./Mo. = 90 bafches/unit/Mo. 8 Hra./batch/unit Dechlorinators: T, T10 botches/Mo. = 12.4 units on TCP 90 batches/unit/Mo. 14 " Dechlorinators (3 750 G a l."nickel clod, jacketed, agitated Shell: 350 psig. oper. press; Jacket: 150 psig. oper. press. 3 Rows * 4 dechlorinators " barricaded with rupture disc vent liner tCB (Ground) = 88,000^/day = 440 Drums @ 200^ = 147/shift NaOH (Flake) = 53,000^/day = 110 drums @ 400^ 110 drums @ 100^ MeOH (fresh make"up) = 5,400 Gal./day 2*25,000 G a l. Alcohol Storage " Drum handling facilities for dechlorinator charging. 3 " 10,000 G a l. NaTCP (dirty) Storage "304 S/S, agitated w/coil. 2 Hold Tanks " 6,000 Gals, with vent condensers 2 Stills " 3,000 G a l. Monel clad, agitated, jacketed (150 psig) still pots " 316 S/S column 2 Still condensers 1 Alcohol Hold Tank * 304 S/S I ^a rn< n--- Orange r Acid 2,4,5-T 35,100,000 #/yr. 2,930,000 #/mo. 97.500 #/day 32.500 #/shift 4,050 #/hr. 36,600,000#/yr. i 3,050,000 #/mo.; 102,000 #/day 33,800 #/shft 4,230 #/hr. ; !' I 10 " 3,000 G a l. brick lined, agitated (Titanium) Reactors 5 Units on D and 5 Units on T " normally Weigh tank and piping arranged for flexibility for ratio of units on D and T. Basis : Approx.95% operating time. 8 " 4,000 G a l. Glass Lined, agitated, jacketed crystallizers 2 ~ Refrigeration units " i 2 " 10,000 G al. Slurry Hold Tanks " heavy duty " agitated 5 " 6,000 G a l. Slurry Feed Tanks ~ heavy duty " agitated " jacketed 4 " Brine Extraction Column ( 1 for D and I for T ) Haveg 4 " Brine Storage Tanks " 10,000 G a l. Haveg Independent weigh tanks for each reactor 10 " NaTCP weigh tanks ~ 304 S/S 10 " DCP weigh tanks glass lined " jacketed 10 - MCA weigh tanks " glass lined " jacketed 10 ~ caustic weigh tanks ~ steel 6 " recycle liquor measuring tanks " glass lined 2,000 gal. 6 " HCL measuring tanks " Haveg 2 * brine solvent separators ~ 1,000 G a l. " glass lined 10 ~ Centrifuges 48 in. ** 316L S/S , Kynar Coated 5 * Blenders 4 " Conveyor/Dryers (for flexibility between D&T 316 S S / 2,000 - 2,500#/hour 5 " Filtrate Tanks (1 for each 2 centrifuges) 4 00 - Tote Bins (97,500*/day x 7 * 682,000#/Wk. 195 Tote Bins @ 3,500# ) (102,000 #/day x 7= 714,000#/Wk. = 204 Tote Bins @ 3,500#) Aluminum " 90 cu. ft. capacity - 9- Oronge Ester 85,700,000 '/ y r. 7,140,000 #/mo. * 238,00o//day * 9,900 @330 days/yr. 265,000 ;*/day * 11,000 #/ W ' j 10 - 4,000 gal. 316 L S/S, agitated, jacketed, vacuum esterifiers 5 - 4,000 gal. 316LS/5 " " preesterifiers j j. 2 - 4,000 gal. Glassed lined agitated, jacketed recovered acid esterifiers 2 - Vacuum systems (for each 5 esterifiers) ' i 10 - Karbate esterifier condensers j i; 2 - 30,000 gal. Butanol storage tank ji 265,000 ^/day BuE-Mixed 132.500 * /day Bu-T ester = 35,400 132.500 #/day Bu-D ester = 35,000 70,400 ^n-Butanol/day 70,400 - 10,500 gals. n-Butanol/day 6.76 5 - 10,000 gal. Spent Butanol Storage - Sreel (1 for each 2 esterifiers) 4 - 20,000 gal. - Butyl D Ester Storage - steel w/coil 4 - 20,000 gal. - Butyl T Ester Storage - steel w/coil - 10 - Oronge ~ Solvent Cleon Up I i NaTCP clean up 4 " 6/000 G a l. agitated tanks NaTCP clean 6" 10,000 G a l. agitated w/plate coils 2 " D " Clean Solvent 2 - D " Spent Solvent 2 * T " Clean Solvent 2 * T - Spent Solvent 4 - Separator - Decanters 4 - Clean Up Tanks 15,000 Gal." J! 15/000 Go!.- ! 15/000 G a l.- j: 15/000 G a l.- 6 /000 G a l. -- 6/000 G a l. agitated " heavy duty Unloading Stations 1 " Toluene 1 " Methanol 1 - Butanol - 11 - Oronge Waste Bosis: 85/700,000 9 mixed D and T Butyl ester/year 61,000/000 9 NaOH (100%)/yr. N aC I- 90,000,000 9 NaCI/yr. 7,500,000 9 NaCI/mo. 250,000 9 NaCI/day 10,400 9 NaCI/hr (5.4 tons/hr.) Glycollic Acid 5,500,000 V y r . = 458,000 9/mo. = 15,300 9/day = 638 9f a . Oxolic Acid 129,000 9/yr. = 10,800 9/mo. = 360 9/day = 15 9f a . Acetic Acid 1,100,000 9/yx. = 91,800 Vm o. = 3,050 9/day = 137 9/hr. plus all acetyls carried from plant generated HC1. Still Bottoms - Toluene Recovery Still TTSSTOCT^/yrl = T2870O^/mo. = 4,250 9/day = 177 9f a . \ Still Bottoms - Methanol Still 9 9 M 0 ^ T y r r ^ i r , 5 0 0 Vm o. * 2,750 9/day = 115 9f a . Combined Bottoms: 7,000 V day = 292 9f a . Approximate composition 35% Toluene 32.5% TCP Anisole 13.0% Trichlorobenzene 19.5% Tetrachlorobenzene This would generate about 3,200 9/day HCI. By A . E . Sidwell 3/18/67 - 12 - 4L O %J \j o Oronge ~ Utilities Steam (Salt evaporation not included) Air Water ** make up Water ** Cooling tower Electric Gas Inert Gas ! ' i: 1' - Required for Orange ~ 8.0 ! I; i I' j i" Available at Weldon Spring 200,000 lb ./h r. 216,000 lb./hr. (240,000 lb./hr max.) 1,500 CFM 2,000 CFM 10,000,000 Gal ./Mo. 10,000,000 Gal./day (wells"treated) 20.000 GPM 9,000 KVA Liquid Propane 20.000 CFH Not Available - 13 - Orange - Services (Existing ot Weldon Spring, Missouri) Railroads - existing, may need minor additions Roads - adequate Office - adequate Cafeteria - adequate Shop - adequate Storeroom - adequate Warehouse - existing, may be too small and not convenient to process. Laboratory - existing but not available for Orange Locker - Change Facility - adequate - 14 - THE GAS CHROMATOGRAPHIC DETERMI `ATI Oil fsi OF 2,3,7,3-TETRACHLORODI BEMZO-P-DIOXIM , 4 ,5-TRiCKLOECPHEHOXYACET IC ACID '\.o- ^ > - ,5-T SUTYL ESTER, AMD 2 , 4 ,5 - 2-ETHYLHEXYL i ii.H // / ''Edward M. Ha rr is : August 13 , ]/j4 \\ TABLE OF CONTENTS Digest 1 Page O b j e c t i v e ............................................................... .... Re sults and Co nc lu si on s ................................ .......................................... L.lj Experimental Section ! I, i Reagents................................................................. .......................................... ;. i l Apparatus.......................................................................................................... 1.4! Procedure for Preli m ina ry Treatment of the Sample ( ! ) for 2 , 4 , 5 - T ......................................................................................................... 5 E x t r a c t i on........................................................................................1...........5 Alumina ColumnChromatography.................................... 6 Procedure for P re lim in ar y Treatment of the Sample (2) f o r 2 , 4 , 5 - T E s t e r s ..................................................................................... 7 S a p o n i f i c a t i o n ........................................................................................ . .7 E x t r a c t i o n . ................................................................................................. 7 FI o r i s i l Column Chromatography..................................................... . 8 Procedure for the Gas-Chromatographic Determination of 2 ,3 ,7 , 8 - T e t r a c h l o r o d i b e n z o - p - d i o x i n ...................................... ; .9 Results and D i s c u s s i o n ....................................................................................-10 Recovery of 2 , 3 , 7 , 8 - T e t r a c h l o r o d i b e n z o - p - d i o x i n ......................11- Recovery of 2 ,3 ,7 ,8 - T e t r a c h l o r o d i b e n z o - p - d i o x i n from F l o r i s i l Column Chromatography........................................................ .11 L i n e a r i t y of Response of the Ele ctron Capture D e t e c t o r . . . . 12 Li m it s of Dete ct io n ....................................................................................... 12 Graph of Response............................................................................................13 Typical Chromatograms................................................................................... 14 Objective This i s the report of an i n v e s t i g a t i o n to determine the '213,7,8- Tetrachlorodibenzo-p-dioxin (TCDD) content of 2 , 4 , 5 - T and 2 , 4 , 5 - T butyl and 2-ethylhexyl e s t e r s manufactured by T ran sv aal , Inc_._.a.t---- Jacksonville, Arkansas. !\ .. .. ... .......... :I \ The compound of i n t e r e s t , TCDD, may be produced as a by-product\ / in the manufacture of 2 , 4 , 5 - T , and i s of s i g n i f i c a n c e due to i t s , 1 / i alleged high t o x i c i t y to humans------------ ----------------------------------- -------^ The o b je ct iv e of t h i s i n v e s t i g a t i o n v/as to determine the amount / of TCDD produced in the 2 ,4,5^T_and i t s butyl'and 2-ethylhexyl e s t e r s manufactured, hv T r a n s v a a l , Inc_.____________________________________________ - Results"arid Conclusions t ' The a n a l y t i c a l method developed in t h i s i n v e s t i g a t i o n was based on methods by Dow Chemical Company, Hercules Incorporated, and D. A. Elvidge.^ Samples of 2 , 4 , 5 - T acid were di s s ol ve d in aqueous a c e t o n i t r i l e and extracted with hexane. The e x t r a c t s were concentrated and then analyzed for TCDD by gas chromatography using a flame i o n i z a t i o n detector. A nal ys is of samples of e s t e r s involved a pr eliminary s a p c n i f i c a t i c procedure followed by ex tra ct io n of TCDD from aqueous dimethylformamide 1 E lv id g e , D. A . , A n a ly st , 96, 721-727 (1971). !Pace 2 with hexane. The concentrated hexane e x t r a c t s of-'-the e s t e r s Iwere analyzed by gas chromatography using an el ec t r on capture d e t e c t o r . 1;l!' None of the samples of 2 , 4 , 5 - T acid and 2 , 4 .a.-'T'eiters examined : /- / / l.i - contained TCDD at a concentration g re at er tn.en/0.1 ppm./ EXPERIMENTAL SECTION Reagents n-Hexane Acetonitrile Aqueous A c e t o n i t r i l e E q u i l i b r a t e d n-Hexane Diethyl Ether Quality suitable for pesticide residue an al y se s. (Burdick and Jackson L a b o r a t o r i e s , Muskegon, Michigan) i ; Quality suitable for pesticide residue analyses. (Matheson, Coleman, and 3 e l ! ) Solution of 90.0 a c e t o n i t r i l e and 100 d i s t i l l e d water by volume. | n-Hexane saturated with the aqueous ac eto n itrile solvent. Quality suitable for pesticide residue analyses. (Burdick and Jackson L a b o r a t o r i e s , Muskegon, Michigan) <1 '-"n a 1004.4 Page 3 Chloroform Ethanol Methanol 25% Ether-Hexane Chloroform-Ether, 1:1 Double D i s t i l l e d Water N,N-Dimethylformamide Methylene Chloride Sodium S u l f a t e Potassium Hydroxide Ammonium Hydroxide: Water Sol utions Aluminum Oxide Fiorisi 1 Quality suitable for pesticide residue- anal ys es. (Matheson, Coleman, a n d ! B el l) :! !j I-I; Reagent alcohol. (Anderson La bor atories1, ; Ft. Worth, lexas) !j" i.! I! Anhydrous, Reagent grade (Mallinckrodt) 1 | A. C. S. Reagent Grade (Baker and Adamson) Sp ect ro q u ali ty Reagent (Matheson, Coleman, and B e l l ) Anhydrous, G r a n u l a r A. C. S. Reagent Grade (Mallinckrcdt) ! Reagent grade p e l l e t s (Mai 1inckrodt) ; 1:1 and 1:2 by volume (using 25:i NHLOH and double d i s t i l l e d water) Woelm, b a s ic ( c a t i o n o t r o p i c ) , A c t i v i t y Grade I PR Grade, 60/100 mesh (Supelco, I n c . ) : TCDD Reference Material - Obtained from D. F i r e s t o n e , U. S. Food and Drug Admin is tr ati on. TCDD Standard So l u t i o n : 2.5 milligrams of TCDD were d i s s o l v e d , with warming, in 10 ml of diethyl ether contained in a 25 ml volumetric f l a s k and adjusted to volume with ethe r. D i l u t i o n s were made, with .8 Page 4 I: I ;fj ' i ; 25% ether-hexane to y i e l d s o l u t i o n s containing TCDO at concentrations o f 20 ng per m i c r o l i t e r and 0.2 ng per m i c r o l i t e r . Apparatus ' j ;. I : II ' All glassware was cleaned in chroinic-sul f u r i c ac id mixture, washed with water, dried and rinse d with hexane p r i o r to use.; | i A Tracor MT-220 gas chromatograph, equipped with a flame ionizacin d et ec t or , an el ec tr on capture detector (with a 10 mCi Mi s ou r c e) , a 1-mV Honeywell E l e c t r o n i k 194 Recorder, and an In f o t r o n i c s automatic d i g i t a l i n t e g ra t o r , was used. Chromatographic Columns - Two s i x - f o o t g la ss columns of 2 mm i . d . were packed with 3 per cent 07-17 ( P i e r c e Chemical Company) ;0 n 80/100 mesh Chromosorb G (Johns-Manvilie Company) and conditioned at 250 C. for 24 hours before use. One column was attached to the flame i o n i z a t i o n detector and the other to the elect ro n capture detector. Operating Conditions The following operating conditions were used: (A) For 2 , 4 , 5 - T : o Detector temperature - 260 C. Recorder chart speed - 12 inches per hour C a r r i e r gas - Nitrogen ( P re p u r i f ie d grade) Column temperature - 200 C. o I n j e c t i o n port temperature - 250 C. C a r r i e r gas flow r at e - 30 ml per minute ` Hydrogen flow r at e - 60 ml per minute A i r flow r at e - 1.2 cu. f t . per minute : Page 5 `I It ;. ;'. |; jj Attenuation s e t t i n g s were adjusted to give at l e a s t a 25 percent f u l l - s c a l e recorder d e f l e c t io n for an i n j e c t i o n of 40 ng 2 , 2 j7,8-TCDD. (8) For the butyl and 2-ethyl hexyl . e s t e r s : ( El ec t r o n capture detector) ! j' Detector voltage - 12V ! !' ; ' Detector temperature - 230 C. '' Chart speed - 12 inches per hour C a r r i e r gas and purge gas - Nitrogen ( P r e p u r i f ie d Grace) Column temperature - 200 C. I n j e c t i o n parti),.temperature - 250 C. - ; ; C a r r i e r gas flow rat e - 30 ml per minute Purge flow - 20 ml per minute Attenuation s e t t i n g s were adjusted to give at l e a s t a 25 percent i f u l l - s c a l e recorder d e f l e c t i o n f o r an i n j e c t i o n of 0.4 ng 2 , 3 , 7 ,3-TCDD. Methods and Procedures Procedure fo r Prelim inary Treatment of the Sample: (1) For 2 , 4 , 5 - T : E x t r a c t i o n : Twenty grams of sample were weighed in a 500 mi. separatory funnel and d is sol ved in 100 ml of warm aqueous a c a t c n i t r i l e . Then 100 ml of e q u i l i b r a t e d hexane were added, and the funnel.shaken vigorously fo r 30 seconds. A fte r the phases sepa rated, the lower phase < o . - *7 Jio U .-i. ' Page 6 ( A c e t o n i t r i l e ) was t ra n s f e r r e d to a second 500 ml-funnel. The f i r s t 500 ml funnel was s w i r l e d to recover traces of a c e t o n i t r i l e adhering Ii ; 1: i*: to the funnel w a l l s , and these drai nin gs were t r a n s f e rr e d to t h e - ` :i a c e t o n i t r i l e phase. The hexane phase wasiadded to a 1 - l i t e r funnel ' i , i containing 500 ml of d i s t i l l e d water. !- !' i i : i I .' The p a r t i t i o n step was repeated twice more, using 100 ml | o f n-hexane each time. The a c e t o n i t r i l e phase was tr a n s f er r ed between i; | the two 500 ml funnels and the hexane phase added to the 1 - l i t e r ' funnel a ft e r each p artitio n . Following the third p a r t it io n , the a c e t o n it rile phase was discarded. The three combined hexane phases in the 1-1 i t e r funnel were, then-washed by shaking with d i s t i l l e d water for 30 seconds. A f t e r the phases separated, the aqueous wash was drained o f f and discarded. The hexane phase was dried by passing i t through a four- inch g l a s s funnel containing a small cotton plug and 50 g of anhydrous Na^SO^. The hexane was c o l l e c t e d in a 400 ml beaker and the separator was rinsed with several TO ml washes of hexane. The washes werepassed through the funnel to wash the Na^SO^ and c o l l e c t e d in the same beaker. The hexane phase was evaporated j u s t to dryness on a steam bath using a gentle stream of dry nitrogen to aid in the e v a p o r a t i o n . : Alumina Column Chromatography - A column was prepared in a g lass tube, 150 x 10 mm, having a porous g lass plug, by f i l l i n g the tube with ether and adding alumina wh ile gently tapping the tube to r e l e a s e any a i r bubbles. The alumina was added u n t i l i t reached a height of 8 cm. The column was then washed with 50 ml of e t h e r , followed by 50 ml of n-hexane. JL 9 1 8 The residue from the evaporated hexane p ha se' in the ex tr a c t io n step was di ss ol ved in a small volume (about 1-2 ml) of diethyl 'ether and tr a n s f e rr e d to the alumina column. The beaker was rinsed with i. j ' several add itio na l ether washes, and these were added to the!column. !, ! The column was then eluted with 50 ml of 25.* ether-hexane s o l u t i o n . The ether-hexane fr a c t i o n was evaporated j u s t to dryness on a steam bath under a gentle stream of dry nitrogen. The residue was q u a n t i t a t i v e l y t ran sf err ed to a 4 ml screw cap v i a l , using a mixture of 1:1 Chloroform-Ether to accomplish- the t r a n s f e r . The sample'was evaporated j u s t to dryness once more, and the f i n a l residue dissolved in 0.5 ml of 25;i ether-hexane s o l u t i o n . Procedure for Preliminary Treatment of the Sample: (2) F o r 2 , 4 , 5 - T Esters: S a p o n i f ic a t i o n : About 10 g or' e s t e r sample was a cc u ra t e l y , weighed in a "400 ml beaker and d is s o lv ed in 50 ml of e t h a n d . A ft e r the sample was d i s s o l v e d , 10 g of potassium hydroxide d i s s o l v e d ; i n |; i a few ml of water were added, followed by the addition of 50 ml of double d i s t i l l e d water. The s ol u t io n was heated under r e f l u x for three hours, shaking o c c a s i o n a l l y . The s ol u ti on was then evaporated on a hot p l a t e u n t i l no noticeable odor of butyl or 2-ethylhexyl alcohol was present. The r esidual s o l i d s were d is so lv ed in 100ml of N,N-dimethylformamide and 200 ml of double d i s t i l l e d water with s l i g h t warming and t ra ns fe rre d to a 500 ml separatory funnel. E x t r a c t i o n : The solution was then extracted with 5 x 50 ml portions of n-hexane, the combined e x t r a c t s being c o l l e c t e d in a 500 ml :' i i Page 3 ! : !'' separatory funnel. The combined hexane e x t r a c t s were then washed with i i-{ 60 ml of 1:1 NH^OH and 30 ml of 1:2 NH^OH in that order, and: f i n a l l y washed three to f i v e times with 50 ml of double d i s t i l l e d w a t e r , ( u n t i 1 i . jwash water was n e u t r a l ) . The e x t r a c t s were dried by the addition of 30 g of sodium s u l f a t e to the separatory funnel and the funnel Contents sw i r l e d and allowed to remain in contact with the sodium s u l f a t e for jI `; 30 minutes. The e x t r a c t s were then f i l t e r e d throuch a funnel containing i.. a cotton plug and about 3 g of sodium s u l f a t e into a 600 ml beaker, and evaporated to dryness on a steam bath under a gentle stream: of dry nitrogen. F l o r i s i l Column Chromatography: A column was prepared by f i l l i n g a g l a ss tube, 150 x 10 mm, having a porous g l a s s plug, with n-hexane and adding F l o r i s i l while gently tapping to r e l e a s e any a i r bubbles. The F l o r i s i l was added u n t i l i t reached a height of 8 cm. The column was then washed with 50 ml of n-hexane, followed by 50 ml of ;20% methylene chloride-hexane solution. !, The residue from the evaporated hexane e x t r a c t s was d is so lv ed in i: a small volume (1-2 ml) of n-hexane and t r a n s f e r r e d to the F l o r i s i l column. The beaker was rinse d with several a ddi ti ona l hexane washes, and these were added to the column. The column was then eluted with 50 ml of 20% methylene chloride-hexane s o l u t i o n . The methylene chloride-hexane f r a c t i o n was evaporated j u s t oo dryness on a steam bath under a gentle stream of dry nitrogen. ;The res idu e was q u a n t i t a t i v e l y t r a n s f e r r e d to a 10 ml volumetric f l a s k using the 20% methylene chloride-hexane s o l u t i o n to accomplish the t r a n s f e r , and the so l u t i o n was d i l u t e d to volume. < jl Oo qJp*f- lu Page'9 Procedure for the Gas-Chromatographic Determination.of 2 , 3 , 7 , 8 - ' Tetrachlorodibenzo-p-dioxin Standard TCDD S o l u t i o n s : ' M; i i ! : Solutions were prepared containing 20 ng of TCDD per ul in i; j 25% ether-hexane and 0.2 ng of TCDD per ul in 25% ether-hexanei These solu ti ons were used as standards for flame io n i z a t i o n de- j; I, I tection and el ec tr on capture d e t e c t i o n , r e s p e c t i v e l y . The standard used in flame io n i z a t i o n detection corresponds to a TCDD content!', in 2 , 4 , 5 - T of 0.5 ppm, and the standard for el ec t r on capture de--1 te ct i o n corresponds to a TCDD content in 2 , 4 , 5 - T e s t e r s of Q .2 ppm. E x t ra c t s ol u t io n s of samples of 2 , 4 , 5 - T and 2 , 4 , 5 - T e s t e r s prepared as described were chromatographed under the conditions j' described. For 2 , 4 , 5 - T samples, a 2 ul i n j e c t i o n o f standard TCDD, ;: f was followed by i n j e c t i o n of a 2 ul a li q u o t of sample s o l u t i o n . | For the e s t e r s , the i n j e c t i o n volume f o r standard and samples was 1 u l The re tention time f o r TCDD in 2 , 4 , 5 - T samples was about i ten minutes and in the e s t e r samples about s i x minutes. The con-; cen tr ati on of TCDD in the samples was c a lc u l a t e d using the following formula: r _ Au Vs Cs " As Vu ,,^ where f = - ^ f o r e s t e r s , f = for 2,4,5-T, and Cu = concentration of TCDD in o r i g i n a l sample, ppm Au = peak area of TCDD in a li q u o t of sample i n je c t ed JL 8S21 Page! 10 i i' As = peak area of TCDO in ali q u ot of standard i n j e c t i o n j |i Vs = i n j e c t i o n volume of standard, yl ': : I' : :1 j; Vu = i n j e c t i o n volume of sample, yl ; |; i j Cs = concentration of TCDO in standard, ng/yl iI I l` W = weight of sample taken, g j : ! ; Res ul ts and Disc us sio n: | i A total of 15 samples of 2 , 4 , 5 - T and 15 samples of 2 , 4 , 5 - T ; e s t e r s were analyzed fo r 2 , 3 , 7 , 8 - t e t r a c h l o r o d i b e n z o - p - d i o x i n . j The. e s t e r samples chosen for a n a l y s i s 'were of e s t e r s manufactured from 2 , 4 , 5 - T analyzed in t h i s work, with the exception o f one sample of agent orange he rb i ci d e . The date of manufacture o f the samples ranges from 1966 to the present. Only four butyl e s t e r s were analyzed, whereas ten 2-ethylhexyl e s t e r s were analyzed. This i s proportional to the quan tit y of manufacture and use of the two e s t e r s . The e s t e r s required a more e f f i c i e n t clean-up procedure than did the 2 , 4 , 5 - T samples, owing to the use of the el ec t r on - c ap t u r e detector which has greater s e n s i t i v i t y , but i s more e a s i l y contaminated than the flame io n i z a t i o n d etector . Clean-up by F l c r i s i l column chromato graphy proved to be very s a t i s f a c t o r y in removing i n t e r feri ng sub- s tances ------- ---------------------------------- A ll of the samples contained l e s s than 0.1 ppm of 2 , 3 , 7 , 8 t e t r a ch lo ro d ib en z o- p - d io x in , except the sample of agent orange \ h e r b i c i d e , which contained 6.21 ppm. The agent orange was re ceived ' from t h e . A i r Force and has been stored for about two years at t h i s location. 1 I: Page 11 I: Recovery of 2,3,7,8-Tetrachlorodibenzo-p-dioxin: : |! I.. One ml of a sol u ti on containing 2 ug of TCDO per ml was added to 20 g portions each of four samples of 2 , 4 , 5 - T that were f r e e |from ! the impurity ( l e s s than 0.1 ppm), and the samples were analyzed by : I. the method described. The addition produced the equivalent of 0.1 ppm TCDO in the 2 , 4 , 5 - T , which was detected by the flame i o n i z a t i o n detector. A 0.5 ml a li q u o t of standard s ol u t io n containing 0.7 ug TCDO per ml was added to 10 g portions of each of two butyl and two 2- ethylhexyl es t er s that were f r e e from the impurity ( l e s s than 0.1 ppm), dissolved in 50 ml eth anol, and the samples were analyzed ; by the method described. The spiked samples contained the eq ui val ent of 0.35 ppm TCDD in the e s t e r s . Recoveries of 43 to 60 percent were obtained. Recovery of 2-,3,7,8-Tetrachlorodibenzo-p-dioxin from FI o r i s i l Column Chromatography: A 2 ul ali q uo t of standard sol u ti on containing 0.7 ng TCDD per ul was spotted on a F l o r i s i l column prepared as described e a r l i e r . The sample was then eluted with 50 ml of 25% methylene c h l o r i d e hexane so lu t io n . A f t e r evaporation to near dryness and d i s s o l v i n g . the residue with 0.5 ml of 25% methylene chloride-hexane s o l u t i o n , a 2 ul a liq u ot was i n j e c t e d into the gas chromatograph. A recovery of 95% was obtained. 188 Page 12 L i n e a r it y of Response of the Electron Capture Dete"ctor:` Portions of 0 . 4 , 1 . 0 , 1 . 2 , 1 . 4 , and 2. 0 ul of a standard s ol u ti on containing 7.0 ng of TCDD per ul were i n j e c t e d on to the 0V-17 column connected to the e l e c t r o n capture d et ec to r. The attached graph of peak area versus nanograms of TCDO on column appears to be l i n e a r up to 8.4 ng TCDD over the range examined and passes through the origin. Limits of Detection: Under the conditions of the method the lowest leve l of TCDD detectable corresponded to a sample concentration of 0.1 ppm TCDD in 2 , 4 , 5 - T and i t s e s t e r s . Typical chromatograms are attached. A* M * 4 C i l rfiT O h n i* '. J. Ford - Research Center J. M. E t g u - Synthetics 0 0 0 0 3 4 2 k= i.cluf" 1 cc I.# C _ Vilnlagton, Oelavnre ., February sfc, 15u6 TO: FH3t 3. Z. Wilder - Jacksonville Z. Z. Chri3tofr.no - Medical - Hoae Office the I'd Ilia to tine; snd effort yaxopuressp*enty-eaxppplraeicniiantgiotnhetpolaynotu end Or. effort S l d y U rfor-^, ^ In-^qv^roBPeni&l control.! There has been a narked inprovaosnt during the past year and if the proersa continues at this rate even nlnor problem: vill be under control.! One potential hazard ctons froa the use of supplied air casks vhen elecaing the Sharpies centrifuc*. Under certain clrcvmstsnoes It la possible to G e n e ra te carton nonoxide In oil lubricated air esepreaaore. If non breathe this air for extended periods their acuity nlGht be impaired, but the effects would not be pronounced If the breathing air contained less than ICO ppa of CO. EOteruination of the CO content of breathing clr is Justified, and the enclosed literature describee a systes for nonit.riag breath.lug air. i .. Sr. Savon and Mr. Cholak (representing the nACfeasdblldty -study, tess) appeared satisfied vlth the precautions taken to^prevent occupational lllnesa-at--Jachsoavllle. They noted a unique opportunity to study possible hsalth-icallcatloaarbecauce this plant is the only one entirely* devoted to phono^r herbicides. They are not a w e of occupational illneas associated vlth the nnnufacture or use of these anterlols but they v l U probably recomead a nor*^thorough study of exposure to rev pntcrials, solvents iniersediates cod' finished products, lb addition they would like to see some nedljal: data such as urine analysis. Their report vlll be sent to you vhen it is received. Dr. Sldvell agreed to fsrvnrd ccsplcs of C , k , 5 , - T production atrerno and recycle cr vast* stream:. Cne pound of each s p l e should be sent to J. J. Ford at the Research C-nter. Those copies vill then be used In preparing nzze r i d for test by cioassay techniques for chlomone or SEP retention. Z3C:wh En clo su re : * H m . 