Document dDNzMVnVv1eVGR8K9ow5RyojQ
STRUCTURE
STATUS
October 24, 1979 , F.C.M. SUMMARY
DIOXINS - DIBENZOFURAMES
POLYCHLOROPHENOLS ECEls.
* POLYCHLORO DIBENZO-P-DIOXINS (PCDD) (Tetra - 2,3,7,8 - TCDD)
Polychlorinated biphenyls
PCB's
* Polychloro dibenzofuranes (PCDF) (Tetra - 2,3,7,8 - TCDF)
SCTWE OROER.
\Q \9.0
* Contain one or more, but not necessarily all, chlorine atoms
Vfj
9
\*
i9* *
C
tyO
GOO 1 8 0 8
OTHER PRECURSORS '
CL CL CL
CL
(X = 1 - 6 ) CLX
Ot h e r
halogenated
aromatics
- Nitrochlorobenzenes? Ch l o r o a n i l i n e s ? ETC.
CHEMISTRY - CONDITIONS
- Ca n b e f o r m e d f r o m a v a r i e t y o f a r o m a t i c c h l o r i n a t e d
COMPOUNDS WITH HEAT AND TRACES OF HoO, Oo, COMBUSTIONj
CHLORINATION OF PHENOLS (BIPHENYL) AT ELEVATED TEMPERA TURES CATALYZED BY ALKALI MORE LIKELY TO PRODUCE THAN OTHERS.
- OCCURENCE
- Mo t y e t s h o w n t h a t c o m b u s t i o n p r o c e s s e s (p o w e r p l a n t s ,
ETC. - CLAIMED BY Dow) WHERE ORGANICS AND CHLORINE
CO-EXIST WILL PRODUCE MEASURABLE QUANTITIES ( > 1 0 PPT)
OF CDD .OR CDF,
- Precursors - PCB's, 2,4-0, 2,4,5-T, e t c ., some of w h ich
ARE UBIQUITOUS, IN THE ENVIRONMENT, PROBABLY REQUIRED.
G001809
BIOLOGICAL EFFECTS IN ANIMALS - CDD and 1CDF
Some of the m o s t t o x i c m a t e r i a l s k n o w n - c a r c i n o g e n i c , REPRODUCTION, OTHER EFFECTS
Ch l o r i n a t e d D i b e n z o D i o xin s
Tetra-(2,3,7,8) TCDD L50
Guinea P ig Ra t Mo u s e
2|*g /kg 25-45 p g /kg
115p g /kg
Di (2,8)
LD50
Guinea Pig
300,000 PG/KG
Octa (1,2,3,A,6,7,8,9) LD50
Gu i n e a P ig
Tetra (2,3,7,8) TCDD
Ca r c i n o g e n i c i t y ,, (s e v e r a l s i t e s )
Teratogenicity
1,000,000 p g /kg 2.1 p g /kg/d a y 2.1 p g /kg/day
Ch l o r i n a t e d D i b e n z o f u r a n e s
Tetra-(2,3,7,8) TCDF LD-j^qo
^hicks
5 p g /k g /d a y
L iver Da m a g e Ch i c k s
5 p g /k g /d a y
He a r t In f l a m a t i o n Ch i c k s
5 p g /kg/day
Im m u n e s u p p r e s s i o n Rats
5 p g /kg
Im m u n e s u p p r e s s i o n Gu i n e a P igs 1 p g / kg
Ge n era l Toxicity
Ca . 1/5 - 1/10 OF TCDD
goods 10
MONSANTO INVOLVEMENT
Fr o m t h e f o r e g o i n g o u t l i n e , s o m e o f our p a s t a n d c u r r e n t INVOLVEMENTS ARE OBVIOUS!
NITRO
Early (19A9) TCP - 2,4,5-T a c c i d e n t and PRODUCTION TO 1969
WGK .
PCBPe n t a c h l o r o p h e n o l s , c h l o r o p h e n o l s , (PCP AND PCB NOW DOWN)
Possible c h l o r o b e n z e n e s , nitro c h l o r o b e n z e n e s ,
CHLOROANILINS, ETC.
ANNISTON PCB - Early 1930's a n d 1960's - H igh temp
PRODUCTION OF HIGHER ISOMERS
All OF THE ABOVE INVOLVED CHLORACNE CASES.
