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                    <text>Item D Number

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Young, Alvin L

Corporate Author
Form Letter, subject: Literature Request

Journal/Book Title
Year

000

°

Month/Day
Color

D

Number of Images

3

DBSOripton Notes

Contents of folder labeled: "Form Letter for Herbicide Orange
Technical Reports."

Wednesday, January 16, 2002

Page 4215 of 4258

�DEPARTMENT OF THE AIR FORCE
HEADQUARTERS AEROSPACE MEDICAL DIVISION (AFSC)
BROOKS AIR FORCE BASE, TEXAS
78235

REPLY TO
ATTN OF:

SUBJECT, Literature Request

1. Per your request for literature, the following documents on Air
Force studies of the environmental fate of 2,4-D, 2,4,5-T and TCDD are
attached.
2. The first three Technical Reports are pertinent studies on the fate
of 2,4,5-T and its trace contaminant TCDD in an ecosystem treated with
massive quantities of phenoxy herbicides. Technical Reports AFATL-TR74-12 (Atch 1), AFATL-TR-75-49 (Atch 2) and AFATL-TR-75-142 (Atch 3)
detail ecological studies conducted on a unique 3.0 km2 military test
area (Test Area C-52A, Eglin AFB FL) that received approximately 73,000
kg 2,4,5-T and 77,000 kg 2,4-D during the period 1962-70. Significant
results included:
a. At the termination of spray equipment testing programs in 1970,
significant levels (ppm) of 2,4,5-T soil residues were found throughout
the test area. However, no residues of 2,4,5-T were detected (detection
limit of 10 ppb) in any soil samples collected during 1971-1972.
b. Fifty-four (54) soil samples were collected to a depth of 15 cm
from throughout the test area and analyzed for TCDD. TCDD levels ranged
from &lt;10 to 1,500 parts per trillion (ppt). The median concentration
was 30 ppt while the mean was 165 ppt.
c. An ecological survey extending over a five-year period documented
the presence of more than a 123 different plant species, 77 bird species,
71 insect families, 20 species of fish, 18 species of reptiles, 18
species of mammals, 12 species of amphibians and 2 species of molluscs.
At least 170 biological samples were analyzed for TCDD, including 30
species of animals. No TCDD was found in any of the plant species
examined. However, TCDD was found in nine species of animals including
two rodent species: beachmouse (300-1,500 ppt, liver) and hispid cotton
rat (&lt;10-210 ppt, liver); three species of birds: meadowlark (100-1,020
ppt, liver), mourning dove (50 ppt, liver), and Savannah sparrows (69
ppt, liver); three species of fish: spotted sunfish (85 ppt, liver)
mosquitofish (12 ppt, whole body) and sailfin shiner (12 ppt, whole
body), and one reptile, the six-lined racerunner (360-430 ppt, muscle).
A composite sample of insects (whole bodies) contained 40 ppt TCDD.