1)7 tOOM 1 -U !U 1 I Miarn v.44 18925 H ER C U LES PO W D ER COM PAN Y C0**0Af(0 \ JA CKSO N VILLE. ARKAN SAS FIRST AID FOR i CAUSTIC |;M0I70CHL0R" :! ' If splashed with any of these materials, PHENOL 1. ) Go as quickly as possible to a Safety Shower. 2. ) Call for help on the way. 3. ) Get under the shower. 4. ) Wash repeatedly with water. Rub lightly over areas affected to hasten the removal of caustic or monochlor. 5. ) While being rinsed with the water, have someone help remove clothing which may be contaminated with the splashed material. 2.) Wash for at least five (5) minutes. Continuous washing and rinsing with water is best for the removal of caustic or monochlor, or solutions of these. For phenols or phenol solutions, after flushing with water and removal of affected clothing, pat dry the areas immediately affected -- do not rub -- and apply a generous layer of glycerin. Allow this to stay on for approximately one (1) minute and then flush off with water. Repeat this at least two (2) to three (3) times. Finally, pat dry and apply a layer of glycerin. If any of the materials are accidentally splashed on the eye lids or;into the eye, immediately flush with water, using an eye fountain. If splashed generally and incidentally in the eyes, rinse eyes while in the shower. Never rub an eye to help remove something, only flush it. Have a helper hold the eyes open if you find it impossible to force yourself to do this. Report all accidents to supervisor or have someone do it. Rememberi Prompt Flushing with Water, Removal of Affected Clothing, Care to be sure that all body areas are washed, otherwise an area may be overlooked which may cause more trouble than the area first noticed. 1892-6 AESidwell:bg 11/21/63 : Emll C. C k rla ls ftM Isd iu iru i Hygieniat !H rn lti Incorporated Hercule Tower 910 Markat Scraat jWllnungton. Da U a ra 19499 3 aar Cbria: T M t la a belated r a p ir *o your la n a r o< Octobar 14. 1944. A d a ta r In replytng ta for two raaaan a. T ir t. 1 wantad a ckaAca to avalala orna o tba inform ation wa had to aaa hor It agra ad a u k your conclaaiona and aacood. to conaidar furtbar. tba adviaabillty pi publication o aucb Information ot tbla tim a. In regard to tba iir a t queatioo I im noe at ail aurprtaod at your confinatone witb re g a rd to tba liv ar iunctlon taata 1er a bava obaarvad aeanlially tba ama Inconaiataacr la reaponaea. I dn aol ballava thia ia uaipua ior tba acaagan ycu maatlooad (or 1 tbink It la trua o m nnr otbar bopatotoxic aubatancaa. I aal paita confidane tbat if ona anta to r a lr on aucb taata. tbaa a good aiaad group of anim ala would bava to be uaad at each doaaga lav al. Individual v aria tio n la atm niy too grani to p erm it aaiag tba data frora am ali groupa. On tba otbar hand a bava atill found tbat tba rabblt a r taata to bo quita conalatant and valuation of porbapa . tb raa anim ala aaam a to glv ua v ary good aeeaye. :' In regard to publlcatio I am no* aatiafied tbat wa a ra ra a d r to ; publia b on tba aubject r* t. I think thia rap u iraa a co aaid arab ia : araount o thougbt aad prm ditation wtth regard ta poaaibla : conaapuaacoa. I inai tbat lt wouid bo a m lataka to kick tbla ta tba public ye until aucb tim a a wa bave aaew ara to obvtoua quaatioaa Beat wiahaa for 'Happy Hnliday and P .o ap cro u a New Y a a r. I Sincarely your a. V. K. K o .. S io cA tm icit n A rc k b o ra to rv 1401 B u ild in g VKB t <c h 0 : 'j w* m a7 1 r "W" Th c h i|f|K * n nuhr_well eorrLtd ilh do r.or co i . t T ^ conact and duration, vn ia anim al ha ip p aram i y t{nificanl ({et. Although am poaitlv r i m i l i t r i btaiad Uh dioata ltH, th uahlaoaa o thia tochnigu aa a bloaaaay for th prsaco o dlojda ia quaatieaablo. H01501 \< r i U JuU m H O - T U T frbtattmm .'m e. '*0 MO*,r*C 0*3 j *iOr " U O O .'w w iN O i| ! I400* O ctober 10, 114 O r. S. t . Chrlatoaao t Madieal Departm ent Marala* Incorporata* TIO M arhat S tra a t TTUmagton. Dala a r a 1MTT Daar Chrlat C oclea** la Om ab a trac t o A * p ap a r to b* n k m l t u ta SOT for a u x y a a r 't m eado*, M arch T -U , 1T4T. Th* aarm tu ia U "InAaaac* a i Dinota oa t i r e r J>iactfoa La tha R abbit. " Bart regarda. Sincerely youra. 1 MUCrpah S ac loaura M .1 1 . K apU acer, n u O. A u n t u t Laboratory D iractar h 0 ! 'j 0>( A CU LES POW OER COMPANY ***< : ce: Mr- Paul Mayfield - Executive Mr- Charles Maddock - Legal Or- Lemuel C- McGee - Medical Mr- P- J. Reno - Synthetics Mr. R. T. Yates - Synthetics _ Mr. C. L. Dunn - Synthetics -Mr- J. M. Eagan - Synthetics -- Mr- H. E. Wilder - Jacksonville Mr- A. 0. Sidvell - Jacksonville Mr. Ashworth Burslesf"t\Advertising Vilming March 26 TO: Mr. John G. Copeland - Synthetics Department THOM: John ?. Fravley - Medical Department Report of Meeting with Dow Chemical Company on the Toxicity of Trichloropher.ol Impurities____________ At the invitation of Mr. V.^K.-Ro w t ,' Biochemical Research Department, Dev Chem i c a T ^ m p S h y T "M r . C. L. Dunn and the writer (along with representatives of other TCP producers-- see letter attached) met in Midland on March 2**, 19^5* to discuss impurities in TCP. ---- --- "A Mr. Rove and Dr. Holder of Dow reported that 60 to 70 employes of Dow over the past t w o !years have developed chlo.racne-from-exposures to materials in their TCP operation.i ;Chloracne is a^dlsfIguring diaeaaa-lnvolving blockage and inflammation; of the sebaceous glands of til's- skin7"P*^icuIarly of the face. It is believed to j be a systemic disease and requires several years after exposure for the condition to di sappesr. Dow h a s ;conducted considerable research to identify the cause of this condition and has concluded that several impurities, sometimes present in TCP, are responsible.; They have identified one of these impurities which they believe is the principal acnegen-- 2,3j7,8-tetrachlorodibenzo-p-dioxin. They have developed (anl supplied to all attendees )\a chemical method for the detection of this serial which; is sensitive /to I\ppm (gas chromatography and flame ionization). There was considerable' icusslon of the clinical aspects of the disease and the toxicological research Dow has conducted. In brief, 2,3,7,8-TCDHD has been shown to produce the disease in rabbits at a concentration of 1*0 PI after one application of 0.1 ml to the ear, and at a concentration of 0.1* ppm after eight applications. No evidence of the disease has been produced by concentrations up to 20 ppm;for a. single application and up to 0.1 ppm for twenty-five applications rabbit ears.; The compound has also been demonstrated to be a potent liver textear.t by oral or skin exposure. As little as 0.017 mg/kg is lethal to ra3=--s by the oral route. Dow has analyzed cocaercial samples of TCP of producers and has found up to 2C^ppm of 2,3*7,8-TCDED in some* In finished samples of 2,l*,5**acid they *"*ave -ound up to 10 ppm. No Hercules sample-analysed contained any significant acnegen. Lav has reduced their TCP capacity and is cHecking-all^production to v* zhat ':t contains less^than 1 ppm 2,37778tTCDBD. Currently,'Dow is"' al wastes and con.ttaAmmiinnaAtteeddT~mKa*t.enri^a*i frvoom thhieir' TCP plant since they are \ 18829 V _:S P O W D ER COM PANY Mr. John G. C o p e la n d Page 2 March 26 , not positive that burning will completely destroy the acnegen*. Dov's intention in requesting; this meeting vas to inform all TCP producers of this information so that they car. take steps to control the quality of their TCP production. A sa.-j.-e c. 2, for analytical control vas supplied to each company. Tne^-Michigan State Departaen^-of Health has been consulted on this problem b e c a u s e cfj^box^reiationa-probreas. Gov suspects...that .the .Federal Government has become .a v a re ^ a ^ h e -p ro b le m ,. " ................. '-- 'I reccmmerrd-that Hercules take immediate s t eps to determine whether any acre gen's are formed in our TCP process. Thia^should be determined by chemical analyses and biological assays. If any such materials)are formed, ve should c.etc-.cine the fate of these materials in jour plant--whether they are chemically destroyed,;burned, or discharged in the waste stream", etc. We should also ccnside: the desirability of constant monitoring o K o u r TCP or 2,4,5-dJ-acid production by chemical methods to protect against illegitimate claims of acne from users of our products. -J L MSXCUblS 18930 f-J-4 < u. j wI s h ju * ; t o * H t l M * Tfc* " M v t i . C. m i l i -- Inloroollonol *. g. (tellM A M - * * i tU A H l >* A-C* g. M U - ptMtlc* ! A. X. Co-- r * A--1 W> > C* J. Mr* *Mi< I.C. JL INCORRORATEO V RAHTMflV rtun^fM. 9(W*| !< ir i 1966 ' Ikae--k o l. Xaot. 4r U 3T A.O f c M n M l t f A ll-- 30 ; <T U M p U M Mala M u c U ta . t a c fn ftM o r Ostial: ; i Xeet lyt--M r {1965) <rtoc a r lilt U j w la to ra to ry , o < l t n i i 4 tM l u u l i aoooelat* ttfe Um produetlea of tricaieropaeol. I reviev* *1U fom U t reeeat mi e f eAlaniea la tM UtUU4 l u u i airl ye r i r t i w tM | n i U M t* la i *7 7011 t s u t u n t | i l u t 1 M t m i M o f ta lla r I t M l i o | 1 a M t Ay M 3> 0m o f yor B i t holaful omu a U a t ]M aalyao a l l Alpe ra t of lacala trc a lo re pMool for cA leraca-taa Ay oa o ra l 1 Atolelal aaeay proeodure al*A ye t e n rala--. T-- alao o ffo ro i Xa aoaar ao-- ot oar. a--le s a c m rila g u ta i i r n t u r t . S i --1l * t u r o f Pori M r 36 1965 X to d ieo u t a i o e14 --e l %Me oa--lee la tt> ooar (V iv o , fo r a ce--1--t i -- ef n m o m , I t Aae tea-- o a til n to a i--11 tM apio alea o ronalOtr aot epprepriato. V ilaooroly Mpo U a t yetar o ff r 1 t l l l arallaA le to --. Oa tM aaoiarptlaa U e t j w t i l t l l l M Alo t a y t r f b n ik l ` u m t i , aa ta ra Alp--d 13 oa--! (10-gnaa --cA) o f pbrooxj MrAlel# fialM 4 predeca aa latnM dlata aeo--torod la tM lr aauTaeviro ta M . Al-- Piala--a o f oar (-- O m e o . Vo Pavo ak4 Mr. Olola--a to c w la c t yo te arranco a n l t i U e tla a ( I r y t n -- 1 tlir a n r o f tkM a--loo to ye. Xa a d d ltl-- , M *111 Aa* a --a l l aaplo o f 2 ,},7 ,& - i* tn e * lo r o d .* o o f9 ^ i* M iA , alea cea Ao ao4 ao a m :J. i i -*! -; Q g' - -- ...i AM rerar y o u lU o i tfeooo aa--loo M*o Moa -- ly w l fo r ' lala* c--t --t Ay aa Aro--toc--pay oa n v t l l M ory gla ta oacAaac ta i iafer-- to s t u ye la -- ffo rv te oorola* tM roU aA lU ty o f tM Are--tegragAlo procour . P o stra r, ye Arel o-- Hat ao-- o f tM -- yl c--ta ta -- . to eta 11 *lala*; oUoro o o u ia trm 1 ta 35 y-- odo ' l ala* orn etM ro -- ral Aa-- o-- u m u e u o f 'lala* alca M i t o M la --rapta r . I TM aa--le o aro laM le aed U o o tlflo ao fOllo ra ; oapleo n tM T ^ l- 1 4 .3 -a -5 gtandar* 3,k,5,-T AeU t u a-- Btoala - h0 1VjO J c H A o \/ The Cancer Epidemic: Part 1 I ;.! !:____________ by Jam es Morion interest of the most powerful men in the world--they would be better off avoiding the epidemic of cancer IN `THE UNITED!STATES the most profound con -! Their investigative exploits in this area are not likely to sequence of the environmental crisis is the epidemic rise i be rewarded. in the incidence of cancer. Ih is epidemic indicates more than an ever increasing occurrence of a fatal disease; it indicates that the body chemistry is being so disrupted by environmental toxins that our abilities to resist dis ease and reproduce healthy children are also failing. Cancer is for us what hunger is for the people of El Sal vador, the cutting edge of the survival issue. Itis ourrev olutionary issue, j I . ; ; *If our children are to survive we must have a com prehensive analysis of the epidem ic First, w e must un derstand and be able to articulate in common English the empirical data that define the parameters of the epi demic and their full range o f implications. The debate on cancer cannot'continue to be confined to the world of the epidemiologist and oncologist Second, w e must understand the social forces that propel the epidemic and the implications for political action. Tofail to under stand ether the physical or social nature of the epidemic w ill be suicidal. : j ' It is significant that yu ar likely to be first read ing about the epidemic of cancer in a smalljournal of the revolutionary left: The National Cancer Institute and the American Cancer Society, the primary state and pri vate institutions responsible for representing the inter est of the public in:these matters, contend that the dis ease is only rising in response to cigarette smoking. The bourgeois press follow s the official line. Even the liberal and left press has been unable to confront this issue. - While the failure!of the left to confront the epidemic of cancer is more problematic and w ill be discussed in a subsequent article, it is obvious w hy the institutions of the right must deny'the epidemic of cancer Capital, or at the least its leading sector, can only stop the cancer epidemic by committing suicide as a class. This is be cause the aetiology; (cause and origin--ed.) of the epi demic is found in the,petrochemical transformation of the postwar economy. :: P ' j ' \ . The use of these synthetic, chemical poisons plays an irreplaceable rol in the process by which capital ex tracts surplus value and maintains control over the process of production. That they can be manufactured, employed and disposed of with little or no concern for the toxic consequences to the environment is an essen tial condition for th eu se of petrochemicals in the capi talist world system .' ConsequentIy,' when intrepid academics, bureau crats, and journalists' begin to sense that they are pursuing an issue which is in fundamental conflict with the James Morton is 44, a resident ofthe countryside near Chapel Hill, North Carolina, and in the process cffinishing a book on political economy ofspecies extinction. He gratefully acknowledges the assistance ofBartJordan in preparing this article. ;, 1 There are three reasons why the cancer epidemic rep resents the single greatest threat to our lives. First is simple arithmetic: Humanity cannot continue to endure an ever increasing incidence of a fatal disease. For in stance the most conservative estimate has cancer inci dence increasing at .9% annually, with approximately 965,000 new cases reported in 1987. With this rate of in crease that within 400 years over 10% of the U.S. popu lation would be contracting cancer each year. The second reason is that any compound that is capable of promoting an epidemic of cancer is also likely to disrupt the entire process of cellular reproduction. Thus arithmetic alone is too vulgar a tool to measure the impact ofcancer At the current rate Ofincrease w e could as species essentially be dead--that is, unable to repro duce--very soon, even within decades. Cancer is a disorder in the process of cellular repro duction, propelled to epidemic rates by the introduction into the environment of new agents which disrupt that process. Cellular reproduction is the signature process of a living creature. In a human it is the reproduction of . arterial walls, blood, nerve cells, organ tissue, skin, sperm or ova, and the genetic material that w ill deter mine the physical evolution of humanity. It is also the reproduction of the body's defense against "foreign" in vaders: the immune system, that 'complex network of specialized organs and cells...w hich equals in complex ity the intricacies of the brain and nervous system ' and whose success depends on an 'incredibly elaborate and dynamic regulatory-communications network. M illions and millions of cells, organized into sets and subsets, pass information back and forth like clouds of bees swarming around a hive.' (Understanding The Immune System, National Institute of Health, 1) The success of the immune system or the reproduc tion of organ tissue relies on chemical messages which originate within the nucleus of each cell. Petrochemicals are capable of penetrating the protective membrane of the cell wall and causing a rewrite of the message by which the twin strands of DNA (basic genetic material) coiled w ithin the cell direct its reproduction. A petrochemical that is capable of scrambling the cellular message to cause some of the cells that repro duce the tissue of the liver, testes or ovaries to run amok and produce a cancerous tumor can also damage the genetic material that was being passed to future genera tions, cause sterility, miscarriages, birth defects arid a weakened immune system which can itself lead to cancer This same chemical may also influence the bio chemical mechanisms that are part of thinking, making love and feeling good. An epidemic of cancer is indica tive of a failure in the life process. 18934 AGAINSTTHE CURRENT 19 The third reason why the cancer epidemic is our tion of petrochemicals in the United States was 1 billion greatest threat is the pervasiveness and durability of pounds, by the 1950s the figure was 30 billion, by 1960 petrochemicals. In the forty years since they have come it was 100 billion and today over 400 billion pounds are into common use our lives have been saturated in petro produced each year: chemicals. Every day every person in the United States Cancer really occurs as a series of small epidemics, breathes, eats, drinks, and absorbs petrochemicals most often bound in place and time to the production through the skin. and use of petrochemicals. W hile everyone in the Uni Residents of industrial dries "live under a bubble ted States is more likely to contract cancer at a variety of of toxic gasses.' Those who enjoy a more bucolic exist sites than they were ten years ago, the working class ence inhale a wide range of dioxin compounds via the bears the brunt of the cancer epidem ic The highest rates indnerarion of munidpal garbage. Even arctic w ildlife occur among folk w ho live around the places where or is contaminated by air-bom petrochemicals. A single ganic compounds are manufactured, dumped or applied carrot may have five different pestidde residues on it, a and among the workers who make them or employ them tomato three and a meal of a salad, baked potato, green- and their children. beans and meat will contain a hundred or more differ There is a dose relationship: the workers who use ent petrochemicals and synthetic hormones, most of the chemicals the most or the people w ho live closest to which were introduced to nature the last twenty years. thedum psufferthe very w orst New )ersey, capital's en The typical American city's water supply is con vironment of the future, sports the nation's highest taminated by a thousand or more organic compounds. cancer mortality rates, ranging form 50% above normal When you bathe you breathe chemicals in the water to 150% in the counties with densest concentration of vapor and absorb them through your skin. Hundreds of petrochemical waste. Another geographic analysis finds billions of pounds of these chemicals are dumped into excess of all sorts but particularly of the bladder, liver, our environment each year and one way or another they and lung in the 139 counties where the chemical in move into the sea, the source of all terrestrial life. dustry is most concentrated. Petrochemical compounds also accumulate The epidemic of Non-Hodgkins Lymphoma, which throughout the human body. They can do this because is showing striking increases among the general popu they are produced from oil and thus have a carbon base lation, is60% more likely to occur among Kansas farmers and the ability to bond with other carbon-based com who use the dioxin tainted phenoxy herbicides. If the pounds. The cellular structure of any life form has a farmers use it for more than twenty days per year; there carbon base, but because these compounds are oil is a 600% excess cancer rate. And if they mix and apply soluble they have a particular affinity for an oily sub it--as well as frequently use it--they suffer an 800% stance such as human fa t The highest concentrations excess of lymphoma. are found in fat tissue or the part of breast milk that is Children have their own type of occupational ex richest in fa t As the National Adipose Tissue Survey posure, as their parents bring the chemicals the work shows, you can determine a person's approximate age place home on their clothes, skin, and in their breath. and geographic residence by the range and volume of The risk of leukemia, which provides almost a third of contaminants found in fat tissue. They are also routinely the cancer aggregate for w hite children, is 3-1/2 times found in blood, urine and semen. the national average for children w hose fathers worked The cancer epidemic then is not a discrete process, with chlorinated solvents, 4-1/?, times if the fathers simply one of many fatal diseases, but an unequivocal worked with dyes or pigments and twice as high for signal that the life process of humanity is failing. Every those w hose fathers worked worked with spray paints aspect of our environment becomes each day more sat w hile their mother was pregnant with them. In each in urated with the agents of our extinction. What w e see is stance the risk grew with duration and intensity of ex an unsustainable accumulation of quantitative change: posure to the organic compounds. too many poisons in the environment, too much poison To understand the relationship in time between in our flesh, too much cancer We can anticipate a qual petrochemicals and cancel; one must bear in mind that itative change long before simple quantity overwhelms cancer is a disease which typically has a 15-30 year ge us. The evidence and the political imperative is cleac station period. Today's cancer rates are primarily re sponding to the conditions of the 1960s and early 1970s. Arsenic, asbestos, radiation and various heavy Consquently cancer among the working class today metals have all been causing cancer since at least gives an indication of what w ill follow in the general the turn of the century and today they are killing a lotpopulation as the overall chemical contamination of the of people. But there is only one event, one aspect of the environment continues to accelerate. (See sidebar to the modem environment that is capable of propelling an right for som e details.) epidemic of cancer th e petrochemical transformation of the world economy began after the Second World War. Chemicals that were byproducts of petroleum re fining began to be substituted for fertility, genetic re As would be expected w ith a petrochemical pro pelled epidemic, cancer incidence rises at most body sites (18 out of ?5), attacks the immune system sistance and labor in agriculture and forestry; and for (Non-Hodgkin's Lymphoma up 41.8%), the rend sys wood, steel, hemp, rubber; cotton, glass, w ool, natural tem (bladder up 9.3%, kidrey up 17.5%), and the nerv oils and labor in manufacturing. In 1940 annual produc ous system (up 175%). But the best evidence for tire epi^ g 20 JULY/AUGUST Tracking ithe Rise of an Epidemic CANCERINCIDENCEBEGANaserious dieswhichsuggestthatfrom33-47%of exposedtofarmoreorganiccompounds. risesometimebetweentheSecondNat alllungcancerhasanoccupationalaeti Thereforeitisusefulforthoseobscuring ionalCancerSurvey(SNCS1947-50)and ology.Nor does cigarettesmoking ex theextentandoriginoftheepidemicto theThirdNationalCancerSurvey(TNCS plainwhy people living in dries like combinemaleandfemalerates. 1969-71).Mortality,statisticscollectedan nuallyindicatean almostflatresponse between1950and1965,andthenbegina continualandacceleratingrise. AGE SPECIFIC CANCER INCIDENCE RATES IN WHITE MALES 1973/74 -- 1985/86 By 1965SamuelEpstein,aphysician specializing in occupational medicine, began to see evidence that a general M00EXCLUDING LUNG GANGES M00 cancerepidemicwasbuilding,propelled bythepetrochemicalsravagingworkers 1000 inpetroleumrefineriesand inchemical 1000 andrubbermanufacture.By1979Epstein hadenoughdatatopublishtheseminal 1000 work incanceranalysis,ThePoliticsof Cancer(AnchorPress/Doubleday). We nowhavefarbetterdata;provingthatEp 1000 000 steinwascorrect!i j ;i 40*04 00-04 Themostreliabledatawehaveforthe overall increase:of cancer incidence (CASES PER 100.000) beginsin1973withtheinitiationofthe l l tT I - M GANCIO OATH E 2 l 0 0 - 4 GANCIO 0ATIS j U.S. cancer registry, the Surveillance, Epidemiology,and End Results(SEER) NATIONAL CANCER INSTITUTE DAZA ProgramoftheNationalCancerInstitute. TheconstructionoftheSEERregistry avoids many of the inconsistencies of time, diagnostic technique, and geo INCIDENCE RATE INCREASE FOR graphicareawhich made itdifficultto ALL CANCER SITES 1973-85 comparethedatafrompreviousnational cancersurveys. SEER:collectsdata on careerincidenceandsurvivalratestwice ayearfromthesame hospitalsinfour urbanareasandfivestates,representing 12% oftheU.S.population. One ofthemost!common apologies fortheepidemicisthatincidenceisrising mostlybecausepeople'arenotdyingas frequentlyofheartorinfectiousdiseases, \h :k M 04 03 r-- thuslivinglongerenightodieofcancer. SEER disposesofthisargument in V: twoways.Firsttheinformationhasbeen VhlW Moteo Block MoIm VfcjU T 'ageadjusted'tothe1970populationdis tributionsothatin1985thepercentageof elderlysampledisthesameasinthe1970 BRI H I C 3AU C o acan U o U u| L m Tob/BLaco/Ulori BoiUHALcontfnnntbaia population. Second,;SEER gives age- specific incidence rates. Hence in the DetroitandAtlantahavea50% excessof Lungcancerservesruling-classpur table 'Age-Specific! Cancer Incidence lungcanceroverruralareas. poseinthesamemanner.Thestandard RatesinWhite Mates,'whichexcludes Epsteinprovidesthemodelforthefar ployoftheNationalCancerInstituteand lungcancer,theincidenceofcancerfor morepertinentdatainthelastlineofthe theAmericanCancerSocietyhasbeento whitematesrisessignificantlyinseven sametable,whichIhaveadjusted.First publishacombinedincidencefigurefor outofeightagecategories. allbodysiteswhichcomeincontactwith thefirstline,thenfollowwithacombina SEERpresentscancerincidenceasall tobaccosmokeorjuiceareremoved. tionofthesecondlinetosaythatit'sjust sitecompositefigures;andbysitealone. Cervicaland uterinecancersarere peoplekillingthemselveswithcigarettes. Themore thesefiguresarerefined,the movedbecausetheuseofpapsmearsis These days that second linesnows a more they tellus..Forexample, SEER detectingabnormalitiesofthecervixina grossly understated, but nonetheless withdrawslungcancerfromthestatistics precancerousstate,andthehighrateof alarming7.9% increase. togiveusthesecondlineinthetable'In hysterectomiesmeansthatthereareless Lookhow dramaticallytheappear cidence Rate Increase For All Cancer uteritobecomecancerous. ance of the epidemic changes among Sites.'Since the working classare the Theincidenceofcancerisaccelerat women when only smoking iswith heaviesttobaccousersam havethemost ingamongmenatalmosttwicetherate drawn-- nottooalarming-- thenpullthe intensecontactwithpetrochemicals,cig thatitisamongwomen;theonlysignifi siteswherethereshouldbeadeclineand arettesmokingtendstoobscureanum cantdifferenceintheirenvironmentsis theratesbecome terrifying.Again,the berofpetrocancers.Thereareotherstu- foundintheworkplace,wheremenare generallackofdeclineindicatesacrisis. 