Document 65BY68zdyDq37N1Ew80rDwDp6
VII. BASIC CHEMISTRY OF 2 , 4,5-T PRODUCTION - Pag e 25 B. .HYDROLYSIS OF TCB 5. Recognition of TCDD in NaTCP: A Chronology e. Chronology of the Recognition of TCDD
1957
Steps .taken in 1957 to reduce worker exposure included installation of a Fletcher centrifuge, reducing
fume problems by making a more dilute NaTCP solution prior to the condensation step,44 and installing a centrifuge plow.4^
4/1-7/59 Monsanto personnel are not aware of any publication of the BASF runaway reaction.266 Reference is made to
a Thompson-Hayward accident using the ethylene glycol low-pressure process.
6/16/59
E. P. Wheeler acknowledges receipt of a translation of the Kimmig and Schulz article,2^' regrets that Monsanto Research and Mellon and Kettering did not discover the TCDD causative agent.
3/60
Another industrial hygiene survey was done at Nitro.57
3/16/60
L. C. Weger describes results of Diamond Alkali runaway hydrolysis on 2/20/60.268 After 11 days no
new cases of chloracne had occurred; personnel entering the area took protective precautions. Process safety information, specifically TCB feed over a period of time, had been given Diamond Alkali by Monsanto the year before,, but they had not taken the time to install such a system. Weger suggests points for safety review at Nitro.
7/22/60 Dust collector installed at packaging station to reduce dust exposure.65
9/60
Meeting of Monsanto personnel with Dr. Suskind (Kettering Labs) and Dr. H. Oettel (BASF) reviewed the investigations of the two, companies1 runaway reactions. 2^ BASF's bromsulfophthalein retention test in rabbits- as quality control for TCP is described more fully. Dr.'`Oettel stated Boehringer (in Germany) had .experienced a decomposition in NaTCP production and had.had many cases of chloracne for years; their TCP failed BASF*s'bromsulfophthalein test. Oettel and Suskind agreed that the rabbit ear test is unrealistic and non-reproducible.
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VII.BASIC C H E M I S T R Y OF 2,4,5-T PRODUCTION - Page 26 B. HYDROLYSIS OF TCB 5. Recognition of TCDD in NaTCP: A Chronology e. Chronology of the Recognition of TCDD
9/8/60
L. C. Weger discussion with Diamond Alkali indicates
their work on a chloracnegen indicts chlorinated diphenyl ethers.269
1961
Another article, using rabbit ear and ingestion tests, relates TCDD to chloracne and liver damage; continu ation of the 1957 Kimmig and Schulz article.270
8/63
New integrated facility for NaTCP and 2,4,5-T production started up.9 A number of provisions fox less worker exposure were incorporated.
10/22/64 Rabbit ear tests by Younger Laboratories (for Monsanto) showed by-product 2-methoxy4,5-dichloro-phenol and 4-methoxy -2,5 -
dichlorophenol (structures in eq. 8, Section VI) to be non-chloracnegenic, and TCP distillation residue was again confirmed as chloracnegenic.271
2/24/65
In Dr. R. E.Kelly conversation with V. K. Rowe of Dow,
Dow has 20 new cases of chloracne.
They found
3-10 ppm TCDD in five shipments of 2,4,5-T from
Monsanto and were having a management meeting to
decide whether to use them. They are convinced TCDD
is a major chloracnegen impurity. They are confident
of the rabbit ear test. Dow wants a "crash" meeting
with other producers to reach a specification level
for TCDD in 2,4,5-T and related products. Dow has had
chloracne complaints from customers. Dow has heard
..that the U.S.Public Health Service is investigating
chloracne complaints of Dow customers. Monsanto is
unaware of any customer complaints of chloracne, but
will investigate.
3/3/65
No severe chloracne cases were noted.at Nitro 1960-1964; only four cases since new plant startup in mid-1963. No cases of chloracne found at J. F. Queeny Plant in ester manufacture.272
3/23/65 A TCDD sample and hints on analytical procedure were received from Dow by Monsanto Agricultural Division Research, and GLC method development was started.120
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k , lOr.rtEi WORK PRODUCT ATTOHNEf-CLIENT FRiViLEGt
V I I -BASIC C H E M ISTRY OF 2,4,5-T PRODUCTION - Page 27 B. HYDROLYSIS OF TCB 5- Recognition of TCDD in NaTCP: A Chronology e. Chronology of the Recognition of TCDD
3/25/65 First determination of TCDD in Na 2,4,5-T filter cake was about 10 ppm.225
4/1/65 TCDD in Na 2,4,5-T filter cake was not altered by NaOCl treatment.225
4/7/65 The TCDD sample received from Dow was analyzed for C, H, and Cl by Galbraith Laboratories.22^
Comment : Analyses do not reveal highest purity TCDD.