�d. Gross pathology was done on all species collected for TCDD
residue analyses. Histopathological examinations were performed on over
300 beachmice or hispid cotton rats from the test area and a control
field site. Examinations were performed on the heart, lungs, trachea,
salivary glands, thymus, liver, kidneys, stomach, pancreas, adrenals,
large and small intestine, spleen, genital organs, bone, bone marrow,
skin and brain. Initially, the tissues were examined on a random basis
without the knowledge of whether the animal was from a control or test
area. All microscopic changes were recorded including those interpreted
as minor or insignificant. The tissues were then reexamined on a
control and test basis, which demonstrated that the test and control
mice could not be distinguished histopathologically. Similar histopathological studies were conducted on the fish and racerunners with no
significant abnormalities being found.
3. Technical Report USAFA-TR-76-18 (Atch 4) is a summary of Air Force
ecological research on TCDD. It also presents analytical data on the
soil degradation of TCDD when in the presence of 2,4,5-T and 2,4-D.
Significant results included:
a. The half-life of TCDD in soils containing 2,4-D and 2,4,5-T
appeared to be between 225 and 275 days.
b. Studies of bacteria, actinomycetes and fungi from soil plots
treated with massive quantities of 2,4-D and 2,4,5-T (5,000 - 40,000
ppm) confirm that these microorganisms proliferate to such an extent
that they were probably using the herbicides and TCDD as metabolic
carbon sources and, as such, were contributing to their degradation.
c. Movement of TCDD in the abiotic portions of the environment
occurred by wind or water erosion of soil particles, but leaching by
water alone did not occur.
4. Technical Report USAF OEHL-TR-78-92 (Atch 5) contains, in addition
to the above environmental data on 2,4,5-T and TCDD (Chapter III), other
significant data including:
a. Data on the analysis of 492 samples of Herbicide Orange (a 50:50
mix of the n-butyl esters of 2,4-D and 2,4,5-T) for TCDD (See Chapter
I). The levels of TCDD ranged from &lt;0.02 to 15 ppm in herbicide produced
during the 1965-1968 time period. The weighted mean concentrations of
TCDD in Herbicide Orange was 1.98 ppm. The samples were taken from
surplus Herbicide Orange.
b. Industrial hygiene and ambient air sampling data from all
landbased dedrumming/transfer operations of Project PACER HO, the 1977
USAF project to dispose of 2.22 million gallons of Herbicide Orange (see
Chapter II). Results of these sampling programs revealed that under the
worst case noted, the levels of 2,4,5-T (and 2,4-D) vapors were well
below the time-weighted Threshold Limit Value (TLV) for each of these
materials. The detected levels were at least two and, in most cases,
three orders of magnitude below the TLVs. TCDD was not detected in any
air samples. Approximately 200 personnel carried out the dedrumming/transfer

�operations. Comparisons of available pre- and post-operational medical
examinations of military personnel involved have revealed no apparent
physical effects as a result of /these activities.
c. An assessment of the world's scientific literature on the
toxicity of 2,4,5-T, 2,4-D and TCDD in selected laboratory and domestic
animal species (see Chapter IV). Each chemical was critically reviewed
for:
1. Acute and short-term toxicity potentials.
2. Subacute and chronic toxicity potentials.
3. Absorption, distribution, and excretion potentials.
4. Embryotoxic, fetotoxic, and teratogenic potentials.
5. Carcinogenic and tumorigenic potentials.
6. Mutagenic and cytpgenic potentials.
d. A review of available scientific data on numerous incidents
involving suspected 2,4,5-T/TCDD poisoning of humans or livestock (see
Chapter V). Extensive efforts in translating over 30 major foreign
documents permitted for the first time detailed accounts of 23 industrial
episodes that involved exposure of over 1,100 people to TCDD. An
assessment of the medical data from these industrial episodes and other
episodes was made in Chapter VI. Some of the significant medical
conclusions were:
1. Adverse effects of 2,4,5-T herbicide should manifest themselves shortly after exposure. Symptoms arising for the first time
months to years after the last exposure are probably due to an etiology
other than the herbicide,
2. The hallmark of TCDD exposure is chloracne and its absence
makes it unlikely that systemic disorders present are related to TCDD.
Asthenic and vegetative symptoms are often present in overexposure but
are difficult to interpret. They would normally be expected to clear
with time.
3. There is no conclusive evidence at this time that either
2,4,5-T herbicide or TCDD is mutagenic, teratogenic, or carcinogenic in
man.
5. If I can provide additional copies of these documents or further
elaborate on the data^&amp;leyase contact me.

r\

ALVIN L. YOUNG, Captafn, 1JSAF, Ph.D.
Environmental Sciences Consultant
USAF Herbicide Specialist

5 Atchs
I. AFATL-TR-74-12
2. AFATL-TR-75-49
3. AFATL-TR-75-142
4. USAFA-TR-76-18
5. USAF OEHL-TR-78-92

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D

Young, Alvin L.