18'%"J "O'Tv"' AGAINST THE CURRENT 21 demic and the most alarming implications for our species comes from two sites associated with reproduction. While both testicular and breast cancers can now be diagnosed earlier, the ability of the physician to ultimately diag nose them correctly has not changed since 1950. The incidence of cancer at these sites, both of which show heavy petrochemical accumulation, has increased dram atically and in step w ith the produc tion of petrochemicals. Testicular cancerhas risen by 27% over the last decade and by 90% since 1950. The rate of increase and the current incidence rate of 4.4 per hundred thousand per year are an average for the entire white male population, but testic ular cancer only begins to be a major problem at the age of 15 and by age 44 it is well into a steep decline. However, within the 15-44 year old age span it is the most common malignancy. In the peak years of 25-34 the incidence rate rose from 3.8 in 1947-48 to 11.6 per hundred thousand in 1979-80, approximately a 300% jump among the population most severely af fected. Among 55 and older males the inci dence rate has remained stable since 1950. While the Black incidence rate is a fraction of that of white males. Blacks show an identi cal pattern of age distribution indicating that something new is happening to young Black men; either it happens less or it doesn't affect them as much. Similar rates of testicular cancer among U.S. w hites and French, Germans and Swiss reinforce the validity of U.S. data, as do similarly low rates among U.S. Blacks and Afri cans, Japanese and Puerto Ricans. Testicular cancer is associated with occupational hazards, the incompetence of the medical/pharmaceutical industries, and the chemical residues that typify the environment of the cancer epidem ic Working around the crude petroleum, or natural gas extraction in dustries, or the production of crops and livestock sig nificantly increases a man's risk of testicular cancer A finding consistent with the severe reproductive prob lems experienced by men working in the production of the pesticides Kepone and DBCR PCBs, phenoxy herbicides, fire retardants and other assorted carcinogens, mutagen and terratogens accumulate in seminal fluid and possibly in sperm cells. All of these industrial, weed, insect and fungus poisons are becoming partof the biochemistry that recreates the genetic material of the species as they freely intermix in this process o f ultra rapid cellular division and repro duction where millions of spermatozoa are being pro duced each day, a thousand each second-- each repro duction governed by a chemical message. The weight of evidence on reproductive disorders does not approach the uequivocal nature of the SEER data. However what data w e have does suggest that the types of problems in the reproductive system we w ould expect to encounter with an epidemic of cancerare becoming more common. From 1938 (when it was first possible to do accurate 22 JULY/AUGUST Where employers like'to store -their m ost dangerous chemicals. sperm counts) until about I960, .05% of h e male popu lation was functionally sterile and the average sperm count was about 10} million to a milliliter of semen. Today there is evidence to suggest that tliroughou* the industrialized world 20% ot men are sterile and the average sperm count is around 60 million to the milli liter of semen. Today, no one is threatened by cancer more than women are by breast cancer. Even though the inci dence rate for lung cancer among women has climbed by over 50% in ten years, tin s done so on an incidence base that is one-third that of breast cancer. As bad as the 13.3% increase over the thirteen years of SEER is, w e k m c/ that we have been witnessing a horrifying 3.8% annual surge in breast cancer for women above and below the age of 50 since 1980. Among the young women of tire Seattlc-Puget Sound area there has been a 22% increase over the ten year pe riod and among Swedish women 30-39 there has been a 27% increase between 1972-1981. An analysis of incidence data for w hite women col lected from areas common to the Second and Third National Cancer Surveys and SEER show a 6% rise be tween 1950 and 1971, and a 23% rise between 1971 and 1984. N ow breast cancer strikes one out of every eleven 18837 American women. rounds the chemically complex milk producing organs. Millions upon millions of dollars of grant money Thus, within the breast there are the uncontrolled have been funneled into attempts to prove that women chemical reactions of what easily could be hundreds of are contracting more breast cancer because they are eat organic compounds, the most toxic known to science, ing too much fa t The bulk of the fat theories rely on geo many mimicking or enhancing the effects of estrogen graphic comparisons that purport to show a high corre and interacting with the normal cellular reproduction lation between nations with high fat consumption and of the milk glands. The potential extent of this interac breast cancer, which then ignore data that shows ex tion can be measured by the list of synthetic chemical tremely high fat consumption among Inuit (Eskimo), poisons in the mother's milk. Spanish and Italian women but alow incidence of breast "In an overall assessment it may be wrong to look cancer The Inuit women and the Mediterranean women at one contaminant at a time, because these organohaol- consume fat, blubber and olive oil respectively, that is gens have similar targets in the body, indicating a poten extremely low in petrochemical contaminants. tial for toxicological interactions' (Alan Jensen, The The animal data that the fat theorist concocts is Science of the Total Environm ent, 1986). based on stuffing a mouse with massive amounts of cot Women w ho breast feed have, by a factor of about ton, com or safflower oil, which bears a considerable one-half, a lower incidence of breast cancer, with longer burden of carcinogens. The proposition is never con and more frequent the periods oflactation making it less sidered that those sad' rodents possibly suffer more likely they w ill have that cancer We know thatwhen the cancer not because their diet is 40% com oil as against mother lactates she expels many of the petrochemical 10% but because they receive four times the dose of car- poisons in her system at a higher rate than the rate at baryl, methomyl, permetherin, methyl parathion, carbo which she absorbs them from the environm ent In one furan, captan, diazinon, lindane, alachlor, and atrazine. study the levels of PCBs and DDEs (a byproduct of DDT) Moreover,best evidence suggest a substantial reduction in breast milk dropped by 20% over six months and by in fat intake for everyone since at least 1960. 40% over 18 months. Could wom en w ho breastfeed be less likely to Chemical reactions are not confined to the labora develop cancer because they are expelling carcinogens tory. They occur as organic compounds mix in from their systems into the rapidly developing nervous, water systems, fields, salad bowls, smokestacks and biom mune and reproductive systems of their infants? The dies. N o one understands very much about the content class structure of breast cancer rates in the Seattle-Puget or consequences of these interactions--particularly Sound area reinforces that contention. There is a 53% when they occur within !the confines or our flesh. rise among low income women, (those least likely to Cancer is also a poorly understood process. However, breast feed), a 27% rise among middle-income women w e know that it is a complex event often involving a and no rise among upper-income women, (the most combination of agents over a period of time. In human frequent breastfeeders). Also the lower the income ity cancer occurs within a very diverse genetic pool and group the more likely the individual is to work around am ong a population that is consuming a w ide variety of chemical poisons, live near where they are produced cancer-causing agents. Thus it is difficult to pinpoint a and to drink contaminated water specific agent as causing a cancer at a certain body part Among dioxins, insect poisons, fungus poisons, in the general population, i high-temperature lubricants, weed killers mixing and The female breast is essentially fat tissue and milk reacting, who can say which carcinogen in what combi glands. In the fat of everyone in the United States can nation triggers this terrible reaction in women's flesh. be found at the very least PCBs, DDT Chlordane, Hep- But suddenly more wom en in the industrialized world tachloc Aldrin, DDE, BHC, Pentachlorophenol, and begin to develop cancer of the breast, and in their breasts many o f the compounds of the ultra toxic dioxins includ w e find chemicals introduced over the last forty years in g PCDFs and the most toxic of all, TCDD. which are known to cause cancer in monkeys, rats, mice, The presence of the PCBs and dioxin compounds is geibils, hamsters, dojjp, fish and humans. particularly frightening. In a survey of human milk, What an analysis of testicular and breast cancer blood and fat in Europe and the United States, Alan Jen shows is an unequivocal epidemic rise that marches in sen found that dozens ofvariations of these chemicals lockstep with the introduction of petrochemicals. The contaminated almost everyone, but TCDD had a prefer reproductive cycle is in imminent danger of becoming ence for wom en. The residues were unbelievably small, irreparably harmed, with sperm too heavily contami about 2 parts per trillion (ppt); a ppt on a plane of 183 nated to create a fetus and wom en's breasts so toxic that square miles w ould coverthe area of a quarter H owever babies cannot survive. The poisons in the mother's w hen given to a pregnant mouse at 10 ppt, TCDD dam womb and milk--made worse by a contaminated food ages the fetus; rats develop excess cancers at 5 ppt and and water supply--endanger our survival as a spedes. toxic affects are seen in the offspring o f pregnant If w e do not stop this process that moment w ill monkeys at 2 5 pp t come. The cancer epidemic is the most important single In any part of our body fat there are a continuing issue for the First World; it represents the most pressing ries o f biochemical reactions, but unlike other sites danger in our lives and the lives of our children, a crisis where there are heavy accumulations of fat (such as the w ith revolutionary implications to be discussed in the buttocks or upper thigh) the fat of the female breast sur second part of this essay. gq q AGAINST THE CURRENT 23 * by Jam es Morion would be so immense that it is inconceivable that capi talists would ever make them anyway. This, then, is an THE CANCER EPIDEMIC is the most important single issue that they w ill not be able to co-opt issue confronting the left in the first (industrial, capital-' ;"Without chemicals, life itselfwould be impossible" ist) world because it represents the most pressing dan- 1 -- the Monsanto corporate slogan. Except in its most lit ger in our lives and in the lives of our children. While ; eral sense this chemical company slogan is self-serving the epidemic of cancer and environmental collapse in ; drivel. The new products of petrochemistry are mostly the Third World has at least as devastating an impact as toxic substitutes for natural products that usually it does in the first,1there starvation is the survival issue. : served our purposes better. If, conversely, the Monsanto Environmental crisis and the epidemic of cancer public relations department had offered "without petro- can only be successfully challenged through a revolu ' chemicals late capitalism would be impossible," it would tionary transformation of the global economy. Most people have presented us with a profound insight into the cir do not make revolution to secure civil rights; in solidar cumstances of today's world. ity with another people's oppression, however severe; : To understand the value of petrochemicals to capi or in response to forced overtime. They only seem to be tal, one must first observe who composes the most pow w illing to endure the extreme persona] sacrifice that rev erful segment of the ruling class. At the very top of the olution demands when their lives and their children's capitalist hierarchy, there are oil merchants integrated lives are at stake. The epidemic of cancer is the revolu into vast networks of banks, chemical companies, phar tionary issue that is most relevant in the lives of first maceutical firms and various types of manufacturing world people, and it presents a logical strategic focus for and service enterprises. Thus every barrel of oil that is a mass m ovem ent ; sold feeds dollars straight into the maw of the beast We w ill show here that the epidemic of cancer is an Consequently, when it became possible to make issue that capitalism cannot co-op t Nor is the epidemic shirts, bottles, tires, shoes, furniture and so on from oil, amenable to social democratic solutions. The struggle it was an immensely profitable transformation for the for a non-carcinogenic process of production generates most powerful sector of the capitalist class, allow ing it day-to-day antisystemic resistance. to consolidate control of capitalist production. Why then does: the left seem to ignore this Issue? We cannot discount the personal terror that cancer in spires: that w e might contract it, and that our children might, that the only real solution is revolution-- which seems so far aw ay.'u i ! Moreover, the left does not have good information. The Indian economist Narindar Singh has observed that ecological crisis under capitalism is inevitable given capital's insatiable demand for growth, but that the cri sis w e endure has its particular features because the leading sector of the capitalist class are oil merchants. The epidemic was only!becom ing evident by the late 1970s, and since then the public agencies and the bour geois press have relentlessly suppressed the evidence and denied its existence. Discussion has been limited to the small world of oncologists and epidemiologists, few of whom are active in left politics. Also, that school of thought which once held women's and racial issues to be subordinate to and separate from working-class is Capitalism is -- must be-- a system designed to re ward the largest concentrations of capital. Petro chemical production is the most capital-intensive form of manufacture; hence, the centering of the world economy on petrochemicals that has occurred since World War II. This process has favored capital over 1 workers, large capital over small capital and the capital ' of the major industrial powers over that of the Third sues still holds true when it comes to the environment For them the environment is an "extra economic good," a hippie issue, somehow, separate from the struggle of the working class, the most cancer-ridden folk in bour geois society. :ii I; - P 1' An examination iof the political economy of the cancer epidemic first establishes that it is the consequence ofpractices that are essentialfor m aintaining the power ofthe capitalist class. Though it is most likely structurally im possible for capital to make meaningful reformsin its use of petrochemicals, what's certain is that the sacrifices World. Organic compounds are great labor-saving devices, replacing human labor in agriculture, manufacture and forestry. This allow s capital to perform a highly skilled, labor-intensive task such as farming, replacing the men tal and physical labor involved in this process with chemicals. Farmers, forestry and factory workers re placed by chemicals join the army of the unemployed or re-enter the labor force at semi-skilled positions where they are cheap to hire and easy to replace. Within the capitalist class, the war for control is James M orton is 44, a resident af the countryside near fought on multiple levels. The immense resources that Chapel H ill, N orth Carolina, and in the process offinishing are required to establish a petrochemical refinery mean a book cm the political economy of species extinction. H e | that at the primary level only the largest blocs of capital gratefully acknowledges the assistance of Bart Jordan in 1 w ill be able to compete in chemical manufacture, in ef preparing this article. Thefir s t part o f th is article appeared fect eliminating competition from small family-owned in ATC 27. ! firms. This also favors the much richer capitalists of the 18938 AGAINSTTHE CURRENT 29 first world over those of the Third, particularly in the very expensive process of continually advancing the technology of production. Technical complexity acts as a type of first world patent w hile the power of the pro duct is its market justification. Venezuelan capital, for instance, is quite competi tive in the production of the more conventional orgar.ochlorines or phosphates such as malathion and DDT,but does not have the technical expertise to compete with first world firms in the production of the small, fast molecular chemistry that provides the phenoxy acids. The much more sophisticated chemistry of the phar maceutical firms, still a monopoly of the first world, is far better suited for turning out the dioxin-producing poisons of the agent-orange genre, which are today the world's best selling pesticides. The immensely carcinogenic phenoxy acids are at the cutting edge of maintaining the firstworld's markets for commodities and`loans in the Third World. About half of Brazil's foreign debt is for agricultural developm ent Petrochemistry is also a device for maintaining Third World dependency on foreign technology and fi nance, which translates into an opportunity to domi nate their state systems. But nowhere do w e see the irreplaceable role that petrochemicals play in maintaining the world order more clearly than with m odem agriculture. The chemi cal transformation of global food production w as not prompted by its intrinsic superiority as a system for pro ducing food. Traditional agriculture has fed our species for 10,000 years without a single application of chemical fertilizers or pesticides and, along with its contem porary variations; can produce farmore calories per acre and per calories of energy invested than its carcinogenshrouded m odem counterpart This transformation, which began with the intro duction of hybrid breeding, created amass market in ag ricultural commodities. As R.C Lewondn and JeanPierre Berlan explained in their article, "Technology, Re search and the Penetration of Capital" (M onthly Review, vol. 38, no. 3, July 1986), this was not a transformation: of an existing market, but the creation o f a totally new market, w ithout which it w ould be difficult to imagine the post-war boom that the capitalists of the first world have enjoyed. The transfer of wealth and power is astounding. Before World War II, almost all of the world's food was produced by farmers w ho generated about 90 percent or more of their own inputs-- seeds, fertilizer, pest con trol, labor e tc Then, beginning a few years after the war, all the food in the United States-- and now in virtually all the rest of the w orld-- was produced with petro pro ducts. The seeds come from the store and require the farmer to buy chemical fertilizer, insect poison, weed poison, fungus poison and gasoline to run the irrigation equipment, tractors, combines and threshers. All the wealth that had been created by small capitalist or non capitalist farmers now flow s into the center of the capi talist class -- a series of families owning conglomerates that are oil / chemical / seedbreeding / equipment man ufacturing/ financial corporations. 3 SEPTEMBER / OCTOBER 1990 Needless to say, when one can sell food and vir tually everything needed to produce it to a substantial proportion of humanity, large profits can be made. And it does not hurt to be able to do it from a flexible posi tion. If the price of oil is low -- as it has been for the last few years-- Exxon,Arco, Shell ana their colleagues sim ply reap their profits through their chemical products divisions instead. To understand the implications of modem agriculture it is necessary to look at the fathers of the "green rev olution." By the late 1940r,, the Rockefeller Foundation (Exxon) had begun to confront the specter of land re form during the Cardenas presidency in Mexico with a system that would use chemicals to make it possible for major landowners to enclose the lands of tenants and small farmers. Then, in the mid-1950s, as agricultural equipment and truck sales began to slump in the United States, the Ford Foundation turned its attention to world hunger. In the early 1960s, when the Kellogg corporation discovered a method for cutting the cost of fertilizer production in halfw hile doubling the output, it decided to join its corporate brothers in helping their Third World brethren struggle against starvation while coin cidentally eliminating a ferocious glut in the fertilizer market Nor should it be overlooked that Rockefeller et ai. created immense profits for their banks by selling the financing to underwrite this "modernization" of Third World agriculture. The "green revolution* not only meant that the capitalists of the center had made agriculture in the Third World dependent on their financing and tech nology, but also that they had gained a large measure of control over workers all over the world. Chemical -- capital-intensive -- agriculture meant that droves of peasants and farmers w ould be driven from the land and into urban labor markets. This huge army of unem ployed allows capital to control their work conditions and lower their wages. We can't survive consum ing pesticides, but capital ism cannot survive without our doing so. Even the safe employment of petrochemicals, when possible, is cir cumstantially if not structurally against the interest of capital. Any number of chemicals can be manufactured, used and have their waste destroyed in perfect safety, if enough capital is invested in protective systems. However, to do this would push the price of many petro chemical products past the point where they w ould be competitive with the conventional products or processes they were designed to replace. Even when safety precautions w ouldn't price a commodity out of its market, the money would earn the capitalist no return. It makes by far the best sense to screw the workers, dump the chemicals into the river or turn them over to the Mafia. These are some of the reforms capital must make if the cancer epidemic is to be stopped: its mass market for agricultural inputs, disposable plastic and aluminum, must be drastically curtailed or eliminated; production must be retooled to eliminate carcinogenic processes 18940 and the systematic dumping of poisonous waste in the environment All of the waste in the old dumps must be retrieved and if possible destroyed, or at least stored in secure, above-ground, earthquake-proof vaults. In each instance the reforms w ill cost capital billions -- in lost markets, in retooling, and in recovery of waste. Each re form will tend to increase the value of labor. > We should hope that capital will make these re forms -- no one wants to be poisoned to maintain a rev olutionary issue. However, it does not seem likely that capitalists will address the epidemic or the environmen tal crisis with anything other than rhetoric Consequently, no coherent analysis or strategy to confront the epidemic is likely to emerge from the social democrats.Three formations prominent on the left or in the environmental; movement are the Rainbow Coali tion, the "post-Marxists' as represented by Michael Al- HI bert and the staff of ZetaMagazine,and Earth First These are all populated with deeply committed, politically valuable people, but because they do not grasp the role of capitalism in the environment, their analysis is inco herent and their strategic response can result in either a waste of scarce time and resources or in a dangerously racist, anti-labor and misanthropic response. The Rainbow Coalition has been unable to design a meaningful program for a sustainable environment and has given no evidence that it would be able to im plement such a program in the Democratic Party if it had one. All the energy of the Jackson campaign seemed to coalesce at the 1988 Democratic Convention in Atlanta around a series of compromises in which the Rainbow forces would refrain from demanding open debate on a reduction in defense spending, a no-first-strike nuclear policy, an independent Palestinian state and an end to The Cancer Epidemic: Fiction or Reality? SCIENCE FOR THE PEOPLE re-ex cancerforanumberofsectors,butmost andPetointhatcamp,justasEpsteinhas aminedtheirstanceon thequestionof seriously for breast cancer incidence forthelasttenyears.IfIwere'Hester,'I thecancerepidemic1;intheirJanuary/ amongwhitewomen in1983,1984and wouldn'tsignmy realnameeither! February1990issueandreachedacon 1985. StephaniePollack'sintroductoryar clusionthatwasneitherscientificnorin Frumkinattemptstobuttresstheir ticleposesthisquestion:"Letusassume theinterestofthepeopleThiserrorwas argumentsbymisusingastudybyJohn ...thatthereisnomassivecancerepi madepossiblebyafailuretoengagein Ballarand Elaine Smith published in demicassociatedwithoccupationaland principleddebate,!.'j!-. 