4/15/65 Filtration of NaTCP showed an 88% reduction in TCDD content.120 A Dow 2,4,5-T sample had no detectable TCDD in it.120
6/22/65 This is' the date on the Dow Analytical Method (GLC) for TCDD in 2,4,5-T.2?3 it involves extraction, concentration, and GLC determination.
7/13/65 Distillation of TCP (from plant NaTCP) containing 15
ppm TCDD gave distillate with no detectable TCDD and residue with 400 ppm TCDD.225,226
9/14/65
Research data showed TCDD in NaTCP at Nitro plant had averaged 5-12 ppm over the period 1953-1964.?-25
Some much higher values (to 60 ppm) in April 1965 were unexplained. Four autoclave batches were sampled and analyzed during the hold period. Disappearance of TCB, decrease in TCA and increase in TCP and TCDD contents were plotted. It is concluded that a detailed laboratory study of the autoclave reaction could lead to an appreciable diminution of TCDD formation, and such a study is in the planning `stage.
10/65
/8 11/66
Dow was contacted concerning removal of TCDD and its disposal, but any information obtained was not in the available documentation. 274,275
A number of projects for reduction of dust and fumes in the Nitro plant were undertaken.1^0
Al T O W O R K FaCOOCT Rev. 1 - 11/5/82 ATTORNEY-CLIENT PRIVILEGE
VII BASIC CHEMISTRY OF 2,4.,5-T PRODUCTION - Page 28 B. HYDROLYSIS OF TCB 5. Recognition of TCDD in NaTCP: A Chronoloqv e. Chronology of the Recognition of TCDD
12/1/66
Dr. R. E. Kelly states that chloracne, while mild, is a continuing problem at Nitro and has occurred at W. G. Krummrich and Luling ester operations.276 ^ new industrial hygienist is being hired for Nitro. Although improved equipment and hygiene practices help, the eventual solution must be avoiding manufacture of the chloracnegen.
1967
Nitro laboratories were set up for routine analyses of TCDD in 2,4,5-T product, will try to analyze NaTCP also.277 Research, Industrial Hygiene, and
Manufacturing debate further approaches to chloracne problem.278, 279, 280 Dust and fume elimination projects were completed.147, 239
2/13/68 Work was started on Research autoclave study to reduce TCDD.282, 283
6/28/68
Dr. R. E. Kelly urges vigorous pace on TCDD reduction p r o g r a m , asks if it is true Dow and Hercules have no new cases of chloracne, and if an attempt should be made to purchase their knowhow.
10/68
Nitro Research process improvement plan calls for
studies on TCDD removal by NaTCP filtration and flash distillation in addition to ongoing autoclave studies. 1*73, 284
1968
Installation of equipment for charging methanol and
NaOH under pressure to their autoclave reduced cycle
time by two hours and halved the TCDD content. 159, 160
1/69
Results of Agricultural Research autoclave study published.155, ,285 Recommended process called for
essentially doubling the methanol: TCB molar ratio and some increase in NaOHiTCB ratio. Predicted TCDD in 2,4,5-T would be consistently below 2 ppm. Immediate testing in the plant autoclave was undertaken. 286, 174, 233 Reduction of TCDD in the NaTCP from
10.5 ppm to 3 ppm was shown in February. 233
Rev. l1 - 1n1//55//882
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V I I .BASIC CHEMISTRY OF 2,4,5-T PRODUCTION
Page 29
B. HYDROLYSIS OF TCB
5. Recognition of TCDD in NaTCP: A Chronology
e. Chronology of the Recognition of TCDD
2/10/69
Preliminary report from Bionetics Research Laboratories on teratology studies on 2,4,5-T commissioned by the National Institutes of Health 289 was received by Monsanto, The study showed
teratogenic effects and liver damage in rats and mice.
Comment: Sample used apparently contained 27 ppm TCDD (see below).
4/8/69
Dr. R. E. Kelly knows of no tests (animal or human) which would prove that current 2,4,5-T with its low level of TCDD was not chloracnegenic.287 No letup in preventive measures should be permitted.
4/69
Agricultural Division Research monthly summary states
TCDD content in NaTCP now 1-3 ppm, and TCDD in 2,4,5-T not detectable.288
Comment: Lower detection limit of analytical method in use at the time was probably about 1 ppm.
10/13/69 Department of Defense was not given toxicity data in Fort Detrick's recommendations to use Orange.290
12/69
Process Amendment authorizes test of shorter TCB addition time and hold time (total autoclave cycle time).182, 184 These could have further reduced TCDD formation. No documentation shows that tests were made.