Ot h e r Mo n s a n t o p r o d u c t s , r e s i d u e s a n d e f f l u e n t s c o n t a i n i n g t r a c e
CDD CDFor c o u l d e x i s t , bu t n o t y e t i d e n t i f i e d .
gOOl811
HUMAN EPISODES from
ACCIDENTAL OR OCCUPATIONAL EXPOSURE In
MANUFACTURE/USE CHLOROPHENOLS - PCB
YEAR 1949*
COUNTRY U.S.
PRODUCTION/
MANUFACTURER/LOCATION PRODUCT
SOURCE
Monsanto/Nitro TCP Accident
.NUMBER CASES
121 (15Of)
1949 1952
W. Germany W. Germany
Nordhein, Westfalen
PCP, TCP TCP
Occupational Occupational
17 60
1952 V. Germany
Boehringer
TCP Occupational 37
1953 W. Germany
BASF/Ludwigshafen
TCP
Accident
55
1954 W. Germany
Boehringer/Ingleheim TCP/ 2,4,5,-T
Occupational 31
1956 France
Rhone-Poulenc/
TCP
Accident
17
Grenoble
1956 U.S.
Diamond Alk/Newark
2,4-D/ - Occupational 29 2,4,5,-T
1960*5* Vietnam
Dow, Monsanto
"Agent Orange"
2,4-D/ 2,4,5,-T
Defoliant
Unknown
1963 Netherlands
Philips-Duphar/ Amsterdam
TCP
Accident
50
1964 USSR
2,4,5-T
Occupational 128
1965-69 Czechoslovakia Spolana/
TCP Occupational 76
1966 France
Rhone-Poulenc/
TCP
Accident
21
Grenoble
______ 12SS* 1968
Japan U.K.
"Yusho" population
Coalite/BolsoverDerbyshire
PCB/PCDF TCP
Accident Accident
1200 79
1973 Austria
Linz Nitrogen Works 2,4,5-T
Occupational 50
_______127.6* Italy
ICMESA/Meda(Seveso) TCP
Accident
135
1979 U.S.
Vertac/Jacksonville, TCP/
Arkansas
2,4,5,-T
Occupational 16
* EPISODES WITH IMPORTANT MEDIA AND PUBLIC EXPOSURE.
TCDDSy m p t o m s - To x i c i t y of
(o t h e r i s o m e r s ?) in Man
Co n s i s t e n t
Ch l o r a c n e
In c o n s i s t e n t ,or Oc c a s s i o n a l
Fa t i g u e ; loss of l i b i d o He a d a c h e Hy p e r p i g m e n t a t i o n (Da r k e n i n g s k i n ) Ir r i t a b i l i t y (Ne r v o u s n e s s , In s o m n i a ) En l a r g e d t e n d e r li v e r Ne u r o m u s c u l a r (Pa i n in c h e s t ; Pa i n ,
Weakness in e x t r e m i t i e s ) H i r s u t i s m (Ey e b r o w s , Te m p l e ) Hy p e r l i p i d e m i a
G001813
CURRENT STATUS - FUTURE ACTIONS
NITRO -
9 He a l t h s t u d i e s (Dr . Su s k i n d ) c o m p l e t e d a t N itro in Ju n e . Re p o r t e x p e c t e d in D e c e m b e r /Ja n u a r y . Ea r l y r e s u l t s o f r e s i d u a l c h l o r a c n e e f f e c t s . o b s e r v e d . Mo n s a n t o m o r t a l i t y s t u d y (19A9 a c c i d e n t 121 CHLORACNE CASES) SHOWS MO APPARENT LONG TERM EFFECTS ON TOTAL DEATHS, CANCER OR CARDIOVASCULAR MORTALITY RATES. ADDITIONAL MORTALITY STUDIES OF CHLORACNE CASES (150+) AND 2,4,5-T WORKERS TO 1969 UNDER STUDY.
G001814
W. G. KRUHHRICH -
Dermatology health study of former pentachlor and CURRENT CHLOROPHENOL WORKERS COMPLETED OCTOBER 4-5 (Dr . Su s k i n d ). Re p o r t t o b e c o m p l e t e d of p a s t CHLORACNE EFFECTS (PENTACHLOROPHENOL) BUT NO CURRENT ACTIVE CASES NOTED.