1986andrelyingon 1981incidenceand environmental exposure to industrial Theproperprocedureforcriticizing mortalitydata.BailarandSmithdonot chemicals...whataretheimplications?' claimsofacancerepidemicisfirsttotake attempttoaddressthequestionofacan ForFrumkintheyincludesomeacquies theprincipalworkonjthatissue,Samuel cerepidemicbut rathereffectivelyde cenceinourpoisoning;we needtobe Epstein'sThePolitics,ofCancer(Anchor/ stroytheNationalInstituteofCancer's 'open minded' on thresholds-- the EtoubJeday,1979),compareitwiththe claimthatwe arewinningthewaron ideathatitispossibletodetermineasafe, latestandmostpertinentdataandshow cancer.IfFrumkinhad used thelatest long-term,low-leveldoseofacarcino whereheisinerror.Theprimarywriters versionoftheSEERdatathatBailarand gen(wearealotclosertofiguringout inSftP,'RickHester,'apublichealthof Smithemployed,increasesthathedis thetechnologyfornuclearfusion). ficial:who used-iajpseudonym, and missedasslightbecome-- inthespace Frumkinfeelsthat'tradeoffsarein HowardFrumkin,aphysicianonthefa offouryears-- classicallyepidemic evitable_somecancermaybejustified cultyoftheUniversityofPennsylvania, Hester'sargumentreliesonthepri byeconomicbenefits...andthatitisnot dismissEpsteinwith:acoupleofsen maryapologistsfortheepidemic.SirRi inherently evil or exploitative that tencesasbeingwrong;withoutaclueas chardDollandhisprotegeRichardPeto. peoplewouldvoluntarilyassumesome towhyheisso. According toHester theyare'among cancerriskinreturnforotherbenefits.' Thesingle,absolutelyindispensable theworld'sforemostexperts'and'the But ina world with a cancerepi bodyofdataforaddressingthecancer dominant explainersofthepatternof demicpropelledby poisons thatmore epidemic, the Surveillance, Epidemi cancerintheUnited States."He even thoroughly contaminate the environ ologyandEndResults(SEER)statistics places Doll on the left, 'politically mentdaily,itisinsanetobeconcerned oncancerincidenceandmortality1973 courageousintheearlypartofhisre about'thresholds'youcross,notjustin to1985,isignored.Thisreportwasre search career, and reportedly denied thoseentirelyunnecessary'tradeoffs' leasedinJanuary1988.(Itssignificance entryintotheUnitedStatesatonepoint youareforcedtoaccepttoearnaliving, and Endingsarediscussedinthefirst becauseofhispolitics." butalsowhenyoudrink,bathe,breathe partofthisessay,ATC27.)For'Hester" What'Hester*doesnotmentionis and eatAn epidemicofcancerimplies and Frumkin tooverlookitisentirely thatDollisdirectorandwardenofGreen revolutionarychange.-- J.M. analogoustolookingforacrimewave College, Oxford, an industrially fi (Readers interested in pursiung the andusingarrestandconvictionstatistics nancedinstitutionthat,inthewordsof cancerepidemicdebate,includingatrench- fouryearsoutofdate.;j - afoundingfellow,isdesignedtobe'a antcritiqueof`thecancerestablishment'and Perhaps 'Hester?landFrumkin ig specialpointofentryforindustrialinter especiallytheclaimsofDollandPeto,areen nore thecurrenteditionofSEER be estswishingtocollaboratewithuniver couragedtoconsultDr.SamuelEpstein's causeitconsistentlyreinforcesEpstein's sitydepartmentsinresearch."Nordoes congressionaltestimony, 'LosingtheWar positionandshowsunequivocallyepi itimpress"Hester" thatDollisanen AgainstCancer.Who'stoBlameandWhat demic*orvirtuallyepidemicincreasesin thusiasticsupponerofindustryefforts toDoAboutIt,"presentedtotheHouseSub to deny the carcinogenicity of the committeeonHealthandtheEnvironment. Epidemiologist* define an epidemic m a 5 percent o r more annual in n t me in incidence of mortality. But cancer it differ* erti bom an mfoctiouadncaaeHich as KmaJlpox.it is almoet al ways fatal and. a disorderof ceUuiar reproduction, Jtpoind toproblem*in everyaspectof survival Evenaverysmaiiamtinuai increase in cancer is of the gravest consequence. Dioxin-ladenherbicides,2,4-Dand2,4,5- ItappearsintheCongressionalRecord, T-- anactthatputsDollsquarelyinthe September9,1987,pagesE3449-E3454,and campofthemostdepravedchemical-in canbeobtainedfromyourcongressperson's dustryhacks.ButthenSEERputsDoll office-- edL) !Hl-3U AGAINST THE CURRENT 31 U.S. support for the oligarchy of El Salvador, in return for Jackson and his colleagues receiving seats on party policy-making boards. The Jackson campaign moved the wretched Duka kis campaign to address key left issues in no discernible way. Will Jackson now be telling Robert Strauss, Lioyd Bentsen [both of whom are oil-linked Texas Democrats -- ed.] and their clients that they must cut their own throats? If he does, are they likely to do so? Post-Marxism attempts to construct a left analytical framework that removes class from the center of politi cal life and, by necessity, anticapitalist struggle from the center of political activity. Albert suggests that social life is propelled by four categories of equal im pact: culture, economics, politics and kin ship. Depending on the circumstances, other spheres of influence -- such as race, gender, and authoritarianism -- emerge mom these divisions as the primary actors in social ev e n ts.! i In South Africa, for instance, Albert w ould have racism rising to the fore as the m otivating force that shapes the apartheid regime. Thus the white folk of South Africa are so repelled by black skin, w oolly hair and superb music that they choose to rob the people of Southern Africa of their resources, labor and liberty, feeding it all into the maw of the voracious capitalist world economy. A post-Marxist analysis w ould not give a clue as to w hat the forces are that propel the cancer epidem ic At no point in this brief analysis of the cancer epidemic does the evidence ever suggest that these chemicals are employed to bash a gay or lesbian, dominate a woman, oppress a ra cial group, or reinforce astate bureaucracy. Nor does the concept of 'econom y* really explain this phenomenon. In the economic lives of the American people, the cost of medical treatment for cancer and birth defects, the loss of productive labor, and the squandering of natural resources far outweigh any savings that come from dumping numerous poisons into the environm ent Even with all questions of the so cial cost of pollution put aside, corporations w ill use chemicals w hen it would be much cheaper in the short term to em ploy labor ! The forces that propel the epidemic of cancer only become clearly visible w hen view ed in Marxist terms, as a process by w hich a ruling class maintains control of the process of production and accumulates profits. The bourgeois state refuses to design and implement laws that w ill protect file public interest, not because the issue is impopular with the electorate-- environmental protection enjoys overwhelming support-- but because it is not in the interest of the capitalist class. Capitalism could be absolutely race and gender blind, indifferent to sexual preference, run by a state sys tem free o f bureaucratic Napoleons, and there would still be a cancer epidemic and an environmental crisis. Capitalism propels the cancer epidemic and destroys the environment because it is what it is. Homophobia, mi sogyny and racism are tools that it employs in its strug gle for profit and control of the process of production. It has lent those tools a dynamism that no previous reg ime of accumulation was capable of giving them. While the "monkey wrench* tactics of Eaith First are right on target, their focus on "technology* and overpopulation is elitist, racist, misanthropic and dead wrong. Technology is a creature of the system that em ploys it; when it oppresses, it does so by choice. Non toxic alternatives exist for modem manufacture. Tech nology is not carcinogenic; capitalism is. Technology represents an immense source of wealth. M ost o f the people in this world need more -- not less -- access to the benefits of technology. Babble about the evils of m odem technology is usually fol lowed by calls for sacrifice. Working people around the world need have no doubt as to w ho w ill be called upon to make the m ost sacrifice and remain forever in poverty. N ot only does placing blame for the epidemic on tech nology mask the real source of environmental crisis, but calls for sacrifice make a lousy recruitment line as welL Overpopulation only exacerbates the ills of capital ism. The poisoning of the environment, the destruction of the tropical forest and the extinction of the seeds of traditional agriculture are propelled by the logic of the market and class rule rather than by numbers of people. If the world's population were halved, the forest would still be cut, the poisons w ould still flow, and the ozone layer would shrink w hile greenhouse gasses accumu lated. Extinction would just advance at a slower pace. Overpopulation is a real problem, but it is a con sequence of the distribution of resources and the op pression of wom en. There are now enough a ^ c u lg r a l 32 SEPTEMBER / OCTOBER 1990 I resources to feed everyone. Population control is a prob safety of the global environment lem when a high percentage of children die before the age of five, child; labor is an important component of family income, parents are dependent on children to Worker democracy and a safe environment are ab solutely dependent on the return of women to the cen ter of political economy. The most important task of the care for them in their old age and women do not have working class and of humanity is the reproduction of control over their bodies -- problems for the most part the species. The left must create structures to insure that caused by the same people w ho are responsible for en the labor of bearing and raising children receives the vironmental crises. An obsession with overpopulation economic and political power that it deserves. is a great misanthropic whine that the problem is "there are too many of us," which actually means there are too many of them, the poor and the brown. W omen, and particularly pregnant women, have always and will likely continue to most power fully represent the interests of children, and thus must An inability to critique capital leads to a capitalist at least have an equal role in deciding what can be pro .analysis of the problem -- that it is the responsi duced, as well as in whatfashion it can be produced. The bility of the mostj victimized -- w hile a class analysisright to refuse a burden of fungicides and high tempera show s why therejis an epidemic of cancer and that a ture lubricants -- hence insuring a degree of safety for strategy to cornet the epidemic is entirely consistent children -- and to be both free horn threats of physical w ith a left program.jWhat follow s is not an attempt to violence and terminate a pregnancy at will are insepa design a left program but to show that an ecological so rable parts of a woman's nght to control her body. cialism is entirely consistent with the methodology and goals of left struggle for democratic socialism, where control of the process of production is centered on the factory floor and in the communities. The working class occupies the physical center of INCREASES IN BREAST CANCER INCIDENCE RATES FOR WOMEN 1 9 4 7 /5 0 -7 7 /7 8 -8 3 /8 4 (CASES PER 100,000) the solution to the epidemic of cancer If a worker is not poisoned at the factory or in the field, or if a working- class family (the ones most likely to live closest to the factory, dump or farm) is not poisoned by the air and water, then no one w ill be. Workers stand at the front line of each location in the process of production where physical injury to the society can occur Workers must have the responsibility and power to make sure that commodities are produced, employed and destroyed safely. The rest of society has the right to demand that workers produce commodities w ith greater caution. 1947-60 BATES E S 1977-76 BATES There must be a system of elected community and C U 196S-64 BATHS national committees regulating the production and dis posal of hazardous materials. The composition of these committees should reflect the geographic movement of NATIONAL CANCER INSTITUTE DATA major air currents and watersheds. Thus type of organi zation w ill insure that no institution within a commu nity, nor any community (at the head of a watershed for example), w ill be able to compromise the safety of other members of the society. All the information that these committees would! employ to regulate the compounds and processes used in the production of a commodity-- as w ell as the methods of disposal and records of their regulatory activities -- should be available to the general public . ' I j i | ; A democratic environmental movement must by definition be anti-imperialist The commodities of na tions that were produced so that the workers and the environment were poisoned must be barred from the U.S. market, as must commodities produced by labor that did not have the right to freely organize. Nor can the Third World continue to be a dum ping zone for first world poisons. N ot only is this practice morally despi cable, but it only delays the impact of these poisons in our lives. Environmental crisis is a social disease pro pelled by undemocratic regimes; only militant support Thefrighteningriseinbreastandtesticularcancerhighlightsthe for socialist democracy around the world can insure the threattobothgenders-- andtodiereproductiveprocess. A AGAINST THE CURRENT 33 It will most likely be impossible to establish a sus tainable, non-carcinogenic agriculture in the first world without the genetic material and technology of tradi tional agriculture in the Third World. Women typically are responsible for most of the labor-- and particularly the seed breeding ;-- in traditional agriculture. Their highly skilled labor and complex science are absolutely essential in maintaining the genetic base of world food production. We can only have such assurance if Third World women have control over their land, just as w e can only finally be sure that Third World manufacture is not slow ly poisoning the globe when Third World women have the same control over the process of pro duction that first world women must have. A successful strategy to confront the cancer epidemic is fundamen tally a struggle for wom en's rights all over the world. If the revolutionary left confronts the cancer epi demic it has an issue that the right cannot co-opt-- one demanding worker democracy, anti-imperialism and feminism, and responding on a personal level to the most pressing dangers in every first world person's life. It is also a program for prosperity. A transition to a non-carcinogenic economy w ill not mean a loss of jobs, but full em ploym ent' Many workers would simply begin to use different processes and materials or begin to employ petrochemicals safely. N ew industries would also have to be created. The safe cleanup of dump sites and aquifers should provide high wages and long-term employment for any chemical-industry workers who would be laid off by the termination of unsafe produc tion processes. : Rebuilding ;the nation's water systems, dramati cally enlarging the rail lines and providing insulation and solar retrofits to buildings throughout the United States are new endeavors that would be constituent parts of a clean economy. The hundreds of thousands of jobs thatw ould be provided w ould be a powerful stimu lation to the general economy. In agriculture and forestry the demand for labor, and particularly: for skilled labor, would rise dramati cally as natural products and labor replaced petrochemi cals. The profits the oil merchant receive from the sale of pesticides w ould be transformed into agricultural wages spent in local communities, and a rise in agricul tural employment would then reinforce the position of labor as it bargained for w ages and control in manufac ture. The specific varieties of a crop most suitable for chemical-free production w ould be least suited for the corporate marketing system. But such a program would be consistent w ith an entire system of food production from the farm to the marketplace that favored small local organizations over transnational corporations. Environmental struggle must be equated with class struggle. Above all, the awful image of the neo-Malthusian elitist must be purged from the environmental m ovem ent As Marx put it, M althus provides an ide ology for people w ho are unable to confront the control of property. Inevitably there are going to be short-term contra dictions between individual groups of workers and left groups about environmental issues as w ell as over 34 SEPTEMBER/OCTOBER 1990 gender and race. Corporations will often threaten to shut down or move, and they will use environmental restrictions as an excuse to lay off workers. H ow effec tively w e are able to resolve those contradictions de pends on the class content of our work. A group that militantly supports working-class struggle and actively seeks solutions for laid-off workers is far less vulnera ble to a fascist response than an el'te organization that focuses only on its own poisoning and ignores the con sequence to workers who can lose everything for which they have been working. The cancer epidemic is coming at us like a bat out of hell and there is nothing that capitalism can or will do about it. O bviously whatever w e do about it is going to have to be quick and revolutionary. Because of the very general nature of the epidemic and its very specific cause and development, there is a w ide potential base to organize that cuts across class, race and gender lines, and which clearly separates the interests of the ruling class from those serving the rest of humanity. The im mediacy of the crisis and the breadth of the affected population does not call for a classic Leninist, vanguard party, but a looser affiliation of independently organ ized groups bound by common principles but respond ing primarily to whatever is most important to their par ticular constituency. For most people in the United States there are crises more immediately important than the environm ent It is hard to imagine a single mother, earning five dollars an hour and terrorized by some brute, then running from her trailer to support a group that does not actively address her oppression. A revolutionary organization that tried to help this woman organize daycare and defend her safety would find her quite w illing to un derstand that capitalism exploits the material conditions in the natural world which support her life, just as they do her labor; and that the bourgeois state is no more w illing to protect her from the physical attack of capi talism than it is from that of violent males. Similarly, an organization that m ilitantly supports Black liberation struggles can anticipate Black support on environmental issues. The failure to overcome racial and ethnic divisions has been the single most crippling event in the experience of the U.S. left Single-issue politics can only ensure that the legacy of failure con tinues. Black and Latino support are essential to the success of any liberation movement in the United States. As Mike Davis notes, equal economic citizenship for them "would require levels of change dangerously close to the threshold of socialist transformation." Nature is dying. Humanity is suffering a cancer epi dem ic Two distinct groups have emerged, comprising- those w ho profit directly from this process and those w ho do n o t Capitalism can only confront the crisis of our im pending extinction by laying the groundwork for its ow n destruction. The day-by-day attempt to respond to this crisis generates antisystemic elem ents of protest and demands political solidarity. The practice w e evolve to survive the epidemic of cancer shall be determined by our analysis of these events. 's s' A "2 `H. i ; : STATE OF ARKANSAS D EPARTM EN T O F PO LLU TIO N CONTRO-L AND ECO LO G Y 3001 NAT'CNAL ORIVE P. 0. BOX 9583 LITTLE ROCK. ARKANSAS 72219 501 371-1701 WATER 501 371-1701 GEN. OFF. 501 371-1136 AIR DIV. 501 371-2130 SOLID WASTE Governor Clinton J a r r e ll Soul JW " Wafer. Solid. H cm idoB,CL i f j l 'm if. Compilante. te,a/.(L- Movember 2j\ STATUS REPORT - VERTAC AT JACKSONVILLE A. The Department i s now in the process of attempting to bring together some "loose-ends" concerning d io x in (TCDD) contamination r e s u l t i n g from V e r t a c ' s o p e ra tio n . Some s t u d ie s which have been conducted under EPA sponsorship have y e t to be completed and reported . Some of the Department's monitoring; e f f o r t s have been d eferred in order th a t o th er f e d e ra l commitments could be met. I t i s a n t ic ip a t e d that m o n it o r in g / a n a ly t ic a l a c t i v i t i e s can be resumed by l a t e December. A meeting has been scheduled f o r November 29, 1979 in v o lv in g V e rta c and the Department. Topics of the meeting are to in c lu d e : (1) S ta tu s of 2 , 4 , 5 - T s t a r t - u p p la n s , (2) compliance with the Department's o r d e r , and (3) d is c u s s io n of monitoring and a n a l y t i c a l e f f o r t s of V e r t a c , EPA and DPC&E. I w i l l update t h i s re p o rt a f t e r the meeting on the 29th. Jacksonvin_gJ3awage Treatment System The o x id a tio n ponds of the c u r re n t v/astewater p la n t are contaminated with TCDD. J a c k s o n v i l l e has completed i n i t i a l plans f o r a new system which would by-pass d e f e c t iv e c o l l e c t o r l i n e s and the old wastewater treatment p la n t . The plans were completed p r i o r to the Vertac in c id e n t. However, the A ir Force claims th at i t i s unable to p a rtic ip a te in the funding of the p ro ject and, as a consequence, EPA w i l l not r e c e i v e the plans f o r review and subsequent funding of a co n stru c tio n g ra n t. ( T y p i c a l l y , EPA pay 75% o f the c o n s t r u c tio n co stsi and------------------------------------------------------------------------------------------- Senator Bumpers e a r l i e r t h i s y e a r was t a lk in g about a s p e c i a l a p p ro p ria tio n to the A i r Force in order th a t we could get the p r o j e c t moving. I t i s h ig h ly d e s ir a b le th a t we do so because we can then i s o l a t e a portion o f the TCDD problem. Your a s s i s t a n c e in g e t t l n g T h e A i r Force or Congress moving would be h e l p f u l . A l t e r n a t i v e l y , the Department co u ld , according to EPA, sue the A i r F o rc e . We stand;ready to d iscu ss the issu e with you. 18945 Governor Cl inton November 26, 1979 Page 2 Meanwhile, J a c k s o n v i l l e i s proceeding with the c o n stru c tio n of an in te rce p to r lin e that should elim in a te the problem of overflowing manholes in the r e s i d e n t i a l area j u s t south o f V e rta c . Th is may, however, create problems a t the c i t y ' s e x is t in g wastewater plant and-&}tHrs-'tfiat the p la n t be by-passed during high flow c o n d it io n s , i l l be watching the s i t u a t i on c l o s e l y le n t Monitoring E a r l i e r commitments to EPA n e c e s s it a t e d suspension of much of the Department's monitoring o f s o i l s , sediments and waters f o r TCDD. We now have a backlog of s o i l samples taken from the r e s i d e n t i a l area surrounding V ertac and hope to be in a p o s it io n to s t a r t working on The Department has conducted some r a t h e r crude a i r sampling on V e r t a c 's p ro p erty. The f in d in g has been th a t TCDD adsorbed on p a r t i c u l a t e matter (d ust) c o l l e c t e d by our sampling device i s in the same range as we have found in s o i l samples on V e r t a c 's property We a re expecting a s e t of more s o p h i s t i c a t e d sampling equipment from EPA to i n s t a l l and operate both on V e r t a c ' s property and in the surrounding r e s i d e n t i a l a re a . We hope t h a t EPA's equipment w i l l give some idea as to the s i z e f r a c t i o n o f the contaminated p a r t i c l e s . Such inform ation w i l l provide b e tte r in s ig h t as to the health hazards involved. S it e Cleanup ;/ V e rta c appears to be reaso nably on schedule w ith requirements of t h i s Department. Paul Means has se n t an i n q u ir y to V ertac which, in e ffe ct, provides a vehicle for fin al determ ination/reconciliation of V e r t a c 's compliance s t a t u s . T h is w i l l be d iscu sse d in d e t a il w ith V ertac on the 29th and a r e p o rt submitted to you. I am very i n t e r e s t e d in e s t a b l i s h i n g a e ro sio n control program on V e r t a c ' s p ro p e rty . .Such a program w i l l reduce wind blown dust (contaminated w ith TCDD) as w ell as reduce the continued contamination o f Rocky: Creek and Bayou Meto. Before f i n a l i z i n g the elements of the program, I would l i k e to have b e n e f it of EPA's r e c e n t ly completed s o i l s |and geology stud y. The r e p o rt o f the study i s now in p re p a ra tio n . An a ly t ic a l'Q u e s t io n s Our contacts w it h in EPA co n tin u e to a l e r t us concerning a n a l y t i c a l q uestions. These questions impact current understandings of the b i o l o g i c a l h a l f - l i f e of TCDD and the p o t e n t ia l f o r TCDD to be degraded:under varying environmental co n d itio n s. At issu e i s the e x te n t to which TCDD i s bound to s o i l p a r t i c l e s , the .stereo ch em istry o f the TCDD molecule and " a c t i v e s i t e s " on the molecule. ,Q4 Governor;Cl in ton November 2 6 J 1979 Page 3 i ; I f you d e s ir e , I w ill provide a d e ta ile d explanation of the is s u e . For purposes of t h is r e p o r t , however, I am merely a l e r t i n g you to the p o s s i b i l i t y that g r e a t e r TCDD c o n ce n tra tio n s e x i s t in s o i l s and sediments than p r e v io u s ly reported and th a t the TCDD h a l f - l i f e i s longer than p revio u sly estim ated. Resumption of 2 ,4 ,5 -T Production V e rta c continues to hold production of trich lo ro p h e n o l and 2 , 4 , 5 - T in abeyance u n t il such time t h a t the s t a t e and EPA approve proposed plans f o r containment and d e s t r u c t io n of TCDD. In a c o n f id e n t ia l rep o rt dated November 5, 1979, V ertac summarized the results of various laboratory sca le experiments for clean-up and d e stru c tio n of TCDD. The r e p o rt a ls o contained flow ch a rts d ep ictin g how TCDD containment, cleanup and d e s t ru c t io n would be accomplished, using the process described in V e rta c 's patent a p p lic a t io n . I t is u n l i k e l y , however, that the depicted process w i l l be placed into o p eratio n because the re p o rt a llu d e s to an a lte rn a tiv e /m o d ifie d process which Vertac has developed which achieves a hundred-fold improvement in TCDD d e s t ru c t io n e f f i c i e n c y (to 99.999%). Presumably, plans and drawings of the improved process w i l l be submitted to the Department and EPA a f t e r Vertac completes amendments to i t s e a r l i e r p atent a p p l i c a t i o n . I have not received comments from EPA concerning V e r t a c ' s November 5 report. Delays are expected because EPA's p rin cip al coordinator, Brucei E l l i o t , has been s t r i c k e n w ith u l c e r problems. EPA and the Department monitored some of V e r t a c 's l a b o r a t o r y - s c a l e TCDD d e stru c tio n runs. Samples were s p l i t between the Department and a t l e a s t two EPA-sponsored la b s . Although the o u tsid e labs have: not form ally reported t h e i r r e s u l t s , p re lim in ary inform ation .suggests there i s s u b s t a n t i a l agreement w ith DPC&E's d ata. Based upon |the foregoing and based upon the Department's a n a l y s i s of V e r t a c 's more recent d e s t r u c t io n e f f o r t s , I am convinced th a t there: are chemical means o f d estro yin g TCDD in V e r t a c 's waste through a d e c h lo r in a t io n / e x t r a c t io n process to a l e v e l l e s s than 10 p a rts per t r i l l i o n . The Department has not confirmed the i d e n t i t y of the products o f the d e s t r u c t io n p r o c e s s . The i d e n t i f i c a t i o n may be accomplished by EPA-sponsored la b s . V e rta c maintains th a t i t i s capable o f i n s t a l l i n g and s a f e l y operating the equipment necessa ry to co n ta in and d e stro y TCDD r e s u l t i n g from the production of t ric h lo ro p h e n o l and 2 , 4 , 5 - T . V e rta c o f f i c i a l s have d iscu ssed the p o s s i b i l i t y o f se cu rin g an EPA grant to a s s i s t in the processing of sto re d waste products and contaminated s o i l s and sediments. EPA appears to be f a v o r a b ly impressed with the idea ;:i : i Governor;Clinton November26, 1979 Page 4 and would, in my o p in io n , fund such a program provided th a t i t was s a t i s f i e d with the chemical d e s t r u c t io n process and provided that you f u l l y supported the p r o je c t . I t i s a n tic ip a te d that the p ro je c t would in c lu d e , in a d d it io n to the chemical d e s t r u c t io n f o r m a t e r ia ls containing high TCDD c o n c e n t r a t io n s , p h y s ic a l se p a ra tio n s and biological degradation of less concentrated m aterials. Please note, however, t h a t b i o l o g i c a l degradation has not y e t been proven. Vertac m aintains th a t i t w i l l not be a b le to a ff o r d the i n s t a l l a t i o n of process equipment f o r the chemical d e s t r u c t io n of TCDD unless i t i s permitted to resume production of tric h lo ro p h e n o l and 2 , 4 , 5 - T . I am'not su re t h a t V e rta c w i l l be a b le -to a ff o r d the safeguards t h a t ' w i l l be imposed i f production i s a llo w ed . U n fo rt u n a te ly , that ^ jw rll remain an open q u e stio n u n t i l such time th a t the engineering rogresses bevond the-cofreeptual staorr ' continue to recommend th a t V e rta c not be allowed to resume production of trich lo ro p h e n o l o r 2 , 4 , 5 - T un less (a) the d e s t r u c t io n o f TCDD- containing waste can be a s s u re d , (b) both the production and d e s t ru c t io n processes can be adequately safeguarded, and ( c ) V e rta c commits to a phased program f o r the d e stru c tio n of stored waste products, inclu d in g h ig h ly contaminated s o i l s and sed im ents. The dimensions the phased program would n e c e s s a r i l y be dependent upon the ^egT^e^fjFedera 1 support obtained. ^ While the conditions described in the above paragraph are necessary, I am n o t ,s u r e t h a t they a r e s u f f i c i e n t . Broader q uestions concerning worker s a f e t y and environmental impacts r e l a t i v e to the use of 2 ,4 ,5 - T must a ls o be f a c t o r e d i n t o ' t h e eq u a tio n . Stu d ie s being conducted o u tsid e o f Arkansas may e v e n t u a lly p rovid e guidance. Recognizing th a t the f a t e o f 2 ,4 ,5 - T r e s t s p r im a r ily in EPA's hands and recog nizing the f e d e ra l reso u rces and r e s p o n s i b i l i t i e s in the f i e l d , I would be h e s i t a n t in attempting a ban, a t the s t a t e l e v e l , on the;m anufacture and use of 2 , 4 , 5 - T . U n t il V e rta c fo r c e s the is s u e by f i n a l l y subm itting d e t a ile d plans and s p e c i f i c a t i o n s f o r the containment and d e s t r u c t io n o f TCDD w a s t e s , I do not f e e l th a t the s t a t e i s o b lig a t e d to take a stand . By then, b e t t e r data could )e a v a il a b l e . 