2/12/70 Dow studies using 2,4,5-T with less than 1 ppm TCDD are showing no teratogenic effect.182
2/19/70
Meeting was held with Monsanto and Hooker represented.291 Dow had analyzed 2,4,5-T used in
Bionetics study, found 27 ppm, TCDD. It was agreed that a specification for TCDD in 2,4,5-T needs to be set with Federal agencies. GLC methods now in use by 2,4,5-T manufacturers (flame ionization detector) are accurate to about 1 ppm TCDD. A new method (FDA) involving an electron capture detector, much more sensitive, is being investigated.
2/24/70 New Monsanto specification was issued for 2,4,5-T including 1 ppm maximum TCDD content.292
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V I I . BASIC CHEMISTRY OF 2,4,5-T PRODUCTION - Page 30 B. HYDROLYSIS OF TCB 5. Recognition of TCDD in NaTCP: A Chronology e. Chronology of the Recognition of TCDD
2/24/70 .FDA and NIH are conducting new teratology studies with . commercial 2,4,5-T containing less than 1 ppm
TCDD.293 v. K . Rowe of Dow stated rabbit ear tests
showed 2,4,5-T used in Bionetics study (27 ppm TCDD) was chloracnegenic, whereas 2,4,5-T with less than 1 ppm TCDD was not.
1/29/71
Reduction of TCDD in a 2,4,5-T ester (specifically the
isooctyl ester) from 1-3 ppm to 0.35 ppm by treatment with a specific activated carbon was shown.294 it
was successfully applied to 650,000 lbs. of material in stock.295
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VII.BASIC CHEMISTRY OF 2,4,5-T PRODUCTION
Page 31
C. CONDENSATION REACTION
2,4,5-T was made by reacting NaTCP with MCA and acidifying to precipitate the solid 2,4,5-T. TCP was converted to Na TCP by equation 9. MCA was converted to NaMCA by reaction with NaOH (eq. 10) or with sodium carbonate (eq. 11). . Solutions of the two salts were ! then reacted to give Na 2,4,5-T (eq. 12). A side ; reaction (eq. 13) was hydrolysis of some of the NaMCA i to sodium glycolate.
(?) 197.45
Cl :\ J i
(10)
TCP ! 1
94.50 1
. ilCHjCooH
MCA, Monochloracetic
Acid '
(11)
94.50
2. CIC^CjioH
MCA ,
4 o;oo -
--
Sodium Hydroxide
40.00 -t t/aO tf ------------
Sodium Hydroxide
105.99 +
Sodium Carbonate
---- >
18.02
219.43
Water
4-
,,-O-, NaTCP
18.02
116.48
^ 0 f cl
Water
NaMCA MCA NA Salt
18.02
tix c
Water
44.01 +C
t C1l1C6U.4^8CO or.tt,
Carbon NaMCA Dioxide
(12) 219.43
116.48
e i-O -c , .NaTCP
+ C( NaMCA
(13) Side Reaction: 118.48 c o o tia. NaMCA
40.00 + Na-Otf
Sodium Hydroxide
58.44
277.47
-
* Naci -t
c l~t Octf^CootJx
CX,
Sodium
Na--2,4,5-T,
Chloride
Sodium 2,4,5-Trichloro-
phenoxy Acetate
58.44
------ A/A d -f
Sodium Hydroxide
98.04
Sodium Glycolate
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Ai te*-.
.--"T h*
EY-CUEHT 0I*|:*|IyI111rut.
VII.BASIC CHEMISTRY OF 2,4,5-T PRODUCTION - Page 32
D. ACIDIFICATION OF Na 2,4,5-T
Na 2,4,5-T was acidified (eq. 14) with sulfuric (or hydrochloric) acid to precipitate 2,4,5-T, which was filtered out and dried.
(14)
277.47
98.07
142.04
255.48
' jQ-r, Na-2,4,5-T
Sulfuric Acid
tl5) Other Possible Impurities:
(a) In MCA raw material:
C f l CK COO H Dichloroacetic Acid
* /Vv 5(kf A-
Sodium Sulfate
VY I
2.4.5-T
2.4.5-
Trichloropheno-
oxyacetic Acid
Ctfj Cootf Acetic Acid
(b) In 2,4,5-T:
Jq -,
Ctf Coat
" bis-T " .
bis-(2,4,5-Trichlorophenoxy)-Acetic Acid
ei
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VII.Bfi.M C CHEMISTRY OF 2,4,5-T PRODUCTION - Page 33
E. RECOVERY OF TCP
Unreacted TCP in the filtrate after separating out the 2,4f5-T was precipitated by reaction with additional sulfuric acid (eq. 6) and the recovered TCP was recycled to the process.
(6) 2X9.43 .
98.07
*c,-U-c, KaTCP
s
*
Sulfuric Acid
142.04
197.45
ci > Na.-jSo^ +
ti- -
Sodium Sulfate
TCP 2,4,5-Trichlo rq
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