OUTSIDE WORLD -
e Av a i l a b l e cu rrent d a t a indicates t h a t where
r e s i d u a l precursors exist (PCB, 2,4-D/2,4,5-T, PENTACHLOR, ETC,) IN THE ENVIRONMENT, TCDD a n d /or TCDF levels in the 10/X00 p p t . ra nge may
b e fo u n d in t h e s o i l , a n i m a l s or f i s h . There IS NO CURRENT EVIDENCE FROM OBSERVATION AND TISSUE STUDIES IN WILDLIFE OF ANY TOXIC EFFECTS OR HEALTH HAZARD AT THESE REPORTED LEVELS.
G001815
^ 4 '4'
FUTURE ACTIONS
o It is a p p a r e n t t h a t w e m u s t d e v e l o p a n a l y t i c a l
CAPABILITIES AND KNOWLEDGE OF WHERE BIOLOGICALLY
r e l e v a n t levels of TCDD a n d TCDF e x i s t to
AUTHORITATIVELY CONFIRM, REBUT OR COMMENT ON OFFICIAL STATEMENTS VALIDLY MADE ABOUT THE
PRESENCE OF CDD's OR CDF'S IN OUR PRODUCTS,
FACILITIES OR EFFLUENTS.
All of our basic processes involving chlorination OF AROMATIC MATERIALS MUST BE SYSTEMATICALLY EXAMINED VIA HIGH SENSITIVITY ANALYSIS FOR THEIR
POTENTIAL FORMATION OF CDD'S OR CDF'S AND, WHERE
FOUND, MODIFIED TO ELIMINATE OR MINIMIZE THEIR FORMATION AS BY-PRODUCTS. THIS SHOULD INCLUDE PROCESSES WHERE SOLVENTS OR BY-PRODUCTS PROVIDE UNOBVIOUS COMBINATIONS OF CHLORINE CONTAINING MATERIALS WITH THERMAL OR MOISTURE CONDITIONS, WHICH COULD LEAD TO EXCHANGES, REARRANGEMENTS AND CONDENSATIONS TO DIOXINS OR DIBENZOFURANES.
G001816
In c i n e r a t o r o p e r a t i o n s in key p u n t s m u s t b e EVALUATED TO DETERMINE WHETHER AND UNDER WHAT
CONDITIONS CDD'S OR CDF's ARE PRODUCED (e .G.
HIGH TEMPERATURES AND LONG RESIDENCE TIMES APPEAR NECESSARY TO DESTROY TOXIC PRODUCTS), Co m p l e t e c u r r e n t m o r t a l i t y a n d h e a l t h s t u d i e s UNDERWAY TO HELP DEFINE LONG TERM EFFECTS OF
TCDD EXPOSURES AND CONSIDER, BASED ON CLINICAL
RESULTS, WHETHER APPROPRIATE MEDICAL MONITORING
FOR CDD OR CDF IS FEASIBLE AND DESIRABLE.
G001817
ANALYTICAL BACKGROUND
It is important t o u n der st and t h e a n a l y t i c a l p r o b l e m s
IN DETECTING TRACE (LOW PARTS PER TRILLION) CDD AND CDF IN MATERIALS, WHICH HAVE BEEN REVIEWED IN A POSI TION paper by Dr . G, E. Pag et (6/29/79).
To SUMMARIZE, THE LOW LEVEL DETECTION OF CDD'S AND CDF'S
GENERICALLY AS A CLASS CAN BE ACHIEVED IN MANY LABORA TORIES, i n c l u d i n g Mo n s a n t o 's . Ho w e v e r , f e w c a n p e r f o r m
th e s p eci fi c 2,3,7,8-TCDD a n d TCDF a n a l y s i s a t h i g h
s e n s i t i v i t y (l o w p p t ) w h i c h r e q u i r e s a c o s t l y , h i g h r e s o l u t i o n GC-m a s s s p e c t r o m e t e r i n s t r u m e n t a t i o n a s s e m b l y , AND SOME THAT CLAIM TO BE ABLE TO DO SO ARE MISTAKEN. Monsanto has just received such instrumentation a n d is
c h e c k i n g it o u t a t Da y t o n . It is o b v i o u s a l s o t h a t t h e
high sensitivity analysis is extremely de m a n d i n g o f ti me
(s e v e r a l d a y s ) a n d s k i l l e d p e r s o n n e l , s u c h t h a t it m u s t BE RESERVED FOR CRITICAL CIRCUMSTANCES AND CANNOT BE UNDERTAKEN ON A ROUTINE OR "QUALITY ASSURANCE" BASIS.
G001818