8 e rBWB T2TCr ?i?& Line r r > t r a c t o f lend s itu a te d in thu Csunty of P u la sk i, S ta te of A rkansas, b,-r.g p a r t o f th u r '- 3f . F r a c t i o n a l S e c tio n 3 1 , Tow nship 3 W orth, F.tr.fro 10 ~ o s t aad a t r t c f th e S i r : 2 o f S e c tio n 5 6 . Township 3 W orth, H in t.' 11 TTaat c f the j t h P rin c ip a l K oridiun and being noro p a r tic u la rly described as fa lle n s : P art 1: (J-212, J-213. J- lL . t J-215) B e g in n in g on th e e a s t l i n e o f s a id S2 !72c o f S e c tio n 3= * s - ? 31-- x h ic h i s 3 .01* 0 3 ' T . , 3 9 6 .6 f o o t f r o c th e n o r t h e a s t c o m e r of s a i d SZg-. l.'E? o f S e c tio n 36; th en ce 3 . u=* 05' 3 - , 607.0 f e e t to a p o in t; th enae 23* i i i ' 2 , li~L. 0 f e e t t o a p o i n t ; th u r.e e K. 26* 2 1 ' S'. . 11." : : e t t s a p o in t or. th e s o u t h e a s t e r l y l i n e o f t i n is a o u .-i P a c i f i c H u ilr e a a C enpar.y's r i g h t o f-w ay ; ch.-nec ? . 5U* 0 9 ' 2 . , 30 n i f e e t a lo n g s a i d s o u t h e a s t e r l y r ig h t- o f - w a y l i n e t o a p e in e ; th e n a o 3 . 26" 2 1 ' 2 - , 1= 0.2 f . e t t o a p e i n t : th u n ee S . 23* U61 77., =1L.0 f e a t to a p a in t; th u n ca S. lie ' 0 5 ' IT., = 21.a f e o t to a p o in t; :hrir.ee a w*J OV T . 77 i*cct to a p o i n t on th e na: l i : of z',no Arhc Ordanr. co e ! .m t "7 - cor ; i c ' L: r. Lr * " T. , ii2.ii ro o t alor.z snid n o rth s n s t_ riy r i' :o ir.t ; 2h o rc o 'V21* 03' 2 . , cC . O w to C pOlaiC f thv 21.2 f a i t to t n i p o in t o f b e g in n in g , c o n ta in in g 0 . 9. a c r e , store o r l e s s . P art 2: (J-21h) 3 e rin n in e on the r.o r^ . lin o cC sa id ? ra c ric n & I S ectio n ;1 a t a w hich i s <7. 87' !i5' 2 = 9 .3 f o o t i r o n th e n o r th w e s t c a a r o:' s a id S e c t i o n p i ; tra .-c e $, 67* L?f 2 . . 5 ii.2 f** t a lo n g s a id n o rth . lin o c; F r a c tio n a l S e c tio n p i to u p o in t; this aco 3 . 2c* 2 1 ' 2 . , 753- 2 f e e t on th e n o r t h w e s t e r l y l i n e o f tho Lite s o u r i P a c i f i e H ail.-cad C en p ar.y 's r i g h t cf-wuy; tr.enca S. 3i* 0 9 ' . ;.2i fee:: alar.g sa id r.o rth ..e s ta rly r ig h t- c f way li n a t o a p e i n t ; t h a a c c K. 26* 21 7e., S ic ,6 f e e t t e c.no p e i n t a f t e ir.r.ir.f, co n tain in g C.5? acr* , ne re or l e s s . rv retit fo r T a ta r Pipe Line C re ssir.;; (j-20ii-A ) A t r a c t of land s itu a te d in the County o f P u la sk i, S ta ts e f A rkansas, being p a r t of t.-.e 2? CHc- o f S e c t i o n 5 c , Township 3 F o r t h . Hangs 11 T e s t e f tr.e pt.n F .-n -.-.-a l r: e r i ii a n , and b ein g more p a r t i c u l a r l y d e s c rib e e as allo w s: B eginning on th e s o u th e a s te r ly lin e e f th e liis s o u r i p a c if ic H ail read C e npar.y's b i r th t - o f - n a y a t a p o i n t v.hieh i s M. 59* 0 9 ' 77. , 393 , s f e e t f r a n th e r .s r t h u s s t c o r n e r o f tho S 2 f Hag- o f s a id S e c tio n 56; th er.ee 3 , =4' 0=!' ; 0 .Q f e e t a lo n g s a id s o u t h e a s t e r l y r i r h t - a i - w u y l i n e t o a p o i n t ; ther.ee .7 . 53* 21* 7 . , ICC.0 f e e t to an tr.y n o r t h w e s t e r l y lira - of s a i d ^ ^ s s . r s i j i ' - s cr F * c i c I la iir e r .d Germany* s r i ^ a t - c f - w n y ; tr.w3C0 y* 7 5 ' I . , ;C .0 a l e a r e a i d .- .c r t h i / o s t- r l y r iir .t- e jf - w a Ua-* to c. o o i a t : f i j a o s S- ;3 * 21* ! . . IwO.O to thu s c ir.t a;' b o iria n ia r # cor.toJ.aia-* G .J7 ac.-os, ccr* or l*joo. p'" 2 -3., i ;j .r ~ l- = r .Toil S ita : Pari 1: A - r a s : ci la n d tis u e a a d ir. Caunsy af r n l s a h i , saso ci A rh a ss a s, b a t jo a c i'. 100 I'j . t af rra c a la a a .1 S c e s ia s 5 1, 'av .o a r.ia ; M -s.-i, Sir.--. 1C '"ass a i she pih "r ih c is a i oridisai, e ansaihtats 9-09 a ra s, aura ar le s s . P-..~a 2 : A. - r a c e lcr.d a ia u a a a d l a aha Caar.ay ci P n l e s i t i , S t a i r a f A rk a n sa s, he l a : p a r a a f aha 377?- t f O ac a ia a 32, awnshiE 5 Mer a h , ?.'_aae 10 'Ta-a a f aha fa.a P r i n c i p a l " a r i i i - a , ar.d a-ai.a h e re p a r t i c u l a r l y i s a a r i t s d as f a l l - . * : a l a r .: She a/eaa l i r a a f s a i d S a e c ia a ; 2 . 1CC.0 f e a t a : a pair.-.; shar.aa a is a and p a r a l l e l aa aha aaaah l i r a a f s a i d j a e s i v s J 2 , h f l .O f a s t a., r. a a i n : ; ahsncs aaush 101.1 fees S; a re in s 'a aha so u th l i r a a f s:.ld S e csiaa 32; s h a re a ttsss a l a r : s a id asvish l i r e aa th e r a i n a o f b e a ih n ia n , c a a s - a lh iz ' 7 .oh CCrtS, ntr*? tr iw'SS ? trt tr.s -,'f p m c ti-s n n l S c s t i r r . T rc n s h ip 2 '.Ic rth , ?.m ~c 1C T s s t t f t h : Jc h P r i n c ip a l .uri'iinn s.r.d c c i o r s e r e p a r t i c u l a r l y d e s c r ib e d r.s ^ i er** r.ecinnins a t tr.a northw est e a rn e r c f sa id F ra c tio n a l S ectio n 7; thenco a a s t o lc u * t h a n o r th l i r e c f s a i d F r a c t i o n a l S e c tio n 5, 7CC.C T e s t t o a p o in u ; sh in e s c u t a ICQ.O f s e t to a s t i n t ; th a n c e w est and p a r a l l e l so tn e n o rth lin o of said F ric tio n a l S ectio n f , 700,0 fo o t to a p o int cn tha w est l i e s o f s a ic r r e .c tio r .a i S e c tio n 7 ; th e n c o n o r th a lo n t; s a id w est l i n e to sr.o p o in t of b tiin n in g , c c n ts in iu s l.oO a c re s , a cra or le s s , P srenccnt Fcscm nc f t r Access Hoad: (j-207) A t r a c t o f la n d s i t u a t s d i n th e C ounty ci P u l a s k i , S t a t e c:'1 A rkansas p a rt a f tne o f F r a c t i o n a l Sac t i e r . 50, c u n s h ip l w o rth , Hz=5j 10 o f th e =sh P r i n c i p a l .u o rid ia n , i n Dupre1 ; A d d itio n . to th e sct.t. a f 1 T ills , A thensta, end asin r h e r. p a rtic u la rly d e s c r ie d a s'fa llo w s; "a r e a l Ai - 3 sci.--.l a : an the s o rtit and so u th q u a r te r U i . c f J s l c 3 ;c s i 30 aa a p o i n t w hich is 1'. 02* C0< . , 3 1 2 .0 f t i t f r e e uh- c e n t e r o f s a id F ra c tio n a l 'S ection 3C; thsnco 0 2 * o o - lh .6 .5 f = o t e l a a r s a id r.arar. sr.d s c u th o u /ira c r li z a Sc a r a i n s ; th o r.co $ . U r OU' Z., 2 3 9 .1 f i a s to a p e in t; Shar.eo 3 . 3 ~~i a:i__2 fa c t t o a p o in t; Shsr.ce 3 . ?6* 37' 2 - , 172-7 t a a acih-a on the-. w .i - r r r l y ri r . t - a f - . r v - U ; e Cf ; : , s . " i ,-r... i v . sT : a h --'.as 1 i b ` , J - ? ii i .2329 ) cr fok:: :* :za::z?i?. iC'CTT ALL "IF!! :Y TnSTS PSZIELTS. T h a t th e T ar S u u a rts ttn t ( T r a n s f e r o r ). ^ c V .n r th ro u g h th e Cocoosndir.g O f f i c e r , A rkansas Ordnance P l.in t, L i t t l e P.osr, A rkan: z s , by these p re se n ts does tr a n s f e r custody, c o n tro l, and a c c s u n tib iiity .tr.to th e ""at A s s e ts A d m in is tr a tio n ( t r a n s f e r e e ) , th e fo llo w in g I r n d and in pro .scr.es t h e r e o n , to " i t : The A rkansas O rdnance F lo r.t l o c a te d ir. P u la s k i C ounty, A rk a n sa s and c o n ta in in g a t o t a l o f sever, bhousand two hundred f i f t y two and n i n e t y - j i i t one h u n d red th s l c r e s (7 2 5 2 .r6 ) th e l e r a l d e s c r ip tio n o f rh ic h i s a tta c h e d h e r e to i s E x h ib it ''A** w hich i s made a o a r t h e r e o f : A ll b u i l d i n g s , u t i l i t i e s .and im provem ents which a r e o r e s e r .t i y l o c a te d on th e Land e r.b rrc ir.g th e A rk a n sa s O rdnance P l a n t , th e d e s c r i p t i o n o f which i s a t t a c h e d h e r e to a s E x h ib i t " I " w hich i s made a p a r t h c r o e f : A ll " in s ta lle d re e l property*1 which is p re se n tly lo cated In the ib cv ei c s c r i b e d b u ild in g s o r lo c a tn d os: th e a b o v e - d e s c rib e d p re m ise s th e d e s c r i p t i o n o f u h ic li i s a t t a c h e d h e r t t o a s I n h i b i t "C" whicr. i s made a p a r a h e r e o f : A ll o f the p erso n al p ro p e rty lo c a te d a t the r.rkansns Crdnar.ce P la n t as d e s c r i b e d cn Forms TFB-1 o r 3 F 5 -1 .1 , OP.D 0 5 -O lii-u b -1 th ro u g h lad5 i n c l u s i v e . T h is t r a n s f e r i a in te n d e d to c o v e r and -marac* a l l rJ . S , O cv em r.en t p e r to n a l o ro p e rty o n cep t m e ta l coK rouents ar.d packaging m a te r ia l f o r w hich th e T ra n s f e r o r i r Accountable. S aid m e ta l ccr.wcncr.ts and p ack ag in g m a t e r i a l "i l l be removed from the prem ises by th e T ra n s fe ro r w ith ir, 50 days .a fte r th e e f fo e civc date h ereo f. The T ra n s f e r e e -.rill p ro c e e d to make such in v e n to r y check s a s he deems r.tp cessary p r i o r to 1 J u l y I9I16 o f th e p e r s o n a l o r o t e r t y d e s c r ib e d in a b o v e , r e n t i e n v d : : r o : 3 ? 3 - l . Any d is c rc c & n s tu s d i s c lo s e d .as a r e s u l t o f such checks w ill be reported by the T ransferee to the T ransferor for accessary adjustm ent by 1 Ju ly IcL/j. The e n tir e f a c i l i t y (in c lu d in g re a l and p ersonal p ro p e rty ) h as bsen cecnr.tar.ir.atwd and ?s s a tis f a c to r y fo r id le stand-by co ndition fo r use in i t s e risin c .1 p u rp o se. Hi* f a c i l i t y has been review ed by a beard of con s u l t a n t s and i t has been r&cosaraendes th a t s e v e n ty -th re e (7 3 ) b u ild in g s ( l i s t e d on P^ge 1 E x h ib i t C) w hich c a n n o t b;* c a n o n ic a lly d e c o n ta m in a te d should be destroyed in the event th e f a c ility is d iseased of for o th er than i t s o rig in a l purpose. The u n d ersig n ed : rin sfe -rc c hereby acknowledges th a t d e liv e ry c f th e s a id iar.d and im proved.-n t s was mad*, by th e t r a n s f ; r c r an d r e c e i p t o f s a i d p ro p erty is hereby ackno*.:I:dgi.d. The undirrsicr.ed Transform s hereby agrees th a t on 1 J u ly liio f u l l a c c o u n ta b ility w ill bo u s s u rtd sv sa id T ransferee f o r a l l n trco n u l p ro p erty l i s t e d or. Forms T H i-l. OKT 0 5 - j l ^ - v j - l th r u CF.T T f-O lii-uC '-'idy and f u r t h e r r c ^ e i f .t a f o r a d ju s tm e n t w i l l bo made t o the T r a n s f e r e r . IT "*ITTE33 T !!E ? .IT r, th e T ar D crartn o n t a c tin g th r e u s h t h e Csrrcar.dir.r O ffic e r, A rkansas Ordnance P la n t, A rkansas, and T ar A ssets A d m in istra tis:., have h e r e u n to s<*.t t h e i r h an d s t h i s l a t h day o f June . " AS EEPAST HI!" (I ra n * f u r o r ) _,_y y ( / / / --ry c T ss.- _<e :::Jesms My-- / C a rt., C rd ./T v ct., { Cc-- .r .a ir.r O f f i c e r Arkansas Ordnance P la n t, Arkansas Vut kzzzzz A r .:i::i3 iH .- .t :o ir ( T r a n s f e r e e ) 3V:0 4 ) iCfczzrJfr. . ) .! r\ ^ r''r* Wilmington September 1 TO: Messrs4 J . G . Copeland, Jr. E. Turk J . M. Ecgan J . Z . Miller K . T. Givens G . A . Seely - Engineering A . L. Larson - Engineering B. W. Dickerson - Engineering H. F. Heckroth - Engineering H. H. McCrea - Engineering H. E. Wilder - Jacksonville DEFOLIANT ORANGE 8.0 Million Gollcns/Vear Mixed Butyl D and Butyl T Esters Welo'on Spring, Missouri ! 18956 I < .I '. I; i ': Orange - 8 Million Gallons/Year Criteria The attached is a basic process criteria for an Orange plant calculated to produce 8.0 million gallons of Orange per year. The liberty was taken to use the data and calculotions and assumptions made in March 1967 as a base line which was calculated to produce Orange at 6.0 million gallons per year. It is realized that several major decisions must be made, namely: i 1. Continuous versus batch MCA process 2 . Clean up process and quality required 3 . Waste treatment and disposal specifications The following is intended as a preliminary criteria from which the final guide lines, project estimate, and the formal proposal will be made. Comments, changes and criticisms are solicited. The following assumptions have been made: 1. The quantities of D and T acid are based on the Government specification ; as 50/50 Butyl D and T Esters by volume. 2 . Production of MCA is based on the present botch system used at Jacksonville. 1 3 . Both 0 and T acid will be dried and handled to Esterification with Tote Bins. 4 . The acid reactors will be 3,000 gallons maximum working capacity to avoid unknown agitation scale-up problems especially on T acid. 5 . The glass lined vessels will be 2,000 and 4,000 gallon standard reactors and Chemstor tvpe storage tanks to minimize delivery time. 6 . Dechlorinators will be nickel clad 750 gallon copacity reactors built for shell operation at 350 psig. and jacket operation at 150 psig. 7 . Solvent clean up is based on the present multi-stage batch process currently' being used at Jacksonville. 8 . An entirely new-and complete waste disposal system must be designed and installed. 9 . Approximately seven-day capacity has been used for raw materials and in-process storage. - 5'" 1 - 1- V Co leu loHons Basis 100% Acid & Ester Orange - 8 Million Gollons/Year Assume average wt./gal 10.70 lbs. Wgt./Wgt. (Hercules) 42.8 MM Lbs. 42.8 MM Lbs, &6. MM Lbs. Voi ./V o i. (Gov't.)" 4 MM Ga I . Butyl-D* 4 MM G o l. Butyl-T \ 8 MM Go I. Assume sp. gr. Butyl-D - 1.245 10.35 lb ./gol. * " " Butyl-T - 1.325 11.02 Lb./gol. 1.245 x 8.33 x 4 MM 1.325 x 8.33 x 4 MM - 41.48 MM lbs. Butyl-D = 44.15 MM lbs. Buryl-T . D Required Lbs. T Required Difference Lbs. Ester 1.32 MM 1.35 MM Lbs. Acid Represented 34.24 MM 35.10 MM Difference 33.18 MM = -1.06 MM D Acid 36.20 MM = +1.10 MM T Acid Hove built Into estimate sufficient capacity to go either way. By A . E. Sidwell 8/25/67 -2- 8 fr-  J . . .'J ./V . Py--C.V..I.ia * CCM PANY <u\ v`wetia----i-*>..t--.* ,.*: m. yv ce: J. X. - Syn. H. A. Tares . B. . J. J. Tord - K. C. A. Z. Canner - R. C. A. 0. Sldvell . Jacksonville a-'.'J. Vllalngiao-,'"Eelavare Xovenber 10, 1965 L. Duna Synthetics Drparwnt TSQfc X. X. Chrlstofano - Medical Depajtaent (.1 ' ' t`'aM..r 1 * 7 eO * ** Is?/ '.* Use follovlng casent* vlll unserlse tb/_lvllx*llon centetlate chloraen# possibly associated rtUT2,A,5.T citer*. 1. Indisehe/Uses'* bloassay technique to check each batch of TC? purchased.W?heir kbit consists of feeding each of three rabbit* with a ofcjssf with a determination of braneolphalelB retention after .3 dajn*. lure than JJ of BSP retention 1* eu*#"-/or' rejection of the batch. Sensitivity 1* elalaed at 3 ppo. 2 . fey bloassays by a ribblt ear palatine technique, the Internal turfacc of eoc rabbit car 1* painted dally vlth 0.1 al. of a ehlorofora olutlon of te*t naterlal (10 or SO?) of an extract of TC? In chlorofora. Unless aeeere Irritation 1* noted lOjJoaes are applied, the car* are observed for tun additional veeks for the appearance of folliculitis and C7*t forsatlon. they have noted fatalltlc* fro* a Ingle pplleatlon and liver damage ha* acccs^anled the chloracne reaction*. Sen*ltlvlty 1* s y be aore *en*ltlve, the Badlsche nethod In order to evaluate both nethods ve recceemd 1*1 to Badlsche for their teatlng and alsultaneouily 'data la a caserclal laboratory. Because of a toxicity of la-process naterlal*, the** latter __ . after oral toxicity ha* been determined. Ter thl* first Yv*gx_ih-*tut oral IX50 studle* vould coat approxlMtely $300. Subsequent adnegen (tudle* on theee Mterlal* are expected to cost about $,000,'hovetWr, an accurate eetiaate la not possible until Stage 1 Is complete. Preparation of the anpla* and subsequent analysis 1* estlaatad to coat $500.| m*# * 1, r. i 1 .j ^ ' j f TV DOW C H E M IC A L U.S.A. November 1, 1978 BENNETT BUILDING 2030 DOW CEN TER MIDLAND. MICHIGAN 48640 Mr. John Calloway Vertac Consolidated Suite 2414 5100 Poplar Avenue Memphis, TN 38137 Dear John: Re: 2,4,5-T ACID - YOUR LETTER OF OCT. 24, 1978 John, we are issuing the purchase order this date to cover the movement of 500,000 lbs. of 2,4,5-T Acid in accordance with my letter of October 9, 1978, subject to the following addendums as noted and accepted__in_yonrletter of October 24, 1978: 1) Will agree to accept your clause stating^thai--Dow wiHOTpurchase any product that you^ have in inventop r ^ Q r ftTM-7 aV The time of any government action that'"bans '"the sale,"manufacture or Importation -of -2 ,-4.-S^-T-Acid.,________ 2) Trip leases of Dow cars will be 15 days for 10,000 gallon tank cars and 21 days for a 20,000 gallon tank car. Detention charges shall be as per my letter for days beyond this. 3) There shall be no imbalances in raw materials input and materials supplied to Dow. Vertac will supply materials to Dow to b a l a n c e <~m f ar> y p -k c p ^ s in trichlorophenol supplied by Dow. 4) Specifications: We will temporarily suspend the 2,4-D Acid specification subject to further discussion. John, as I pointed out on the telephone, I feel that there should be no problem on the movements for the majority of this product; however, there are some small applications for which we may have to have a much tighter 2,4-D Acid specification. However, to allow us to begin to move product to areas that will require it in December and January, I think we must proceed leaving this one particular ambiguity. Appreciate your cooperation in this matter. Sincerely, E. R. Russell Supply Manager U.S.A. Purchasing* o p e r a t i n g u n it o f t h e d o w c h e m ic a l c o m p a n y 8 QAJ f. O r> A  o a x< m n n w n * r Ol `*B** T H , OTgmnjta *j "*n . v m *j *o **a ** Wtrw in u l JfjB tm tt r * t* m m * n w i m *J w t B M H | R ) W X M JLu m l { ; r ft* M * * **m *i*m m **< .m ^ i K i t ** H-- a T- l t M < H I * *WI M* vm m 'rnrm H n * m it pw W I *T *?MC >pn^ H L. w * w " i p 4 * t* w m *nj m * Ma r i y n>-- m m n " ' o `W i `r t - 4 t w i o t : mb j j p j^ :* %* p* " P ! U i wo m < u n m iw >tg t m n o ^ , w O M M i M *** M *M Ttv M `e e tltw w f f m i h m t M C 1 WWfl s o tti * ` H W T* a **1>W*H I t**W i l q * n u v i* w aw d*a MI ) A w >"i DM -- a w u lM 4 M iai; O*! *r -c iVv! .`t 0000343 Kr. V. K. Pcve Biochemical research Laboratory The Dow Chemical Company 1701 Euilding Midland, Michigan Dear Mr. Rove: As you may recall, Hercules has been attempting to develop a bioassay technique to simplify detection of dioxin In herbicide formulations. Based principally upon vork Initiated by Dr. Oettel at BAS?, the tests 1 measured:liver function changes which result froo feeding rabbits with t herbicide. ;We feel such a technique offers several advantages over rabbit V ear painting tests. .i *. Unfortunately, ve have been unsuccessful. But to state It so bluntly Is really unfair. First, ve attempted to determine the sensitivity of liver ;change by feeding test materials with known additions of dioxin. The toxicity of test materials prevented use of liver function change os a bioassey ;fcr dioxin even at 10 ppn. Ve then dosed animals with 0.01 U 0.1 ng/kg of dioxin suspended in corn oil. Carbon tetrachloride vas administered as a positive control at 100, 250 and 500 mg/kg. Clinical determinations Including SCOT, SG?T and ES? retention were conducted prior to administration and every two to three days thereafter for at least lb days. Hj Significant elevations In one or more of the clinical determinations were found In some but not all dlcxln animals. The changes vere not veil correlated vlth dose nor vere they consistent vith regard to onset or duration. Animals on the positive control test responded as would be expected vlth ignifleant blood chemistry changes only two days after dosing vlth 100 cg/kg. : Although positive results vere obtained vlth dioxin, the usefulness of this technique aa a bioassay for the presence of dioxin is questionable. : At the Toxicology Roundtable Z mentioned these results to Ken Olsen vho suggested that you might cocr.*nt upon them. But the other reason for vrlting Is to solicit your opinion on the usefulness of presenting our data at the Society of Toxicology meeting next spring. Certainly such a presentation vould raise questions as to the reason for conducting an unsuccessful study. Mr. V. K. Rcwe -2- October 16, 1968 On the other hand, someone night be spared useless effort If such negative information were offered to the scientific comuaity. I'd lihe to have your consents before ve proceed. Sincerely, EEC-.rba Sail E. Chrlstofano Industrial Hygienist 189  . K. I , f k m . I r . U t . jlc. I M A nal. H f . JU6. Ortater U, 19& i I r a f M a r X* O a tttl fta u c a ln l. ! u i i Car 0tX f A.9* t teauRteZor AUn 9 7 W v i'i'a r a ThttMf arttecM aoX ` >/s/*4 J 8b*r T ra ite * CaitaAi Hr r4a 31*1 a f oor Ka;aa f l b u m t m i i ty c n a* k li U U n t i l a : r> : t a h n i K l n H * l( v ttb >wu a a i tkr. I b t s a aa tk l tU # f A *^art. I lae-rrix 7> v :l* v Cb* c o u rtc c r l" n**l to H r. C lelajaa tw la ; ta la T ld `. va } t v U b 'iv U r,'! Ca ha* i r f c r r t l K tareX ( K i'.ia a i va m X itb Z v i l l altacp t U irrv sr. Xa w r ra^ '* * f 2r tb i n a n T a ^ v t e# |Z}*T i r i : f ** 4o o cl taoZ aia tiU .M .ra jli'n l Zt ta to r t i l a ruasaa U a t w 4U aav a a ! a? V ri- *hl?ra;4ra?X . Xt u krw m yo m U b i ah la va U a lK Vta a^ylca o a r .tir . t;lilsr3 v i.:r.a* .a, .`i l ,5*X : t l , a l A .1 h c t/l v ruallaa Wcmuat o tb* c--uv*r t u l d v r o u k t t e a a n stv lT tt/ 7 y s w M a la ^ a a l u u y t 'A l a r l a ' la y n o t t e m p ^ a t BlcZaraa a ta la l t t e t t t e a ? l lo a l arpia a f Ifl p o n a vauZl a si W l a ^ a t i la r j w aaca;-. A rrw lla ;A r, vy l a n b lp o i lx c c tly to .o U b jitU if a p n d r i U l X3i p a a * i l l t l n a l o f arp laat UJlS5TTllO-*j5i--Zl XUlVV^O^-55!3*-11 X1l>J.iS0C-3-T b o j-1 a a ia r a f S',b ,J * f (14 aadlua r ( S3>irlchlorspbcaat-a oa aay<rXll*i>* fte s tlo a (boa p la o t proeaaa v h a n u > i! d |v 4 ZCD c r r i a f M f l a Id ao tlftaA aa< U ST ^U f,k ,J-T a c il v fc lrt la t a m .-a> aa praviana acrrAa AXU 7 -l l, te*. fi-sa a l l u n t p ta ta rtla a tetes. C a ; I ai.pt?* rro'j^Aas l a>v a l l r l d ` d .i< Xf you v ite to *14 l'x iS f U u f r o v la aaspl* > 1 5 .'^ ^ * r a l p ir* H a d a u a r t* M>X* ( l l j s 'j ox?it k 1 a t o ts iw t ta f a i v i *Z * *k ? U f U n triiM c r a - pto-.a-'V ailbe, va d j n a i r a v s o r t X ,' u . l o . ; t i l a taU rlrX # y I-a i fi;* 't a*^X a o f rula TXT* fre s o v {Macoca c sv jU U / f s r ytwc taa?r- po*e*. ta la arp ia (ZOO ( e s ) bteaaa oa llaaa Wte oua aaxZl 1 il'Xx l.ilfl olnX* . aa J?Al 2LUW$j.. t e la -ro lrv l a te * . Uk n atu ra c f t t e M < u y o n lflib U f t t n l o a p tav la u a l? cllor V Ef CZala-as* 7.J a o c u la r a f tte n c a -ti^ o n in a b la too m o uva h O J *J.2 t w FtvfM M r O rtM l: r 4 .w * :< : k 3 r 0 P, 2 0 1 8 h*. : n w-Yi; A I -3 5 ;? | e s Ks i I h I 1. 73 M |PKdlw,-<np 5 1 * o".5 H W M -r*sy*>s js.-S a ^^o-3ip f'<St N* )v> f*I I. 1 1*5 - I E S 4 J 25 g "J tJ*W1 W - ,.g 3 :2 ,iC Trl*i*:?VIM#3O^j| t#* f --i t *2 s "*o-.i* v: iaa m.* .< * < M e v 3..iVlf.-uaiSsiii* 1 I. n C jiS , {s -3 * V ''i s1 SI V -X M-- Ui *1 :! 1z 5 5* *a w 0 fri h j ~ i t :: IwmmJ-.I5l iSfSyEc, 115 ta K1 -#**IP#I*K*.**4!W*J*j#K6j * 4 4 * Im'.*>J wr UI s.i i .i. A & -4 d I 4 .3 * - * 4#M J K. - ; 2 3 s r 5BI KV -^ VV 5 P. V w *, 39 *WI HK-mfi*`.4TtI.f I M H U h r V f H 1 H . 2 * g : a J i I: i `< 4 V B l e : : . . s . MUj yI I* Ui *3 *r4s --i i MJirf 4 "- i ' S i s 5 1i l j iM * S ||s mi*h ai -i* w fl t oi *7f*34 v's a3 - * " . . ( I 5 3 k j -, I - <| K * * i i f wv / J5l C 5 5 4c#*f*a4fI 4wM^4*4SM;** /.SS *"*1**3 -p j t- it s* si 2- !A : 57 rVS'4f35u* 4> 1 1 I 3 : r. O I !_ 4-* ^4 HI Ni.i*. ; 5 M UtV iH V * ! 1 1^* j l.) vAi QD CO <' "'1 i\3 0000343 Kr. V. K. Pave Biochemical research Laboratory The Dev Chemical Company 1701 Euilding Midland, *<1chican Dear Kr. Rove: As you may recall, Hercules has been attempting to develop a bioassay technique to simplify detection of dioxin in herbicide formulations. Based principally upon vork initiated by Dr. Oettel at 3AS7, the tests 1 measured liver function chances which result free feeding rabbits with 1 herbicide. We feel such a technique offers several advantages over rabbit *' ear painting tests. \ Unfortunately, we have been unsuccessful. But to state it so bluntly is really unfair. First, ve attempted to determine the sensitivity of liver change by feeding test materials with known additions of dioxin. The toxicity of test materials prevented use of liver function change as a bioassay for dioxin even at 10 ppm. Ve then dosed animals with 0.01 & 0.1 mg/kg of dioxin suspended in c o m oil. Carbon tetrachloride vas administered as a positive control at 100, 250 and 500 sigAg. Clinical determinations Including SCOT, SG?T and ES? retention were conducted prior to administration and every tyo to three days thereafter for at least lU days. Significant elevations In one or more of the clinical determinations vere found in some but not all dicxln animals. The changes vere not veil correlated vitt dose nor vere they consistent with regard to onset or duration. Animals on the positive control test responded as would be expected vlth significant blood chemistry changes only two days after dosing vlth 100 mg/kg. Although positive results vere obtained vlth dioxin, the usefulness of this technique as a bioassay for the presence of dioxin is questionable. i At the Toxicology Roundtable I mentioned these results to Ken Olsen vho suggested that you might cocr.eot upon them. But the other reason for vrlting is to solicit your opinion on the usefulness of presenting our data at the Society of Tcxicolocy meeting next spring. Certainly such a presentation vculd raise questions as to the reason for conducting an unsuccessful study. Hr. V. K. R_e_w_e - 2- October 16, 1968 '.II On the other hand, soneone nirht be spared useless effort if such negative inforzati on vere offered to the scientific c c m u n i t y . ;I I'd like to have your consents before ve proceed. Sincerely, IC:rba fiali E. Christofano Industrial Hygienist 1 i J I -v.*. .VCNOAI* COWOn*r <c: D r. R . S . C i| D r. R. R. S<( M r. K . S. P . Bellinger M r. J .M. C|<* M r. R.T . T u n M r. J . H. Neal D r. 3. P . T raw ley . Medical M r. 3.C . Kuaikalm Legal TO: PROM: On M arch 24 D r . 3. P . T ra w le r and 1 attended a 'Mftlni at the Dow C h e m ica l Company B io ch e m ica l R e e e a rch Lab o ra to ry at the invitation ml M r. V . X . Rowe, Aaaiatant D ire cto r ml the-laboratory^ At~lhJt~meeting we waro informed of Dow*a finding te ia tin r-iP -h ith lr tonic im purttica that m ar occur ia 2. 4, S-trichlorephenol. Methoda for delecting th eie'im p u rities in 2. 4 , S .trich io ra p h e a o l and product auch aa 2 . 4 , $ - T w ore alao given. Dow die cava rod that a change in th eir m anufacturing pvoceaa cauaed the appearance of chlorpacaegene in their trichioropfeienol. Plant poraannol have ahowa m ild to^aevere^aaea of c U o r u c t m a~canagunce aif enpoaure _^to a m a ll amountm/mlrtar Jram -th e-p ro cee a;-- R e co v e ry fro m chJoroacne m ay re q u ire everaLyoa> ^ thar 1 no effective^theraovv. S in ce dlagnaeing the--c au ae. Dow m o d iiied ita procaa~aad haa boon operating without incident f a r jh e - paarfive Dow aaya that th e ir anam ination of th e ir own and competitor 2 , 4 , S - T product ahowa that aome m ay contain what they te rm "a u rp tia in g ly high" amouata_eLtha_loai_impuritiee. T h eir analyeia-of-Hercuiea.2, 4,jb _T_ haa given a low value fo r there tonic im p u rltfoe. ie view ef the erious problem that can a ria fro m the preaence af~avon m inuteg yantitiea of auch im purltiee, I recemmend-that-a-program deeigneito-eaam w e.and . _ i teat cu rre n t production of t r ic hioroohewol and T C P proeeea w a it he tarted, | and that a ayatem of am ple reteation and m ridic~ ttihK "of'TC P-and/or---- itfb V ** * if ' ! * $ 3a u ! I advlaed Mr. Ttsrtvur that I did nut think V M > 1 proper gaeetlsn for ae and that be ehruld fee cutelle drier froa private eenaultant If be doubted '.be aavlee ef hi* run tezlc3lc.lt:i. I printed cud that considerable Individual profeeelcnal Judgseat wruld be involved In eetabllchlag * epeei n eatloo cr this type because all ef the Important factr are r.oc ensue. He then rdated that. Qtv vat ex* ready frightened that tbla slttatloa \algh*. explode, flier are arare that .htlr-.roopetlicre-are-aaraeting-o,li^5-T'which contains *alaral^ _aaoun'-i" of aer.egen and 11 the roveraaent leant of tbls the u^ole Industry util suffer. They are"par*.!eulirly faaxful~e? a Congreielohal j l.-nx-*-*-t-l-C-t-i-o-n and. azeeael*ve rtft-rl--e-t-l-r * 'elation cc nufaclure ef pectieides-"^ whleh etgt't "" 1 advised It. fVoHac^hai we chared hlT~fear~but .very act aware ef hie allegation that the competitor!' prodiists werv-hazardous. He asked If Hercules bad established an Intsrnai epeelfleatlon. I stated that hr cbould dlaeuae this with eoaeooe In our aanagsaent and referred hla to Mr. Copeland. I reminded hln that we bad xperienerd great difficulty lr. conducting the analyte( for the senegas by the Dew procedure, anu that only within the part few weak*, following a vlrit of our chLists to Midland, have we been able to obtain any useful information. I suggested that If he wanted any additional ir.foraatlcn on hi. prsblea he ehoula talk to Mr. Copeland. He acs-d that he be transferred to Copeland. (Af.er the call vac traneferrrj I learned thet Mr. Copeland was ou* town and Mr. ffcrnhas left wera that he w: ult call on M'nday, July 1C). . u_-/ ll0 1 J w * l c U a u ra *(7 vr HERCULES INCORPORATED y- Wilmington September 1 TO: Messrs, J . G . Copeland, Jr. E. Turk J . M. Ecgan J . Z . Miller K . T. Givens G . A . Seely - Engineering A . L. Larson - Engineering B. W. Dickerson - Engineering H. F. Heckroth - Engineering H. H. McCrea - Engineering H. E. Wilder - Jacksonville FROM: A . L. Tre" ' ' Synthetics Department DEFOLIANT ORANGE illion Gollcns/Vecr Mixed Butyl D and Butyl T Esters Weldon Spring, Missouri Orange - 8 Million Gallons/Vear Criteria The attached is a basic process criteria for an Orange plant calculated to produce 8.0 million gallons of Orange per year. The liberty was taken to use the data and calcu lations and assumptions made in March 1967 as a base line which was calculated to produce Orange at 6.0 million gallons per year. It is realized that several major decisions must be made, namely: 1. Continuous versus batch MCA process 2 . Clean up process and quality required 3 . Waste treatment and disposal specifications The following Is intended as a preliminary criteria from which the final guide lines, project estimate, and the formal proposal will be made. Comments, changes and criticisms are solicited. The following assumptions have been made: 1. The quantities of D and T acid are based on the Government specification as 50/50 Butyl D and T Esters by volume. 2 . Production of MCA is based on the present batch system used at Jacksonville. 3 . Both D and T acid will be dried and handled to Esterification with Tote Bins. 4 . The acid reactors will be 3,000 gallons maximum working capacity to avoid unknown agitation scale-up problems especially on T acid. 5 . The glass lined vessels will be 2,000 and 4,000 gallon standard reactors and Chemstor tvpe storage tanks to minimize delivery time. 6 . Oechlorinators will be nickel clad 750 gallon copacity reactors built for shell operation at 350 psig. and jacket operation at 150 psig. 7 . Solvent clean up is based on the present multi-stage batch process currently* being used at Jacksonville. 8 . An entirely new-and complete waste disposal system must be designed and installed. 9. Approximately seven-day capacity has been used for raw materials and in-process storage. - 1- V Calculations Basis 100% Acid & Ester Orange - 8 Million Gallons/Yeor Assume average w t./gal. 10.70 lbs. Wgf./Wgt. (Hercules) 42.8 MM Lbs. 42.8 MM Lbs. 5.6 MM Lbs. V o l./V o l. (Gov't.) 4 MM G a l, Butyl-D* 4 MM G a l. Butyl-T \ 8 MM Ga I. Assume sp. gr. Butyl-D - 1.245 10.35 lb./gal. " " " Butyl-T - 1.325 11.02 Lb ./gal. 1.245 x 8.33 x 4 MM = 41.48 MM lbs. Butyl-D 1.325 x 8.33 x 4 MM = 44.15 MM lbs. Buryl-T . D Required Lbs. T Required Difference Lbs. Ester 1.32 MM 1.35 MM Lbs. Acid Represented 34.24 MM 35.10 MM Difference 33.18 MM = -1.06 MM D Acid 36.20 MM = +1.10 MM T Acid Have built into estimate sufficient capacity to go either way. By A . E. Sidwell 8/25/67 - 2- x / 'i P O  * ammmama^m 1* ' . . tz-2-fz ^^ ' - . . w id .- attachment y % C5 * ' J THE COW CHEM ICAL COM PANY i ^ rsr r This 1 to l i U n 7 *u that vc k iv t W v lt k V. C. Kratx, C * l i l , I Corp* o f Zagiaosrs la L r m C ity, Missouri', U t v* 4o mat intend to kid a thair s o lic ita c lr a So. ZUCA4]-**-l-0001, datrJ Scpteahor 7, 1947* ' p r *Ths M ilt roaoo for our d M iiir a 1 4m to r r it ( M l factors M tlls 4 kloir: * .s Xb* tin* a llo tte d for f u t e iu lM o f kids, S ;ta W r t , 1947 to , r October 12, 1947, is so t as!* tor preparation o f kids on o project o f this aefnltuda. f t f f i i n t i t i m r f oltonsil*.* 4 t t l ^ ot iM Stim other, than C t lit s Sprint war* precluded kecon** 1 the t la ; s llm o for propers tiro o f a r r ip m iiv t kid la answer to >-or s e lir lt a t t n a . "Vi would 12k* to sum op (a t other reasons for not presentlag a kid a t th is t i n , as follows: *a * * 1 ThcVeldoa Spriap a it* , orated as i t i s kvtworn th* University r f ittM rari L p c r l a a u l fo n t and the August Busch Xosurre, preseats too -Mich o f a haaard to Ch* plant 11f* la those arose. In cos* o f on accidental rolaas* o f product* itam the Orange M oat- ^ ORANGE - 8 Million Gallons/Vear (Basis: 6.0 million gcllons/year estimate dated March 17, 1967) 27.600.000 V y r. 21,000,000 V y r. 20.200.000 V y r. 26.400.000 #/yr. 27.600.000 V y r. 64.500.000 V y r. 2.300.000 V n o . 1.750.000 Vm o. 1.685.000 Vm o. 2.200.000 Vmo. 2.300.000 Vmo. 5.370.000 Vmo. (2,000 gal.) (2,000 gal.) ( 750 gal.) (3,000 gal.> (3,000 gal.)/ (4,000 gal.) 17.000 */b>atch 20.000 /batch 2,000 /bwtch 4.600 4.600 ^/tatchy 16,500 /batch ors for 8 million gallons Orange: Basis: Government Specifications - by volume 4 million gals. Bu-D @ l245 s p .g r . = 10.35*/gal. 4 million gals. Bu-T @ 1.325 s p .g r . = ll.Q 2 */g al. D = 1.245 x 8.33 x 4,000,000= 41,500,000 Vyear Butyl "D" Ester T= 1.325 x 8 .3 3 x 4 ,0 0 0 ,0 0 0 = 44,200,000 Vyear Butyl "T" Ester 85,700,000 Vyear Total Mixed Ester Ester "D" Acid 6MM 8MM 64,500,000 f mixed x 1.328 - --> 85, 700,000 * mixed 26,400,000 *(2 .4 4 ) = 85,700,000 2.44 = 35,100,000 V y r. "T" Acid 27,600,000 * (2.34) = 85,700,000 = 36,600,000 V y r . 2.34 54,000,000 * 1,700,000 V y r. Total "D" and "T" Acid Ester Acid D T 85.700.000 */yor mixed 50/50 by weight. 71.700.000 Vyear mixed "D"and "T". "35,100,000 Vyear 36.600.000 Vyear TCP = 20,200,000 x 36,600,000 * T @ 8 M? 7,660,000 * T@ 6 M2 26,700,000 Vyear TCP i i, 1 V DCP = 21,200,000 x 35,100,000 D @ 8 M2 26,400,000 * D @ 6 M2 MCA = 27,600,000 * x 71,700,000 * Total Acid (8M2) = 54,000,000 * Total (6M2) -3 - 28,200,000 Vyear DCP 36,600,000 Vyear MCA 18902 Oronge ~ MCA **6,600,000 # /y r. = 3,050,000 % o . = 102,000 '/d a y = 4,250 #/W . 17,000 * MCA/batch = 720 h r s ./ m o ---65 hrs./batch/unit = 180 Batches/month 11 Batches/Unit/Month Chlornators: @ 2,000 galions ( @ 4,000 ga lions 180 Batches/Month 11 Batch/Unit/Month = 16 .4 Units on MCA = . 8 Units?) 2 - Rows of 8-2,000 gallon glass-lined, acketed agitated reactors. 7 - Chlorinating each bank - 1 prechlorinating. 2 - Weigh tanks - acetic acid with plate coils, glass-lined. 16 - Primary condensers. 16 - Secondary condensers. 2 - Weigh tanks - phosphorous trichloride - stainless. 2 - Chillers - one for each chlorinator bank. 8 - Pumps - 1 for each 2 chlorinators. 2 - Absorbers - 1 for each 8 chlorinator row. -4- Oronge - PCP 28,200,000 V y r . = 2,350,000 */mo, = 78,200 */day = 3,260 V hr. 2,350,000 * DCP/mo. 20, 000 * DCP/bafclT 117 Batches/month. 720 Hrs ./mo. 60 Hrs./Batch/Unit 12 Batches/Jnit/Month 117 Botches/Month = 12 Batches/Unit/Month 9 .8 -- Say 10 Units on DCP @ 2,000 gai. 2 - Rows of 5-2,000 gal. glass-lined, Jacketed, agitated reactors. 2 - Absorbers - 1 for each bank of 5 chlorinators with temperature controls on makeup water. 5 Pumps - 1 for each 2 chlorinators. 2 - Chillers - for chilled tempered jacket water, 1 for each 5 units. Also chilled tempered water on absorber condensers (2). 2 - Weigh tanks - 2,000 gals, glass-lined with plate coil vent tied into absorbers. -5 - Orange - Chlorination - Outside Tanks Chlorine: 58,500,000 #C l?/yr. = 4,880,000 % o . = 162,000 */day 162,000 = 81 fons/day = 8 1 = 1.5 cars/day (55 tons/car) 2,000" 55 Use railcars to store chlorine Vaporizors: 8 - 2 for each of 4 chlorinator banks Phenol: 1,500,000 ^/mo. = 17.3 cars/mo. @ 10,000 gal. each 4 - 12,500 gal.-glass Chemstor storage tanks - (50,000 gal.) Acetic: 1,700,000 to 2,000,000 tymo. = 25.3 cars/mo. @ 10,000 gal. each (Mix) 6 - 12,500 g a l.- (75,000 gal.) >6- 1 J ^rr DCP: 28,200,000 #/ y r . = 2,350,000 #/mo. = 78,200 # /d a y = 3,260 #/hr. (11.6 V g a l . 2,430,000 g a l . / y r , = 202,500 g a l . /mo. = 6,750 g a l . / d a y = 280 gal ./hr. 4 - 12,500 gal .-glass lined tanks (50,000 gal. = 7.4 days) V MCA: 36,600,000 #/yr. = 3,050,000 #/mo. = 102,000 */day = 4,250 (11.5 ^/gal.) 3,180,000 gal ./y r. = 265,000 gal ./mo. = 8,800 gal ./day = 366 gal./hr. 4 - 12,500 gal .-glass lined tanks (50,000 gal, = 5.7 days) HCI: 20 (32%) - Average from MCA " " DCP = 122,000 */day = 105,000 */day _________ 227,000 /day = I?.7-'9 . = 23,500 gal./day ^*7 containing phenolics, etc. 240.000 gal. (6 - 40,000 gal) Rubber Lined Tanks 125.000 gal. (10 - 12,500 gal.) Glass Lined Tanks 32% HCI purchased = 415,000 gals./yr. = 415 T/C's = 1.1 T/C per day Acetic Anhydride: Phosphorus Trichloride; Brine: For Secondary MCA condensers 2 - 4,000 gal. wood (1 - for each chiller) Oronge - Chlorination - Outside Tanks (Cont'd.) Tempered water: For phenol condensers 2 - 4,000 gal. wood (1 - for each tempered system) Unloading Stations - Chlorination 3 - Chlorine Tank car 1 - Acetic Tank car 1 - Phenol Tank car 1 - HCI Tank Car 1 - Acetic anhydride tank truck -7 - oq ur oq Oronge " TCP 26,700,000*/yr. = 2,250,000*/". = 74,500*/day = 3,100*/hr. 2,250,000*/mo. ~ 1,110 Botches/month = 37.2 batches/doy 2,000*/batch 720 Hrs./Mo. = 90 batches/unif/Mo. 8 Hrs./batch/unit Dechiorinafors: T,T 10 botches/Mo. = 12.4 units on TCP 90 batches/unit/Mo. 1 4 " Dechiorinafors @750 G a l."nickel clad, jacketed, agitated Shell: 350 psig. oper. press; Jacket: 150 psig. oper. press. 3 Rows " 4 dechiorinafors " barricaded with rupture disc vent liner tCB (Ground) = 88,000*/day = 440 Drums @ 200* = 147/shift NaOH (Flake) = 53,000*/day = 110 drums @ 400* 110 drums @ 100* MeOH (fresh make"up) = 5,400 C al./d ay 2"25,000 G a l. Alcohol Storage " Drum handling facilities for dechlorinator charging. 3 " 10,000 G a l. NaTCP (dirty) Storage "304 S/S, agitated w/coil. 2 Hold Tanks " 6,000 Gals, with vent condensers 2 Stills " 3,000 G a l. Monel clad, agitated, jacketed (150 psig) still pots " 316 S/S column 2 Still condensers 1 Alcohol Hold Tank " 304 S/S I837 -8 - .Orange " A d d 24,5~T_ 35,100,000 '/yr. 2,930,000 '/mo. 97.500 '/day 32.500 '/shift 4,050 '/hr. 36,600,000'/yr. 3,050,000 '/mo. 102,000 '/ay 33,800 '/shift 4,230 '/hr. 10 " 3,000 G al. brick lined, agitated (Titanium) Reactors 5 Units on D and 5 Units on T ' normally Weigh tank and piping arranged for flexibility for ratio of units on D and T. Basis : Approx.95% operating time. 8 " 4,000 G a l. Glass Lined, agitated, jacketed crystallizers 2 " Refrigeration units " 2 " 10,000 G al. Slurry Hold Tanks heavy duty ** agitated 5 " 6,000 G a l. Slurry Feed Tanks " heavy duty " agitated " jacketed 4 " Brine Extraction Column ( 1 for D and I for T ) Haveg 4 " Brine Storage Tanks * 10,000 G a l. Haveg Independent weigh tanks for each reactor 10 " NaTCP weigh tanks ~ 304 S/S 10 " DCP weigh tanks " glass lined - jacketed 10 " MCA weigh tanks " glass lined " jacketed 10 ~ caustic weigh tanks " steel 6 * recycle liquor measuring tanks " glass lined 2,000 gal. 6 * HCL measuring tanks " Haveg 2 ~ brine solvent separators " 1,000 G o l. ~ glass lined 10 " Centrifuges 48 in. " 316L S/S , Kynar Coated 5 " Blenders 4 " Conveyor /Dryers (for flexibility between D&T 316 55/ 2,000 - 2,500'/hour 5 " Filtrate Tanks (1 for each 2 centrifuges) 4 00 - Tote Bins (97,500'/day x 7 = 682,000'/W k. 195 Tote Bins @ 3 ,5 00 ' ) ( 102,000 '/day x 7= 714,000'/Wk. = 204 Tote Bins @ 3,500') Aluminum " 90 cu. ft. capacity -9 - Oronge Ester 85,700,000 #/yr. 7,140,000 #/mo. * 238,000 */day * 9,900 */hr. @330 days/yr. 265,000 #/day * 11,000 #/W . 10 - 4,000 gal. 316 L 5/5, agitated, jacketed, vacuum esterifiers 5 - 4,000 gal. 316 L S/S " " preesterifiers 2 - 4,000 gal. Glassed lined agitated, jacketed recovered acid esterifiers 2 - Vacuum systems (for each 5 esterifiers) 10 - Karbate esterifier condensers 2 - 30,000 gal. Butanol storage tank 265,000 f/day BuE-Mixed 132.500 9/day Bu-T ester = 35,400 132.500 9/day Bu-D ester = 35,000 70,400 ^n-Butanol/day 70,400 = |o/500 gals. n-Butanol/day 6.76 5 - 10,000 gal. Spent Butanol Storage - Steel (1 for each 2 esterifiers) 4 - 20,000 gal. - Butyl D Ester Storage - steel w/coil 4 - 20,000 gal. - Butyl T Ester Storage - steel w/coil - 10 - R u ;: v.-' Orange ~ Solvent C leon Up NaTCP clean up 4 " 6,000 G a l. agitated tanks NaTCP clean 6" 10,000 G a l. agitated w/plate coils 2 " D " Clean Solvent 2 " D " Spent Solvent 2 " T " Clean Solvent 2 " T " Spent Solvent 4 " Separator _ Decanters 4 * Clean Up Tanks 15.000 G al." 15.000 G a!.15.000 G a l." 15.000 G a l." 6.000 G a l.6.000 G a l. agitated " heavy duty Unloading Stations 1 " Toluene 1 " Methanol 1 " Butanol -n - 1.0 90 Oronge Waste Basis: 85/700,000 9 mixed D and T Butyl ester/year 61,000,000 # Na OH (100%)/yr. N c C l- 90,000,000 9 NaCI/yr. 7,500,000 9 NaCI/mo. 250,000 9 NaCI/day 10,400 9 NaG/Tv (5.4 tons/Tir.) Glycollic Acid 5,500,000 #/yr. = 458,000 9/ m .o . = 15,300 9/day = 638 #/hr Oxalic Acid 129,000 9/yr. = 10,800 9/mo. = 360 9/day = 15 9/hr. Acetic Acid 1,100,000 V y r . = 91,800 Vm o. = 3,050 9/day = 137 M>r. plus all acetyls carried from plant generated H O . Still Bottoms - Toluene Recovery Still 1,530,000 V y r . = 128,000 '/mo. * 4,250 9/doy = 177 M ir. Still Bottoms - Methanol Still 990,000 V y r . = 8,500 '/m o. = 2,750 9/day = 115 9/hr. Combined Bottoms: 7,000 9/day - 292 9/hr. Approximate composition 35% Toluene 32.5% TCP Anisole 13.0% Trichlorobenzene 19.5% Tetra chlorobenzene This would generate about 3,200 9/day HCI By A . E . Sidwell 3/18/67 Oronge ~ Utilities Steam (Salt evaporation not included) Air Water " make up Water " Cooling tower Electric Gas Inert Gas Required for Orange - 8.0 Available at Weldon Spring 200,000 lb ./hr. 216,000 lb ./hr. (240,000 lb ./hr max.) 1,500 CFM 10,000,000 Gal ./Mo. 2,000 CFM 10,000,000 Gal ./day (wells"treated) 20.000 G PM 9,000 KVA Liquid Propane 20.000 CFH Not Available - 13 - `3 8V ' Orongc - Services (Existing at Weldon Spring, Missouri) Railroads - existing, may need minor additions Roads - adequate Office - adequate Cafeteria - adequate Shop - adequate Storeroom - adequate Warehouse - existing, may be too small and not convenient to process. Laboratory - existing but not available for Orange Locker - Change Facility - adequate - 14 - o o, r o A QCiuS UUiHMfe! ; it - S S & lO Z 1* k STATE OF ARKANSAS DEPARTM EN T O F POLLUTION CO N TRO i. AND ECO LO G Y 3001 NATIONAL DRIVE P. 0. BOX 9533 LITTLE ROCK. ARKANSAS 72219 The Department i s now in the process of attempting to bring together some "loose-ends'1 concerning dioxin (TCQD) contamination r e s u l t i n g from V e r t a c ' s oper ation. Some s t u d ie s which have been conducted under EPA sponsorship have y e t to be completed and reported. Some of the Department's monitoring e f f o r t s have been deferred in order th a t other federal commitments could be met. I t i s a n t i c i p a t e d that m o n i t o r i n g /a n a ly t i c a l a c t i v i t i e s can be resumed by l a t e December. A meeting has been scheduled f o r November 29, 1979 in vo lv in g Ve rta c and the Department. Topics of the meeting are to i n c l u d e : (1) St atus of 2 , 4 , 5 - T s t a r t - u p p l a n s , (2) compliance with the Department's o r d e r , and (3) d i s c u s s io n of monitoring and a n a l y t i c a l e f f o r t s of V e r t a c , EPA and DPC&E. I w i l l update t h i s re p o r t a f t e r the meeting on the 29th. Jacksonvin_g__Si3wage Treatment System C" The oxidation ponds of the c u r re n t wastewater p l a n t are contaminated \ \ with TCDD. J a c k s o n v i l l e has completed i n i t i a l plans f o r a new \ system which would by-pass d e f e c t i v e c o l l e c t o r l i n e s and the old wastewater treatment p l a n t . The plans were completed p r i o r to the Ve rta c i n c i d e n t . However, the A i r Force claims t h a t i t i s unable to p articip ate in the funding of the project and, as a consequence, EPA w i l l not r e c e i v e the plans f o r review and subsequent funding of / a cons tr uct io n g ran t. ( T y p i c a l l y , EPA pay 75% o f the c o n s t r u c ti o n / ^costs__and__the -commimi-ty -pays--25% ------------------------------- ------------- --- ------- j Senator Bumpers e a r l i e r t h i s y e a r was t a l k i n g about a s p e c i a l app rop riation to the A i r Force in order tha t we could get the p r o j e c t moving. I t i s hi g hl y d e s i r a b l e that we do so because we can then i s o l a t e a portion of the TCDD problem. Your a s s i s t a n c e in g e t t i n g ' t h e A i r Force or Congress moving would be h e l p f u l . A l t e r n a t i v e l y , the Department could , according to EPA, sue the A i r Forc e. We stand ready to discuss the issu e with you. Governor Clinton November 26, 1979 Page 2 Meanwhile, J a c k s o n v i l l e i s proceeding with the c on s tr u c tio n of an interceptor lin e that should elim inate the problem of overflowing manholes in the r e s i d e n t i a l area j u s t south of V e rt a c . This may, however, c r e a t e problems a t the c i t y ' s e x i s t i n g wastewater plan t and^j^jq^4rs''tfiat the p l a n t be by-passed during high flow conditions, w i l l be watching the s i t u a t i o n d o s t Tent Monitorinq E a r l i e r commitments to EPA n e c e s s i t a t e d suspension of much of the Department's monitoring of s o i l s , sediments and waters fo r TCDD. We now have a backlog of s o i l samples taken from the r e s i d e n t i a l area surrounding Ve rtac and hope to be in a p o s i t i o n to s t a r t workino on them t he, l a t t er - pa rt o f .-Qeeemfee-r-:------ - The Department has conducted some r a t h e r crude a i r sampling on V e r t a c ' s property. The f in d i n g has been t ha t TCDD adsorbed on p a r t i c u l a t e matter (dust) c o l l e c t e d by our sampling device i s in the same range as we have found in s o i l samples on V e r t a c ' s property. We are expecting a s e t of more s o p h i s t i c a t e d sampling equipment from EPA to i n s t a l l and operate both on V e r t a c ' s property and in the surrounding r e s i d e n t i a l a re a . We hope that EPA's equipment w i l l give some idea as to the s i z e f r a c t i o n of the contaminated p a r t i c l e s . Such information w i l l provide b e t t e r i n s i g h t as to the health hazards involved. S i t e Cleanup Ve rtac appears to be reasonably on schedule with requirements of t h i s Department. Paul Means has sent an i n q u i r y to Vertac which, in effe ct, provides a vehicle for final determination/reconciliation of V e r t a c ' s compliance s t a t u s . Th is w i l l be d i s c u s s e d in d e t a i l with Vertac on the 29th and a re p o r t submitted to you. I am very i n t e r e s t e d in e s t a b l i s h i n g a ero si on control program on V e r t a c ' s property. .Such a program w i l l reduce wind blown dust (contaminated with TCDD) as well as reduce the continued contamination of RockyCreek and Bayou Meto. Before f i n a l i z i n g the elements of the program, I would l i k e to have b e n e f i t of EPA's r e c e n t l y completed s o i l s and geology study. The re po rt of the study i s now in pr epara tion. An a l y t i c a l Questions Our contacts w i t h in EPA continue to a l e r t us concerning a n a l y t i c a l q u e stio n s. These questions impact c u r re n t understandings of the b i o l o g i c a l h a l f - l i f e of TCDD and the p o t e n t i a l f o r TCDD to be degraded under varying environmental c o n d itio n s . At is s u e i s the extent to which TCDD i s bound to s o i l p a r t i c l e s , the .stereochemistry of the TCDD molecule and " a c t i v e s i t e s " on the molecule. .0' Q Governor Clinton November 26, 1979 Page 3 I f you d e s i r e , I w i l l provide a d e t a i l e d explanation of the i s s u e , ForI purposes oWfI twhillis/ ri e p o r t ,J h. wo.w--e-ve-r,j --I a--m........m..--er-e'lVy a l --e'r t" i n gA Wyou to th e p o s s i b i l i t y that g r e a t e r TCDD concen tr atio ns e x i s t in s o i l s -and seddiimments than preevv i o u s l y reported and that the TCDD h a l f - l i f e i: longer than previously estimated. Resumption of 2 , 4 , 5 - T Production Ve rtac continues to hold production of trichlorophenol and 2 , 4 , 5 - T in abeyance u n t i l such time th a t the s t a t e and EPA approve proposed plans for containment and d e s t r u c t i o n of TCDD. In a c o n f i d e n t ia l report dated November 5, 1979, Vertac summarized the results of various laboratory scale experiments for clean-up and des tru ct io n of TCDD. The repor t a ls o contained flow c ha rts depicting how TCDD containment, cleanup and d e s t ru c t i o n would be accomplished, using the process described in V e rta c 's patent a p p lic a t io n . I t i s u n l i k e l y , however, that the depicted process w i l l be placed into operation because the rep ort allud es to an a l t e r n a t iv e / m o d i f i e d process which Vertac has developed which achieves a hundred-fold improvement in TCDD d es t r u c t i o n e f f i c i e n c y (to 99.999%). Presumably, plans and drawings of the improved process w i l l be submitted to the Department and EPA a f t e r Vertac completes amendments to i t s e a r l i e r patent a p p l i c a t i o n . I have not rec eive d comments from EPA concerning V e r t a c ' s November 5 report. Delays are expected because EPA's principal coordinator, Bruce E l l i o t , has been s t r i c k e n with u l c e r problems. EPA and the Department monitored some of V e r t a c ' s l a b o r a t o r y - s c a l e TCDD d es tru c ti on runs. Samples were s p l i t between the Department and a t l e a s t two EPA-sponsored l a b s . Although the outside labs have not formally reported t h e i r r e s u l t s , pr elim in ary information suggests there i s s u b s t a n t i a l agreement with DPC&E's data. Based upon the foregoing and based upon the Department's a n a l y s i s of V e r t a c ' s more recen t d e s t r u c t i o n e f f o r t s , I am convinced that there: are chemical means of destroying TCDD in V e r t a c ' s waste through a d e c h l o r i n a t i o n / e x t r a c t i o n process to a l e v e l l e s s than 10 parts per t r i l l i o n . The Department has not confirmed the i d e n t i t y of the products of the d es t r u c t i o n pr oc es s. The i d e n t i f i c a t i o n may be accomplished by EPA-sponsored la b s . Ve rtac maintains t h a t i t i s capable of i n s t a l l i n g and s a f e l y operating the equipment necessary to contain and destroy TCDD r e s u l t i n g from the production o f t r i ch lo ro ph en o l and 2 , 4 , 5 - T . Vertac o f f i c i a l s have discussed the p o s s i b i l i t y of securing an EPA grant to a s s i s t in the processing of stored waste products and contaminated s o i l s and. sediments. EPA appears to be f av o r ab ly impressed with the idea c0 Governor Clinton November 26, 1979 Page 4 and would, in my opi nion, fund such a program provided that i t was s a t i s f i e d with the chemical d e s t r u c t i o n process and provided that you f u l l y supported the p r o j e c t . I t i s a n t i c i p a t e d that the p r o j e c t would i n c l u d e , in addition to the chemical d e s t r u c t i o n fo r m a t e ri a l s containing high TCDD co n c e n t r a t i o n s , p h y s i c a l sep aration s and biological degradation of less concentrated materials. Please note, however, t h a t b i o l o g i c a l degradation has not y e t been proven. Vertac maintains th a t i t w i l l not be ab le to a ff o r d the i n s t a l l a t i o n of process equipment for the chemical d e s t r u c t i o n of TCDD unless i t is permitted to resume production of t ri c h lo ro p he n o l and 2 , 4 , 5 - T . I am not sure t h a t Vertac w i l l be a b le to aff or d the safeguards that w i l l be imposed i f production i s allowed. Unfo rtu na tely , that jw-rll remain an open question u n t i l such time t h a t the engineering the-ccm^pLual s l.ayTT 1 continue to recommend that Vertac not be allowed to resume producl of trich loro phe no l or 2 , 4 , 5 - T unless (a) the d es t r u c t i o n of TCDDcontaining waste can be ass ure d, (b) both the production and destruc processes can be adequately safeguarded, and (c ) Vertac commits to a phased program f o r the d es t ru c t i o n o f stored waste products, including hi g hl y contaminated s o i l s and sediments. The dimensions of the phased program would n e c e s s a r i l y be dependent upon the 'aegT*ee^offederal support obtained. While the conditions described in the above paragraph are necessary, I am not sure t h a t they are s u f f i c i e n t . Broader questions concernir worker s a f e t y and environmental impacts r e l a t i v e to the use of 2 , 4 , 5 - T must a l s o be fac to re d i n t o ' t h e equation. Studies being conducted out si de of Arkansas may e v e n t u a l l y provide guidance. Recognizing t h a t the f a t e of 2 , 4 , 5 - T r e s t s p r i m a r i l y in EPA's hands and recognizing the federal re sour ces and r e s p o n s i b i l i t i e s in the f i e l d , I would be h e s i t a n t in -attempting a ban, a t the s t a t e l e v e l , on the manufacture and use of 2 , 4 , 5 - T . U n t i l Ve rtac fo rc es the i s s u e by f i n a l l y submitting d e t a i l e d plans and s p e c i f i c a t i o n s f o r the containment and d es t r u c t i o n of TCDD w a s t e s , I do not f e e l that the s t a t e i s o b li g at ed to take a stan d. By then, b e t t e r data could e available. State of Arkansas O ffice of t h e G o v e r n o r State Capitol Little Rock 72201 January 10, 1980 BillClinton Governor Mr. Jarrell Southall, Director Department of Pollution Control & Ecology 8001 National D r i v e ____________ Little Rock,._AR..--- .....' ....... Dear Jarrell: On Monday, January 7, my office received a telephone communication from Ms. Adlene Harrison informing us that a letter was forthcoming with regard to the problems surrounding the cleanup operations at Vertac, Inc. in Jacksonville. It is very important that the contents of the letter not be discussed, at this time, with anyone other than members of our respective staffs ,and the staff of EPA. J BC/SS/hnj n .3 o1 u' 9C 1 TM * DOW CH IM ICA I CO M P A N Y D e c e m b e r ilk. 19*( Emil E. C kritlo< uo Industrial H r|iiu<l Hercules Incorporated Hercules Tower 910 Market S tre et Wilmington. De leerere 19(99 Dear Chris: This le a belated reply to your le tte r of O ctober l(. 19((. A delay la replying la lo r two reaeoo a. F ira t. I w asted a chance to evaluate tom e of the laiorm atto n we had to aee how It agreed with your coaclueione aad aecoad, to consider fu rth er, the advisability of publication of such Inform ation at this tim e. Is re(ard to the firs t question I am not at all surprised at your conclusions with r e ta r d to the liv er function te sta for we have observed essen tially the tam e Inconsistency in resp o n se s. 1 do not believe this is unique for the acn a|en you mentioned for I think it is true of many oth er bepatotoxic su b stan ces. I feel quite confident that if one wants to rely on such te sts, then a food tis a d qroup of anim als would have to be used at each d o safs level. Individual v ariatio n la sim ply too (rear to p erm it usinf the data from sm all (ro u p e . On the other hand we have still found that the rabbit ear te sts to be quite consistent and evaluation of perhnpo three animals seem s to five us very good assays. In r e ta rd to publication I am not satisfied that we are randy to publish on the subject yet. I think th is re q u ire s a considerable amount of thought and p rem ed itatio n with reg a rd to possible consequences. I feet that it would be a m istake to kick this In the public eye until such tim e as we have answ ers to obvious questions. B est w ishes for a'H appy Holiday and a P ro sp ero u s New Y e a r. Sincerely yours. i, V. K. Rowe Biochemical Research Laboratory 1(0) Building VKR/ e e h 0 : 'J v . * i 130C Th e h a n jta -'tfr* nithr 11 so rr lat 4 with 4o or connft oa*t and duration, vn io animal ahowyic-'fppar>ty'i{nifi<ant ((c, Althoufh to m i potiti rult wr obtained with dioa la itaal. tha uaafuina o thia taehniqu a a bioaaaay (or th praac o diada la quaatioaabla. H05Q1 JL m m m m am m H ER C U LES POW DER COM PANY % JA CK SO N V ILLE. ARKAN SAS CAUSTIC FIRST AID FOR 'MONOCHLOR" PHENOL If splashed with any of these materials, 1. ) Go as quickly as possible to a Safety Shower. 2. ) Call for help on the way. 3. ) Get under the shower. 4. ) Wash repeatedly with water. Rub lightly over areas affected to hasten the removal of caustic or monochlor. 5. ) While being rinsed with the water, have someone help remove clothing which may be contaminated with the splashed material. 3.) Wash for at least five (5) minutes. Continuous washing and rinsing with water is best for the removal of caustic or monochlor, or solutions of these. For phenols or phenol solutions, after flushing with water and removal of affected clothing, pat dry the areas immediately affected -- do not rub -- and apply a generous layer of glycerin. Allow this to stay on for approximately one (1) minute and then flush off with water. Repeat this at least two (2) to three (3) times. Finally, pat dry and apply a layer of glycerin. If any of the materials are accidentally splashed on the eye lids or into the eye, immediately flush with water, using an eye fountain. If splashed generally and incidentally in the eyes, rinse eyes while in the shower. Never rub an eye to help remove something, only flush it. Have a helper hold the eyes open if you find it impossible to force yourself to do this. Report all accidents to supervisor or have someone do it. Remember1 Prompt Flushing with Water, Removal of Affected Clothing, Care to be sure that all body areas are washed, otherwise an area may be overlooked which may cause more trouble than the area first noticed. 19C AESidwell: bg 11/21/63 C-; A *' -- J Ford - Rrsreh Center M. F*Grn - STithtic 0000342 K p -',f .. VlTnlngton. Delaware -'T*C cc< jin! - February ui 1J6 TO: J KJ - H. I. wilder - Jacksonville c C- 2. E. Chriotofeno - Medics! - Esos Offles I'd like to express y nt>oresiatian to you tad Dr. Sld> ^ the tlsK nd effort you spcnLt-*mplalaiS45 ths plant efforts In-^afficteoaBente-l control, lhcre has teen a narked Improvement during ths past year and if the progfua continue a at this rats even minor problems vill bs under control. % e potential hazard stems from the use of a-.ppliad d r masks vhen cleaning ths Sharpies centrifuge. Ifader certain circumstances it is possible to generate csirbon nonouide In oil lubricated air esepresaore. If men breathe this air for ertended periods their acuity sight bs impaired, but the effects would not be pronounced if the breathing air contained less then ICO ppm of CO. Determination of the CO content of breathing d r is justified, and the enclosed literature describee a system for monit.ring breathing air. -- --- ' 5r. Cavan and Mr. Cholak (representing the HAC feasibility study- team) appeared satisfied vlth the precautions taken to^prfgvent occunational Illnecjs^t-Jacksoaville. They noted a unique opportunity to study possible h5dth_Jrplications^becauce this plant is the only one entirely devoted to phenaty herbicides, lhey are not aware of occupational illness associated vlth the nnnufacture or use of these materials but they vill probably recommend a more _thoroivcix study of exposure to raw materials, solvents intermediates end*finished products. In addition they vould like to see some medical data such as urina analysis. Their report vill be sent to you vhen it la received. _ Or. Sidvell agreed to forward sp i e s of ,k,5,-T productiva strerno <uad recycle cr vasts streams. One pound of each sarnie should be sent to J. J. Ford at the Research C.nter. These weepies vill then be used in preparing material for test by cioascny techniques for chloraene or 3TP retention. E3C:wh Enclosure MHIoStT. I1397m *s0.011.44 l-M 1UU V. ;1:.-: - .'irt.fc..r,, ' :h r. Skua-. - 6> *r.'ft-r.e C. 1m rVrji - 3yr.zbm-.irt H. t . M iller - J i u i e r T t U ` i Art. Attn: At-. A. I. 1:j U J. C. Atunlhcla - l-.pal L. C. AteGee - Medical HQTE TO -'AJaar.-TLIX AMJLSSAH HJLTT H U . fi-: OLlU Or. A U t 9, 19fcS, At B*rl JUrnhae of Dev Chemical Co^any `lroboned ae stating that he * e)Ur^ at the request of Mr. Donald felavlr., Vit-e-pyeilent of Dew tn inquire ho eri-ue 1 isroUrrM the chloracne problem ie relation to the eonavser use of Vh.er. 1 tusKvsted that be should discuss 'hl< with Hercules aanagasAent rather than with mm, he stated that on the drier of their toxicologists Dew ha* gone.re greet expense to altar *heir aanufhe'urlng ecr.dltlana In erdtr to produce acid vhleh haa leca than 1 ppn acnegra. Since stveral man-ha ago Itr had aade available :o all ether producer* the tame data which crnvinced their tealsc logouts -.0 tet an Internal ipeelflcatlon of 1 ppe on the acid, they had aacuEed that the ether preducer* m u l d tab* stellar action. Or. the bvsi of their chdeal analysea, they are convinced that nr one elae haa done anything to reaove the aenegea from their |A,i-T and consequently, they ranted ay opinion whether they had been ala*edvlsed by their own toxicologists. 1 adrlaed Mr. rarehas tltat I lid not think thla was a proper question for a* and that be should *eea rut tile advice froa a private ccnaultant if he doubted the aavlce cf hi* rwn tczleolc.'liti. I printed rut that considerable Individual profeaaisnal Jud^ient wculd be involved In eetabllsblng a specification cf thla type becauae all cf `.be lrpcrtant facts are not knave. He than stated that Dew waa ex-rmsely frightened that this situation \algSt explode. They are aware that iheir_.eaopeti.tcrs-are-mnrwev;ng-eylij5-T~vhieh contains *aiaraiag_aounti* of atr.-ger. aid if the forerraaent learca of thla tha t^tole Industry will suffer, they are'parileularly fearful of a Congressional Investigation and excessive restrictive legislation cc manufacture cf pej which aQgh.t_result.______ _ I advised Mr. Thcaiaethat we shared hlJ~faar~but jara net aware cf his allegatlcn that the competitors* prodHTta were-hazardous. he asked If Herrules had established an lntamal specification. 1 stated that be should discuss this with someone In our smnagsaent and referred hla to Mr. Copeland. I reminded his that we had experienced great difficulty in conducting the analyses for the aenegtn by the Dew procedure, anu that only within the past few weeks, following a visit of our chemists to Midland, have we been able to obtain any useful lnftraatlcn. J suggested that If he wanted any additional lr.foraa*.lsr. on `hi.* p.-ctim he should talk to Mr. Copeland. He acx-d that he be transferred tc Mr. Copeland. (Af.er the call waa transferred I learned thet Mr. Copeland was ou- cf town and Mr. ffcrnhas left w e n that he w: ul: call on Monday, July 11). cuts* ^I 1,0 .- ii 7KJ M OD O.V t.'; 00 i, - I,.,. , I TOfc 93V . co Cj c Co .!' 0" t* k. X _' acuLfiS P O W O ER COM PANY cc: Mr. Paul Mayfield - Executive Mr. Charles Maddock - Legal Dr. Lemuel C. McGee - Medical Mr. P. J. Reno - Synthetics Mr. R. T. Yates - Synthetics -- Mr. C. L. Dunn - Synthetics -- Mr. J. M. Eagan - Synthetics -- Mr. H. E. Wilder - Jacksonville Mr. A. D. Sidvell - Jacksonville Mr. Ashvorth BursesT"^\Advertising Vi liningt March 26 TO: M r. John C. Copeland - Synthetics Department FROM: John ?. Fravley - Medical Department Report of Meeting with Dov Chemical Company on the Toxicity of Trichloropher.ol Impurities At the invitation of Mr. V ._K.-RoVftv Biochemical Research Department, Lev Chenicar-Conpany^Mr C. l T Dunn and the vriter (along vith representatives of other TCP producers-- see letter attached) met in Midland on March 2U., 1 9 6 5 , to discuss impurities in TCP. ------- Mr. Rove and Dr. Holder of Dov reported that 60 to TO employes of Dov over the past tvo years have developed chloracne-from-exposures to materials in their TCP operation. Chloracne is .a^dlifiguringjdiseajS-e-involving blockage and inflammatio of the sebaceous glands of ti^e~TkTn7T?^icuIariy of the face. It is believed to be a sV^tislp disease and requires several years after exposure for the condition to disappear Dov has conducted considerable research to identify the cause of this condition and has concluded that several impurities, sometimes present in TCP, are responsible. They have identified one of these impurities which they believe is the principal acnegen-- 2,3j7,8-tetrachlorodibenzo-p-dioxin. They have developed (and supplied to all attendees')\a chemical method for the detection of this material which is sensitive/to In ppm (gas chromatography and flame ionization). There was considerable'^discussion of the clinical aspects of the disease and the toxicological research Dov has conducted. In brief, 2,3/7,8-TCDED has been shovr. no produce the disease in rabbits at a concentration of UO ppm after one application of 0.1 ml to the ear, and at a concentration of O.k ppm after eight applications. No evidence of the disease has been produced by concentrations up to 20 ppm for au single application and up to 0.1 ppm for twenty-five applications to rabbit ears. ! The compound has also been demonstrated to be a potent liver toxicant by oral or skin exposure. As little as 0.017 mg/kg is lethal to raooits by the oral route. Dov has analyzed coraiercial samples of TCP of t producers and has found up 2,3#7,8-TCDBD in some. Is finished samples of 2,kJ5"T"*ci<l they "ave -und up to 10 ppm. No Hercules sample analyzed contained any significant tenegen. Dtv has reduced their TCP capacity jind is checking-aH-production to be certain that it contains less than 1 ppm_2,37778-TCDED. Currently,'tow'is ' burying all vastes and contaminated'material from their1TCP plant since they axe J L 10 POW DER COMPANY Mr. John C. Copeland. Page 2 March 26, r.o- positive that burning will completely destroy the acnegen*. Dow's intention in requesting this meeting was to inform all TCP producers of thi* information so that they car. take steps to control the quality of their TCP production. A sample of 2 , 3,7,3-TCDBD for analytical control was supplied to each company. The^Michigan State Department'-of Health has been consulted on this problem because' of laborerexatioaslproblems! Dow suspects that the._?ederal Government has bcccme""aware- 'I recommend-- chat Hercules take icsediate steps to determine whether any aonegens are formed in our TCP process. This-sHould"be determined by chemical analyses and biological assays. If any such materialsjare formed, ve should determine the fate of these materials in jour plant--whether they are chemically destroyed, burned, or discharged in the waste stream, etc. We should also ccnside: the desirability of constant monitoring o K p u r TCP or 2 , 5 -T-acid production by chemical methods to protect against illegitimate claims of acne from users of our 2yl,5-* products. L SU .L *1 4^- H4ACV14S f U n Walaran * tka *M i. c. rami im oi I. | . C k rliU tM * < l l K. A Tu* *r*> **C . . Sratt Synttetlca A. X. OBnwr Inai #1< * C . J , J . | M Aaai. **C INCORPORATBO wMMurmuf IUIIN4YO. U A t t A I v >4, 19 ' lk u k * l< Z iat. 4 tr k t t f A.O. k d n an te n ta r 4U m 30 T b v l a f l a , taw tockl Bear r r a f titw te tta i: l a a t t a l lir (1969), ta rla a ta l t ta r l a t e n t e r y , e Ik m * tea kaaaita aeaoatate ite U t jtretactlon af trtcfelsrepfcaool. I ra n e I t t tea recm t m i o f e k la n cM la tte Unita Stata# anA m u r l i w UM f n atati ora taAae ky jm to aura a l a a t r v y a t l t l a f a s te lla r s eyU arla a i r l N ky M f . Oaa a f year a sat haifui r a a n u aa U a t jma a a a ly u a l l aklyaaate of laccala te le tta rtrpaaool fa r a i t n c i a p ky aa aaal r a t M otelaal aaaay yrocatar* lek m t e a ra ta . Taa alaa errar te aaaay n a a f aar aaaytaa acconta ta te la re cata . te y l a t t a r a f Pacrat e r 34, 1 9 , t laAlcata te a t a ante aaa tea# aaaylaa te tea aaar ( M t n . I r a ceablaattea a f raaaooa, I t kae UAaa aa atU a te eaarakle tea aaaylaa lek a canal dar a sa t ayyreyrteta. te el-- rely teya te a t yaur effar la e t i l i im ita ti* te ta . t e te a aaeiapttea teat ye 111 e t i l i te akla te fa rfa ra tka?a aaaaya, t e t e aklyyad 14 aaaylaa ( lO ^ n a a teck) a f ykeoesy k a rk lelte m i ite f t a u t a aa tataraaC tataa ancota ta ra la tk a lr M t e u r t te te . U n Olataana a f n r teM O ffice, te t e i i M te . Melaaaa te contact jm te am n a n i t U l i tte e te r yarranal e ll ry a f te a aaaylaa te yoa. la aM ltloa, te H I t e a a l l pia a f 3 ,3 ,7 ,4>t*tnckterad.`k n*y< 41osta, lek raa t e mm aa a ......."*"........ ~- te a r a r yoaalklt, tk a aaaylaa t e t e aaalyta te r 'letta* r a a t t ky aa <fcroaatarapby, a a i v i l i te r y S i te <ckaaa te la t a f a n a t i alte je t te aa a f te te atarai tea raltek lU ty a f tea ckrotafte fra c e ta rv . S e r a n r , yen arai i w te a t a a a f tea aaaylaa ( t a t e -' etettak le ' te tte * ; te a m u l i (te a 1 te 39 ypa U M " lette* aa a tte r a a ratala t e e t r a t t e a f *teste* te le e n t e te a fra ta ra . - -- -- ---- 1 Tka aaaylaa a ra lakateS aad U e a tlfle S fallava: Saeytee nkS67<*l-l : :: 4 j 4 9 Steitfar 3,k,9,*T Ael Ite ateo M u te : ** h 0 l `t 5 0 frofaaaor I . QattaX * Jtty H , 1966 burnita nssao-jA-a -9 fiu t Q ra it J,b,5T Acid altb ta n a __B_iodo iMpitt n$363$$.x 3 -4 -5 n a n i Orai* lo*Iva Tr to t Inr im m oto i t i Mio* Diodo * anylta X1520-56-l a *3 a 5 t I U r l htcyX i i u r *f J,b,5*T t u Mio* Bioaia * lam io H5280-5A-7 booaaponifla b lo fn e tlo o fTom plaot j r loo*lo XX$30O$XO faro 2 ,3 ,7 ,S>totrbloro*lbaoa0-o-*Vado tba aaa^loa e f aottua trietteropOonato (CL52flO-55*l to 5) eoa lo oro aaolly bando* l f ll* u lf lt* by battin e to &)*C> tbo aanyXo mi annoipool n a b la frac tino oaa ba X l* d fla* a t 50*C. ' X eo rtaln tb a t ifeara la m naa* rag ao lo cawtloo m a to boailo ttooao a a ta rla lo v ita appropriato cara. I l la bacano# a f tba *-- * n f I ^ h m t baaa a a to ria lo ta p i aa ara araaaclnc for faraooaX iaXXaarr to ja a by r. m i Inaili. ... . *b aXao plaa u a t l aapt a biola*leaX aaaay by to rn a i i M i i i t M i ta rabblto a t t i ooaa o f tbaaa oaayXaa. Ma 111 ba ila * la mampmrm tbaaa raoulta a i t i yaara, tona tboy ara a ra i la tta . Al tb a tia a o f ay n o l i t s yonr la borato ry , m a 1a d a tto * t b t t jwa tr y la locata a copy f yonr montato n p n r t 00 tba cU sracaa apiionio alca aecarro* a i M lf in X993* IXaaa larcnXaa baa aaaar aapattaaca* a tana a f Mar*eoo, a m al* approdato racalaing a copy o f tfeat ra y o rt, v i t i jftotacraifti ao ( b i t oar ptoplo a i b t botto r i f i m l a u tba fataatlaX a ffa tto o f oaraXaooaooo. Xf j n bota aay ^aaaUono aboot tbooa tonala* fXoooo oootact ao. t o t ao top* tbo t tbroucb tb ia aooyaraUra m i a*or, aa eoa botb p n rM o batta pratocUo* ta tba v ia r ia of botb o f oar m p u l H . b iat mrooaaX ra*aria. Jff/aa CMaf TOaieoiaaiat hi) 4 5 ! IS'< U u B d c i l HC* < la tha C s r l i ao evi fa r roa u -roca t a uod t U n l i m ! u 4 v i t i h f t l l l i i eba eao*.ol&exi| Uij ci U .j t i * ! ; p ili* : i g l t n la Z 5099 tto a r ili4 la r s n o tla o ( i r c i jv a i r i d a l i to A crau o i lo he i t t i 19 I I k o i t h l i a i t a t r i l l i ; v ita h i l i u o r O e t u l . CVtlonalj a Ao a*t li* io r o te a i cor a s i i l t t i r l H kaov^ow ci Uw m e n t i t a l i t i o a l o d i l a aA U f f la i t r i n i ; l a tao l i t m i t i f b a sita p ro to n i i f a p n iii Tea co; si U h lo sta r la to o to e tn le a l AI m u m Im ita r r e f ia a a r jta tto l, hot Z U1 l a n ta t U p u r oo AlaarvUw* ----------------- ------------------ ' ~ fc: IrrtK j r a i K f i X n s n t C a t joo A lar ta ia a a tto r a l; Aia I to li p o p i lo C!t b ; j t a fflo fio n * . ha brut 11 Va p re fir V o l_ j* ^ ^ ' A l a v a 11 Ita ao odo VA > m .j f i a l I t M t f i i i r ) - t > l a f C T l r C n i n r t i v v i l i tao eoa.' . a i u t a i ta r a t i b n t tU a baio y n U a th lU ta z z a h u si s.''i i r l i s nwrrt ti ^r 7r3. rl.ai-.a-3aM^. X v i l i ho tory hae;;?. to A llessa i l V a aosl ileo i i t la t c r l r o ii^ U > lo tla u o s tls a , X top ; t A l l M i n f tr s f r tu r &t*.til u d i n u ^ lo UXt t U i t spiai to h la ori.- c u r u l o : . r o s t a rari m ah. Ma Ctlof flhU alodai jrr/v h n u C. T U lU f t X otam otloaal > I .* : f - T - f - ' M 8 \f I i I i Dm > N ( N w r t a t u i : lu > yng vrr tue- for c i l l l r . t* ay u t n t i the m i e l e r 9 alci. *ae ?Kilau*c U tauie U n u w , tawictfe* viK w ti J, H i - -- (IHM), mt. N i l t n n i co, y ta i t t t ta re i m l i t i H I t la ta t i ; U u , 1 m a aclaals. a to ,/ cl tr-a L.nwli*.. tra n a la tl::. fa r yaur f l i r t . 1 a i m Mitt yaa th a t ta la n j a t i la w y l u t a t i t i , 1 k m ; n < t i i n a t t i n t i la t a n ^ i t : l U i u , Laura atui ( M il u <2 ( I l l e n . k ille t la aauufacxund *y C m n L m i PtWucu (*f Canada), a uiTieion a f l i e fe a n rla -aillla a a C n jic ; a f Canada, U atu .. k v n r .il) f ill ( M i i 2.4-: and . I t a i t Mat In la a l i t aay ham a n u i M t a ,4 l - l inatta.- of -icaw *. i-icatU la t.a -d lc .la ra -iMti4iH,tM l e c u . H u m t i . i i c a i e.)- aa*i net r-fcin/fecterv i . l . i - T , l `. r ; amU- - s k i n p a r c u i r i I t fra a .* a. a t fra* te tti lif f e r v i.t a a a u f a e tu n n . la te ra le 1 a aa*.- naca Sy a* U.e i t . l .e- v - te 'wert e a trarletr af attar u n ic i* * for-- l a U t u , -. at a -lc - cantala 2 ,4 ,j .l . T u fc e ll ##t- U llera'* alca casi I deaeri*# ary her. le i I . f r-.ic u c :. .ic or as.- :.-t c r.itii.' i . l . i - l . To CUT M h k .lc iK t *-11 n i r a t aac-jf u t u r e 2.4.1-1 aa th eir aead tille r aar.tciala* 1,*,5-T m i l l i t * taau junb.a*c* ftoc a./ af b v aale yaadueen. CenaaTwatly, tha aaurc* a f ta r 2.4.1-T i l i a . (.u em a* !/ aa U n it U the* U |M tim cavnct ba Id e n tifie d . I aar* am t a eo, y a f the acac a rtic le to V. . -u* a f a, bat 1 oaw aat h t . i h . a/ c x t x i U frac vi. . Ut I - it. r a . t i a r t , aa c n re ly la . * .a t euraeetefr*; / ta aaiurw e w u i r c i t u t cut 2,4,1-1 p n w rti< " . i t free t * ' I h - il'. . * t i t * Bade te a r attan<t te liana aa/ tae annoia a f tu U tiiM a t. m i ta ran tu t a n wve-1# to achieve dealrad a a n a ltle lty . p art ta lly leceva* l* 2 ,4 ,t-tsic fc l* n ;lm a c y ac * tic c e li Bit u.c e t.r arc i l t.lflc a r.tlr a e rt to a li t --.n trl .la ta i-a e n el. I* a n canti* u le . l e t a tte f.,te to m f i n l... cove.i t r r tic : e f liu ti tv M iirty ir caci. to a i i c i t a p a a ltlv t 35' r-t-.'-iio . .- e r- I r - . i to I f you r . a r t n a v t r y m c m i t i t t-'wae an,-it. h o :<r ? .j 1 I* I I -A i8 \U ar 8T0Z >0 '***CUU!3 NCOIVOWTBO - hr!.Ut<r ". Ultui i: '.7 l i . '.i . . # it , Wfc t i l i a, ;.rcei-v.k Ktrivi:.,' o; 1. u.r rl* u . ra.-^* st . ): . ',r w io . *ccs=pc4 jrour t a i, i~ . j u h te J -;, l-;* . * Jtv `?v.;:'Oi-jo*. Aa ocu u 3T'. blxi^, ;bK .tiiJu ta r./sri,. bill laetact T.ar.la .ala Vr /u.j -tiato:' i.t.'7-t 1:.b.-.~ij.wU>b it.f<iT i. &.iter ;' af .N s t av u t -e.- t* i t t i ce..-.!*. $ fe :i.t.r.ly, ?.*i 9 2j : * i 1 : 'f J.... >\ ;r/l*y. r.... l..ie l jn/c- ut.. Fi** Vi; : V.-:' . . v : .`rsgja s il te fe p l F& s Spi fX r & .S S n '* a: A>::\ 'V v*# ""v fe > & *% V* ; ' !* a, f. - fe i i State of Arkansas O ffice of t h e G o v e r n o r State Capitol Little Rock T2201 January 10, 1980 BillClinton J Governor Mr. Jarrell Southall, Director Department of Pollution Control & Ecology 8001 National D r i v e ____________ _ Little Rock, AR ..... - ^ ' ' Dear Jarrell: On Monday, January 7, my office received a telephone communication from Ms. Adlene Harrison informing us that a letter was forthcoming with regard to the problems surrounding the cleanup operations at Vertac, Inc. in Jacksonville. It is very important that the contents of the letter not be i discussed, at this time, with anyone other than members of our respective staffs \and the staff of EPA. in cerely, ------ BC/SS/hnj. BILL CLINTON Governor y 1 KM*r- I IMBi *72*3 r Pire. Line 2i5:nor.t A tr a c t of lend situ ated p a r t o f t'r.:! c f. True-. and r t of th e 32? the 5 th P rin c ip a l K crid: Fart I: * J-213. - r mzv o f P u la s k i, S ta te o f Arkansas* oj-r.i, Lon J I , T c ra s h ip 3 t c r th , F.tr.p-J 10 " e s t 56, Township 3 a r t h . ?.ingc 11 TToct c f -g acre p a rtie u iirly doscrlbad as fo llo u s; 21= ) 'jZ' ~ i r x on th e o r.s t lia ,- o f s a id S 2 o f S e c tio n 5= *= = F3 i = - r iiic h i s 3 .0 i* 0? 77., 59G .6 f o ^ t f r o c th e n o r th e a s i c o m e r of s-tid G2* s.o f S o o tie r. 36; tr .3r.0C lz` 0 3 ' 2 . . 6 0 7 .3 fo ,-t co a p o in t: th o n o e S . 23* L6' z . , IS'u.Q f o o t t o a p o in t; -.hanse S . 26* 21' r . . I L ! . ' s t t s i p o in t th o s o u t h o t s t o r l y l i n o of tin i s s o u r i P a c i f i c ? .u ilrc o d Ccnar.y1s r . p h t - o f- a y ; th -n e c . r . cli* 09 2 # 50i f o o t l i e n ? S lid s o u tlv e a s to r ly r i g r .t - o f - i lin o to t n p o in t; thonco S . 26* 21' 2 . , "LnO.2 if . c t t o a p o in t: th e n c e S. 25' U6' 51ii.O f o o t to c p o i n t ; th o n co S.. uc* Op1 7: 2 1 .5 f s o t to a p o in t then cc 3 . Cl* 05 ' 7 . , 77 .6 fe e t to 1 so:Lt on th e n o r t h e a s te r ly r i g h t - o f - 'tty l i n -:f t : n Arki.no -.0 Crdna:r.co P l a n t T r.to r 7 - 0 2 Lino Z i s e n n t ; th o n co L " =7* , L2 i f o o t a lo n e sr.id nor-:h c a s t.-TlV r i t h t - o f - " r.y l i n e t o .1 poin:t; 2r.or.co y .c i* 03' 2 - , 6C.0 f o o t to 0 p o in t; th - r .to i,4* 0 3' 2. , 21.2 f o n t to t r n p o in t of b e g in n in g , c o n ta in in g 0 . 9ii o or.-, n s r s o r l e s s . P art 2 : (J-21i) B eginning on th e n o rth lin o c f sa id f r a c ti o n a l S ectio n 31 a t a p o in t v-hich i s S . 87* L5' 2 . , =9-3 f e e t f r t n th e n e r t :1:v /-st c o m e r c f s a id " r a c t i c : S e c tio n 31; th e n c e S. 37* L=' 2*. p li.2 fe e t 1er\z s a id n e r e i 1in s cf F r a c t i s r ;a i S e c tio n 31 to a p o in t; th e n c e 3 . 2c* 21 2 .,. 795.2 f e e t 2o a pci: or. th o r:a r th tr e c te r ly li n e o f the L iis a o u ri .P a c if i,c H c ilre a d Ccnpar. '/ '5 r i g r .t c f-n u y ; tno n co S. =ii* 0 9 ' 77., 30.,^ f a c t a l,zi'.T s a id n o r th w e s te r l y r i g h t - o f - Ojay l i n e t o a p o i n t : th a r.e s F . 26* 2 1 ' 616.6 f e e t to tno p o in t of be- g in n in r, c o n ta in in g C.39 so re , co re or l e s s . r e m i t fo r ~ a to r Pipe Line Cross! no : (J-20ii-A ) .. t r a c t o f lan d s i t u a t e d i n th e C ounty o f P u l a s k i , S t a t e o f A rk an sas, b e in g p a r t c f t n s of- FZr- o f S e c tio n 36, Tov.-nship } F o r th , Pange 11 "Test o f tr.c = th P r i n c i p a l M e rid ia n , and b e in g ir.cr9 p a r t i c u l a r l y d e s c r ib e e as : o11ct. o : Be p in n in g on th e s o u t h e a s t e r l y l i n e o f th e 'M is so u ri P a c if ic Ha il.-o a d Cceaar.y' c t- i- h t- o f - w a y a t a p o in t v.-hich i t 69* 0 9 ' 7!., 3= 3.9 f e e t i r o n th e n s r t h u a s t eor.nor c f th e S2? NE-~ o f s a id S e c tio n =6 ; th e n c e 3 , =4* 0 ? ' JO.O f e e t a lo n g s a id s o u t h e a s t e r l y r i g h t- o f - w a y l i a s to a p o in t; thor.ee T. 33* 2 1 ' !7 ., 1C0.Q f e e t t o o p o i n t on tr.a r .o r th r /o tt.- r ly l i n e c f s a id In o o o u ri ...-- - :19024 .. 1 serssarsro et" ( - - .to r .Toil S lto : r P a rt 1: A i r a s a cl* lo r d a ia n a to d i. aha cou th 100 f u - t cf Frac c i tho Jtfc p rin c ip a l - a r i d C aunty ci* p u la s h a , S ta te c i A rk an sas, s c i n j 1 See l i e n 51, Idocasnap 5 i o r tn , aanpa 1C ..era containing ?.0? acres, aura cr le s s. Para 2: A t r a c t of lend a ir .: zzzd i n th e County os' P u la sk i# S to tc c f A:rfcar.sas, b Lag p a r t of th e 3*7-1 STTf- : f S ee" l e a ? 2 , '- -c r ionic ; erth* H u-tc 10 '.Sosa o f the J t h P r i n c i p a l " J 1 zr.z b e in g a c r e p i r o i s u i u r l y i c c c r i i a d as f e l l r e s : S-oa i m i n g ea a ho s o u th .-.asa e a r n e r tff = -id S c c - i .'i ; 2 ; tr. anco n o r th a l a r .; th e '.vest l i r e or.ir. S o c a ic n .-2, 1CC-.0 :: u p ti:;t ; chorea east and p a r a l l e l to tho s c u th ls*> s i id S s c c i .s ; 2 , iifli.O : 'c - t t.. r. p r i s " ; thenes south 100.0 icca ta a peina :n the south lin e ai said S cotian J2; ato n e c -.asst a lo n e s a id c o u th l i n e aa ado noin n c i b o o in r .ir .;, sa a t.-.in ir.g I.OL a c re s, acre or io s s . p a ra a i ana eTTt i - t - i F r a c t i o n a l S o c a ir n , T.-ousAip 2 Ocra.-., Hr.-,go 10 *7csa c i the -jth P rin c ip a l u r i a n and ic in g a c re p a r tic u la r ly d escrib ed aa icilc.as : .as a i m i n g i t ans n o r th w e s t c o r n e r s i s a id F r a c t i o n a l S s e a ic n 5; th e n c e e a s t i l e a t h e n o r th l i n s c i s a i d .f r a c ti o n a l S e c a io n 5 7 0 0 .0 f e e a t o a p o in t; th en ce seaah 1C0.0 f e e t to a p a in t; th sn e c rasa and p a r a l l e l no the ^ o m h l i n o o f s a id F r i c t i o n a l S e c tio n f , 7 0 0 .0 i c o t to a p e in a en th e 'we3a lin s ci sain F ra c tio n a l Socaicn J; thonco n o rth along said west lin e to tna ooir.t of be,tinning, co n tain in g I.eO e e re s , nora or le s s . ? t m n e n t Cas c ra n e f a r A ccost P.oad: ( J -2 0 7 ) A t r a c t o f lan d ai ren ted in the Count-/ c f P u la sk i. S ta te sf A rkansas, boiag p a r t o f tile i~ ^ o f f r a c t i o n a l S e c tio n JO , 7 en n sr.ip J t i e r t h , Bangs 10 T oot 01 r r i a s i p a l Hu r i d i a r . , in Dupree* s A d d itio n to th e acr.-r. o f Juclcscn- T illo , A ricansac, and bein g a c re p a r t i c u l a r l y d e sc rib e d as f.iiicr.'o P u re si Ai - 3 c c in rin o an ti n e rth ad so u th q u a rte r lin a of sa id Sect: JO a t a p o i n t n h ic h is . 02* CG r ?.2.0 T o it T roc t h j ci-r.tc r o f s i i d F r a c t i o n a l S o c a ic n JO; th a n e c S . 02* 00* r . , lii -3 f o o t a i a n r s a id r.crar. an: so u th q u a r t e r lieu; tc z r o i r . t ' uhor.ea 5 . L l* Oil* S . . 2 2 9 .1 f a c t to a p c i a t ; thenes 5. 3* 'c* 01^.2 is o t t s s p o ia t; thar.ee 3 . J6* 37' . , 172.7 fc- to a p e i n t on the. w e s t e r l y r i r . t - c i '- n v / l i n e c f :t.S . H itt...tv `4 -- --C \ W ^he^r I i i 3SS| l/tlW-sr- c os:: ;? ) r EPT.T ALL i u '.t Zv. Z-SZZ PEEEEi.'T3, T h at th e "a.- Casa.-tr-e-at ( T r a n s f e r o r ) . s s r i n r tk ro u rh th s Cor.sasr.dlng O f f ic e r , A rkansas O rig in s? P la n t , L i t t l e P .ss:, .'.rka.asa s, t " those p re se n ts docs tra n s fe r cu stsd y , c o n tro l, snd a c c o u n ta b ility u n to th e -- r A s s c ta A .d r.in isa ra sio r. ( T r a n s f e r e e ) , t h e fo H aw in g la n d zr.c i.xp rsv -ra n ts theraon, to a it: Tha A rkansas Ordnance P la n t lo c a te d lr. P u la sk i C ounty, A rkansas and s o r .x a lr .in r a t o t a l o f sever, th o u sa n d two h u n d red f i f t y taro ar.d n i n e t y - 1* er.e h u n d re d th s a c r e s (T , fp'2.'r 6 / th e l e r a i d e s c r i p t i o n o f which Is a tta c h e d h e r e to a s E x h ib i t "A" w hich i s nado a t a r t h e r e o f : A ll b u ild in g s , u t i l i t i e s and ir.sro v en en t3 which a re s re s e r.tly lo c a te d on the land er.brrcir.n th e A rkansas Ordnance P la n t, the d e s c rip tio n of s.r.ish i s a tta c h e d h e re to as i n h i b i t "T" w hich is nade a c a r t h e re o f: A ll " in s ta lle d re a l p ro p erty " which is p re s e n tly lo c a te d in the abeve- d cscrib ed b u ild in g s o r lo cated an the ab o v e-d escrib ed p rvnisco the ia s sro p tio n o f which is a tta c h e d h e re to as E x h ib it "0" nhier. i s itade 1 t a r t h e re o f: A ll o f tha personal p ro p e rty lo cated a t th e A rkansas Ordnance P la n t as d e s c r i b e d an rorcio EP3-1 o r 3 F 3 -1 .1 , OP.D O p-O lii-ibb-i th ro u g h IsPp i n c l u s i v e . T h is t r a n s f e r i s in te n d e d is c a v e r and -.sfsrsae a l l s' . 5 . O sv e rrjse n t p e r s o n a l s r o x e r t y e x c e p t r . e t a l nor.ponents ar.d p ack ag in g n a x c r t a l f a r w hich t h a T ra n s f e r o r i s a c c o u n ta b le . S a in n e t s ! c a a s o n o n ts ar.d p ack a g in g n o t a r i a l w i l l be ressoTad fro r. th e p re m ise s by th e T r a n s f e r o r w i t h i n ;0 days a f t e r th e c -ifa e tiv e date k u rto f. The T ra n s fe re e w i l l proceed to ra k e such in v e n to ry cheeks a s he deans n e c e s s a r y p r i o r to 1 J u l y VPii6 o f a h ; p e r s o n a l p r o p e r t y d e s c r ib e d in above ncnticn-.-d P o m s 3 = 3 -1 . Any d is c r e p a n c ie s d is c lo s e d a s a r e s u l t a t such chocks w i l l be r e p o r t e d by th e T r a n s f e r e e Pa sh e T r a n s f e r o r f a r n e c e s s a r y ldiustsicr.t by 1 J u l y IfLi. The e n t i r e f a c i l i t y ( In c lu d in g r e a l ar.d p e rso n a l p r o o e rty ) has bser. accans.-.r.i.anted and i s s a tis f a c to r y fa r id le sta n d -b y ao r.d itio n fo r usa in i t s o r ig in a l p u rp o se . The f a c i l i t y has beer, review ed by a b eard of con s u lta n ts and i t has beer, recossaendcd th a t se v e n ty -th re e ( 7 ;) b c ild ir.c c ( l i s t e d on Page 1 E x h ib it C) w hich c a n n o t b ; eea n o siic e .lly sc c o n tre a ir.itc d should Sc d s s :ra y e d in the ev en t th e f a c i l i t y i s d iro o so d o f fo r o th e r Shan i t s o r i g in a l p u rp esa. Thr. u r .d .rs ig r.v d T r a n s f e r e e h e re b y acknow ledges t h a t d e l i v e r y o f th o s a i d la n d ar.d ia.aravtai.-r.ps eras n ai-t by th u T r a n s f e r o r an d r e c e i p t s f s a i d p ro p e rty Is h ereb y -.skns-.:i:dr.cd. Thu u n d e rs ig n e d T ra n s fe re e h e re b y a g re e s t h a t or. 1 J u ly I f k c f u l l a c - e e u n tv .tillty w ill be assured bv said T ransferee fa r a ll seasonal props say lisa -a d sr. P a m s 0=2 - 1 . OP.: C J-C lie-V e-l th r u CP.: :;-0 1 L - ii6 - e a p ar.d fu r th e r req u ests fo r adjustm ent w ill be node to the T ra n sfe ro r. IP " IT :T e 3 PP.eP.TPr, th e " o r D er-.rtr.-.n t a c t i n g t h r e u i t s Cortas.adinr O ffic e r, A rkansas Ordnance P la n t, A rkansas, and T ar A ssets A d m in istratis:., have h e re u n to s e t t h e i r hand:: t h i s la th dsy of June l? i:6 . " Aa D E =;:T- - ( Tr a n s f e r o r ) ( / </ r r 'S'--.ir. jc :ir.;c n " / --- C-.rr... C r d . ^ b - r -, ! Czrrs.r.r.ir.c O f T ic .r rxnr.rr.-s O r d m n c t P 1r r . t , -.r>:r.::s".s TAJt AE3ETS A~-:i!.'T3T?_ATICK (T r-'.asf t r e e ) ".v: C /kzcrf^-^1-- i , w'-rL::;.*:: rir-.ctrir 19C / //_TRANSVAAL, INC. // THE GAS CHROMATOGRAPH iC DETERM IMAT IOf.1 OF 2,3,7,3-TETRACHLORC'D L5ENZQ-P-QI0XI." ,4,5-TRiCHLORCPKENOXYACET!C ACID (2>4,5-7;, T 3UTYL ESTER, AMD 2,4,5-T 2-ETHYLHEXYL ESTER i; August 13 TABLE OF CONTENTS Digest Page Objective.................................................... 1 Results and Conclusions..................................... 1 Experimental Section Reagents..................................................... 2 Apparatus.................................................... 4 Procedure for Preliminary ireatrr.ent of the Sample (1) for 2,4,5-T. Extraction Alumina Column Chromatography............... 6 Procedure for Preliminary Treatment of the Sample (2) for 2,4,5-T Esters.......................................... 7 Saponification............................................ 7 Extraction.................................................7 Fjorisil Column Chromatography........................... 8 Procedure for the Gas-Chromatographic Determination of 2,3,7,8-Tetrachlorodibenzo-p-dioxin.................... 9 Results and Discussion.........................................10 Recovery of 2,3,7,8-Tetrachlorodibenzo-p-dioxin........... 11 i Recovery of 2,3,7,8-Tetrachlorodibenzo-p-dioxin from Florisil Column Chromatography............................ 11 Linearity of Response of the Electron CaptureDetector.... 12 Limits of Detection......................................... 12 Graph of Response........................................... 13 Typical Chromatograms.......................................14 in in G-1 jl DIGEST Objective This is the report of an investigation to determine the 2,3,7,8- Tetrachlorodibenzo-p-dioxin (TCDD) content of 2,4,5-T and 2,4,5-T butyl and 2-ethylhexyl esters manufactured by Transvaal, Inc..,at Jacksonville, Arkansas. /... - "" .................... The compound of interest, TCDD, may be produced as a by-product' in the manufacture of 2,4,5-T, and is of significance due to its alleged high toxicity to humans____________________________________ The objective of this investigation was to determine the amount of TCDD produced in the 2,4,5-T and its butyl'and 2-ethylhexyl escers manufactured bv Transvaal. Inc._________________________________________ Results^and Conclusions / / The analytical method developed in this investigation was based on methods by Dow Chemical Company, Hercules Incorporated, and D. A. 1 Elvidge. Samples of 2,4,5-T acid were dissolved in aqueous acetonitrile and extracted with hexane. The extracts were concentrated and then analyzed for TCDD by gas chromatography using a flame ionization detector. Analysis of samples of esters involved a preliminary sapcnificatio procedure followed by extraction of TCDD from aqueous dimethylformamide 1 Elvidge, D. A., Analyst, 96, 721-727 (1971). Page 2 with hexane. The concentrated hexane extracts of'the esters were analyzed by gas chromatography using an electron capture detector. None'of the samples of 2,4,5-T acid and 2 ,4,5,-T^i?ters examined ,,/ contained TCDD at a concentration greater than^O*. 1 ppm./ EXPERIMENTAL SECTION Reagents n-Hexane Acetoni tri le Aqueous Acetonitrile Equilibrated n-Hexane Diethyl Ether Quality suitable for pesticide residue analyses. (Burdick and Jackson Laboratories, Muskegon, Michigan) Quality suitable for pesticide residue analyses. (Matheson, Coleman, and Sell) Solution of 90:1 acetonitrile and 10:1 distilled water by volume. n-Hexane saturated with the aqueous aceto ni tri le solvent. Quality suitable for pesticide residue analyses. (Burdick and Jackson Laboratories, Muskegon, Michigan) .9032 Page 3 Chloroform Ethanol Methanol 25% Ether-Hexane Chloroform-Ether, 1:1. Double Distilled Water M,N-Dimethylformamide Methylene Chloride Sodium Sulfate Potassium Hydroxide Ammonium Hydroxide: Water Solutions Aluminum Oxide FI orisi 1 Quality suitable for pesticide residue analyses. (Matheson, Coleman, and Bell) Placent alcohol (Anderson Laboratories, Ft. Worth, Texas) Anhydrous, Reagent grade (Mallinckrodt) A. C. S. Reagent Grade (Baker and Adamson) Spectroquality Reagent (Matheson, Coleman, and Bel 1) Anhydrous, Granular, A. C. S. Reagent Grade (Mai 1inckrodt) Reagent grade pellets (Mai 1inckrodt) 1:1 and 1:2 by volume (using 25% NH.qh and double distilled water) Woelm, basic (cationotropic), Activity Grade I PR Grade, 50/100 mesh (Supelco, Inc.) TCDD Reference Material - Obtained from D. Firestone, II. S. Food and Drug Administration. TCDD Standard Solution: 2.5 milligrams of TCOO were dissolved, with warming, in 10 ml of diethyl ether contained in a 25 ml volumetric flask and adjusted to volume with ether. Dilutions were made, with Page 4 25% ether-hexane to yield solutions containing TCOD at concentrations of 20 ng per microliter and 0.2 ng per microliter. Apparatus All glassware was cleaned in chromic-sulfuric acid mixture, washed with water, dried and rinsed with hexane prior to use. A Tracor MT-220 gas chromatograph, equipped with a flame ionizacien detector, an electron capture detector (with a 10 mCi Ni source), a 1-inV Honeywell Electronic 194 Recorder, and an Infotronics automatic digital integrator, was used. Chromatographic Columns - Two six-foot glass columns of 2 mm i.d. were packed with 3 percent 0V-17 (Pierce Chemical Company) on 80/100 mesh Chromosorb G (Johns-Manvilie Company) and conditioned at 250 C. 'for 24 hours before use. One column was attached to the flame ionization detector and the other to the electron capture detector. Operating Conditions The following operating conditions were used: (A)- For 2,4,5-T: Detector temperature - 260 o C. Recorder chart speed - 12 inches per hour Carrier gas - Nitrogen (Prepurified grade) Column temperature - 200 C. o Injection port temperature - 250 C. Carrier gas flow rate - 30 ml per minuce w Page 5 Hydrogen flow rate - 60 ml per minute Air flow rate - 1.2 cu. ft. per minute Attenuation settings were adjusted to give at least a 25 percent full-scale recorder deflection for an injection of 40 r.g 2,2,7,8-TCDD. (B) For the butyl and 2-ethylhexyl .esters: (Electron capture detector) Detector voltage - 12V Detector temperature - 230 C. Chart speed - 12 inches per hour .Carrier gas and purge gas - Nitrogen (Prepurified Grade) Column temperature - 200 C. Injection port'.',,temperature - 250 C. Carrier gas flow rate - 30 ml per minute Purge flow - 20 ml per minute Attenuation settings were adjusted to give at least a 25 percent full-scale recorder deflection for an injection of 0.4 ng 2,3,7,3-TCDD. Methods and Procedures Procedure for Preliminary Treatment of the Sample: (1) For 2,4,5-T: Extraction: Twenty grams of sample were weighed in a 500 ml. separatory funnel and dissolved in 100 ml of warm aqueous acatGnitrile. Then 100 ml of equilibrated hexane were added, and the funnel shaken vigorously for 30 seconds. After the phases separated, the lower phase O Page 6 (Acetonitrile) was transferred to a second 500 ml '-funnel. The first 500 ml funnel was swirled to recover traces of acetonitrile adhering to the funnel walls, and these drainings were transferred to the acetonitrile phase. The hexane phase was added to a 1-1 iter funnel containing 500 ml of distilled water. i The partition step was repeated twice more, using 100 ml of n-hexane each time. The acetonitrile phase was transferred between the two 500 ml funnels and the hexane phase added to the 1-1 iter funnel after each partition. Following the third partition, the acetonitrile phase was discarded. The three combined hexane phases in the 1-liter funnel were.then- washed by shaking with distilled water for 20 seconds. After the phases separated, the aqueous wash was drained off and discarded. The hexane phase was dried by passing it through a fourinch glass funnel containing a small cotton plug and 50 g of anhydrous Na^SO^ The hexane was collected in a 400 ml beaker and the separator was rinsed with several TO ml washes of hexane. The washes were passed through the funnel to wash the I ^ S O and collected in the same beaker. The hexane phase was evaporated just to dryness on a steam bath using a gentle stream of dry nitrogen to aid in the evaporation. Alumina Column Chromatography - A column was prepared in a glass tube, 150 x 10 mm, having a porous glass plug, by filling the tuba with ether and adding alumina while gently tapping the tube to release any air bubbles. The alumina was added until it reached a height of 8 cm. The column was then washed with 50 ml of ether, followed by 50 ml of n-hexane. '.1 6 m Page 7 The residue from the evaporated hexane phase'in the extraction step was dissolved in a small volume (about 1-2 ml) of diethyl ether and transferred to the alumina column. The beaker was rinsed with several additional ether washes, and these were added to the column. The column was then eluted with 50 ml of 25.j ether-hexane solution. The ether-hexane fraction was evaporated just to dryness on a steam bath under a gentle stream of dry nitrogen. The residue was quantitatively transferred to a 4 ml screw cap vial, using a mixture of 1:1 Chloroform-Ether to accomplish the transfer. The sample was evaporated just to dryness once more, and the final residue dissolved in 0.5 ml of 25% ether-hexane solution. Procedure for Preliminary Treatment of the Sample: (2) For 2,4, Esters: ; Saponification: About 10 g of ester sample was accurately weighed in a "400 ml beaker and dissolved in 50 ml of ethand. After the sample was dissolved, 10 g of potassium hydroxide dissolved in a few ml of water were added, followed by the addition of 50 ml of double distilled water. The solution was heated under reflux for three hours, shaking occasionally. The solution was then evaporated on a hot plate until no noticeable odor of butyl or 2-ethylhexyl alcohol was present. The residual solids were dissolved in 100 ml of N,N-dimethylformamide and 200 ml of double distilled water with slight warming and transferred to a 500 ml separatory funnel. Extraction: The solution was then extracted with 5 x 50 ml portions of n-hexane, the combined extracts being collected in a 500 ml Page 3 separatory funnel. The combined hexane extracts were then washed with 60 ml of 1:1 MH^OH and 30 ml of 1:2 NH^OH in that order, and finally washed three to five times with 50 ml of double distilled water (until wash water was neutral). The extracts were dried by the addition of 30 g of sodium sulfate to the separatory funnel and the funnel contents swirled and allowed to remain in contact with the sodium sulfate for 30 minutes. The extracts were then filtered through a funnel containing a cotton plug and about 3 g of sodium sulfate into a 600 ml beaker, and evaporated to dryness on a steam bath under a gentle stream of dry nitrogen. Florisil Column Chromatography: A column was prepared by filling a glass tube, 150 x 10 mm, having a porous glass plug, with n-hexane and adding Florisil while gently tapping to release any air bubbles. The Florisil was added until it reached a height of 8 cm. The column was then washed with 50 ml of n-hexane, followed by 50 ml of 2011 methylene chloride-hexane solution. The residue from the evaporated hexane extracts was dissolved in a small volume (1-2 ml) of n-hexane and transferred to the Florisil .column. The beaker was rinsed with several additional hexane washes, and these were added to the column. The column was then eluted with 50 ml of 20% methylene chloride-hexane solution. The. methylene chloride-hexane fraction was evaporated just to dryness on a steam bath under a gentle stream of dry nitrogen. The residue was quantitatively transferred to a 10 ml volumetric flask using the 20% methylene chloride-hexane solution to acccmDlish the transfer, and the solution was diluted to volume. 1SC18 Page 9 Procedure for the Gas-Chromatographic Determination of 2,3,7,8Tetrachlorodibenzo-p-dioxin: Standard TCDD Solutions: Solutions were prepared containing 20 ng of TCDO per ul in 25* ether-hexane and 0.2 ng of TCDD per pi in 25* ether-hexane. These solutions were used as standards for flame ionization de tection and electron capture detection, respectively. The standard used in flame ionization detection corresponds to a TCDD content in 2,4,5-T of 0.5 ppm, and the standard for electron capture de- tection corresponds to a TCDD concent in 2,4,5-T esters of 0.2 ppm. Extract solutions of samples of 2,4,5-T and 2,4,5-T esters prepared as described v/ere chromatographed under the conditions described. For 2,4,5-T samples, a 2 ul injection of standard TCDD was followed by injection of a 2 pi aliquot of sample solution. For the esters, the injection volume for standard and samples was 1 pi. The retention time for TCDD in 2,4,5-T samples was about ten minutes and in the ester samples about six minutes. The con centration of TCDD in the samples was calculated using the following formula: r = Au Vs Cs ^ As Vu f where f = for esters, f = for 2,4,5-T, and :Cu = concentration of TCDD in original sample, ppm Au = peak area of TCDD in aliquot of sample injected 9CS9 Page 10 As = peak area of TC00 in aliquot of standard injection Vs = injection volume of standard, gl Yu = injection volume of sample, yl Cs = concentration of TCDO in standard, ng/yl W = weight of sample taken, g Results and Discussion: A total of 15 samples of 2,4,5-T and 15 samples of 2,4,5-T esters were analyzed for 2,3,7,8-tetrachlorodibenzo-p-dioxin. The ester samples chosen for analysis were of esters manufactured from 2,4,5-T analyzed in this work, with the exception of one sample of agent orange herbicide. The date of manufacture of the samples ranges from 1966 to the present. Only four butyl esters were analyzed, whereas ten 2-ethylhexyl esters were analyzed. This is proportional to the quantity of manufacture and use of the two esters. The esters required a more efficient clean-up procedure than did the 2,4,5-T samples, owing to the use of the electron-capture detector which has greater sensitivity, but is more easily contaminated than the flame ionization detector. Clean-up by Florisil column chromato graphy proved to be very satisfactory in removing interfering sub- stances^._______ - -- " All of the samples contained less than 0.1 ppm of 2,3,7,8- tetrachlorodibenzo-p-dioxin, except the sample of agent orange /// L \ herbicide, which contained 6.21 ppm. The agent orange was received ' i from the.Air Force and has been stored for about two years at this location. __.-- -- f Xi v w T Page 11 Recovery of 2,3,7,8-Tetrachlorodibenzo-p-dioxin: " One ml of a solution containing 2 ug of TCDD per ml was added to 20 g portions each of four samples of 2,4,5-T that were free from the impurity (less than 0.1 ppm), and the samples were analyzed by the method described. The addition produced the equivalent of 0.1 ppm TCDD in the 2,4,5-T, which was detected by the flame ionization detector. A 0.5 ml aliquot of standard solution containing 0.7 ug TCDD per ml was added to 10 g portions of each of two butyl and two 2ethylhexyl esters that were free from the impurity (less than 0.1 ppm), dissolved in 50 ml ethanol, and the samples were analyzed by the method described. The spiked samples contained the equivalent of 0.35 ppm TCDD in the esters. Recoveries of 43 to 60 percent were obtained. Recovery of 2-,3,7,8-Tetrachlorodibenzo-p-dioxin from Florisil Column Chromatography: A 2 ul aliquot of standard solution containing 0.7 ng TCDD per ul was spotted on a Florisil column prepared as described earlier. The sample was then eluted with 50 ml of 25% methylene chloridehexane solution. After evaporation to near dryness and dissolving . the residue with 0.5 ml of 25% methylene chloride-hexane solution, a 2 y 1 aliquot was injected into the gas chromatograph. A recovery of 95% was obtained. Page 12 Linearity of Response of the Electron Capture Dete~ctor:` Portions of 0.4, 1.0, 1.2, 1-4, and 2.0 ul of a standard solution containing 7.0 ng of TCDO per pi were injected on to the 0V-17 column connected to the electron capture detector. The attached graph of peak area versus nanograms of TCDD on column appears to be linear up to 8.4 ng TCDO over the range examined and passes through the origin. Limits of Detection: Under the conditions of the method the lowest level of TCDD detectable corresponded to a sample concentration of 0.1 ppm TCDD in 2,4,5-T and its esters. Typical chromatograms are attached. :y <. Page 13 I )- 't i !