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Report/Article TitlB Chapter 10: Long-Term Degradation Studies: Massive
Quantities of Phenoxy Herbicides in Test Grids, Field
Plots, and Herbicide Storage Sites

TftlB

Year

Treatment and Disposal fo Pesticide Wastes: based on

1984

Month/Day
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Number of Images

D

19

Descriptor! Notes

Wednesday, January 16, 2002

Page 4178 of 4258

�10
Long-Term Degradation Studies
Massive Quantities of Phenoxy Herbicides in Test Grids, Field Plots,
and Herbicide Storage Sites
ALVIN L. YOUNG'
Agent Orange Projects Office, Veterans Administration, Washington, DC 20420

Three long-term studies have been conducted on the
fate of 2,4-dichlorophenoxyacetic acid (2,4-D) and
2,4,5-trichlorophenoxyacetic acid (2,4,5-T) when
applied in high concentrations to field sites in
selected geographical locations. The first study,
initiated in April 1970, was of a 208-ha herbicide
equipment-testing area (Test Area C-52, Eglin Air
Force Base, Florida) that received more than 73,000
kg 2,4,5-T and 76,000 kg 2,4-D during the years
1962-1970. The second study, initiated in 1972, was
on the biological degradation of the herbicides when
soil incorporated at rates as high as 4,480 kg/ha
in plots established in three climatically
different areas of the United States; Northwest
Florida, Western Kansas and Northwestern Utah. The
third study, initiated in 1977, was on the fate of
the two herbicides in the soils of two 5-ha sites
(Gulfport, Mississippi; and Johnston Island, Pacific
Ocean) used for the long-term storage of more than
8.4 million L of surplus phenoxy herbicide. The
environmental fate of 2,4-D and 2,4,5-T is compared
between the individual studies.

From January 1962 to April 1970, a program of aerial application
of herbicides was conducted in Southeast Asia by the United States
Air Force (USAF). At the conclusion of this program, considerable
amounts of herbicide were left unused.
One of the herbicides used extensively in this project was a
herbicide designated as "Agent Orange" which was formulated as a
'Current address: Office of Science and Technology Policy, Executive Office of the
President, Washington, DC 20506
This chapter not subject to U.S. copyright.
Published 1984, American Chemical Society

�162

TREATMENT AND DISPOSAL OF PESTICIDE WASTES

50:50 mixture of the n-butyl esters of 2,4-dichlorophenoxyacetic
acid (2,4-D) and 2,4,5-trichlorophenoxyacetic acid (2,4,5-T). In
1970, approximately 8.4 million L of this material were placed in
storage by the Air Force. An analysis of the herbicide stocks
revealed that it contained the highly toxic contaminant
2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD). The concentration of
the TCDD ranged from &lt;0.02 to 47 ppm TCDD in the 492 random
samples taken from the 40,310 208-L drums: the weighted average
concentration of TCDD for the inventory was determined to be
approximately 2 ppm (_y.
Because of the TCDD concentration, the herbicide could not
merely be declared surplus and disposed of on the agricultural
markets. Hence, the Air Force initiated an extensive research
program to find suitable disposal methods that would be both
ecologically safe and economically feasible. Although a major
method extensively investigated was soil incorporation and biodegradation, the final disposal method was at-sea incineration,
a project conducted in 1977. However, in the course of
investigating the feasibility of soil biodegradation, experimental
plots were established and sites were studied where the herbicide
had been extensively sprayed in the course of developing the
spray equipment for Vietnam. When the herbicide was removed
from the two storage sites at the time of its destruction, a
study of the contamination of those sites was initiated. This
paper focuses on the three areas of study that provided data
on the environmental fate of 2,4-D and 2,4,5-T in situations
where the soil was massively contaminated.

Herbicide Spray Equipment Test Grids

The Eglin Reservation in Northwest Florida has served various
military uses, one of them having been the development and testing
of aerial dissemination equipment in support of military
defoliation operations in Southeast Asia. It was necessary
for this equipment to be tested under controlled situations
that would simulate actual use conditions as near as possible.
For this purpose an elaborate testing installation, designed
to measure deposition parameters, was established on the Eglin
Reservation with the place of direct aerial application restricted
to an area of approximately 3 km^ within Test Area C-52A in
the southeastern part of the reservation. Massive quantities
of herbicides, used in the testing of aerial defoliation spray
equipment from 1962 through 1970, were released and fell within
the instrumented test area. The uniqueness of the area prompted
the United States Air Force to set aside the area in 1970 for
research investigations. Numerous ecological surveys have
been conducted since 1970. As a result, the ecosystem of this
unique site has been well studied and documented ( , )
23.

�10. YOUNG

Degradation Studies of Phenoxy Herbicides

163

Although the total area for testing aerial dissemination
equipment was approximately 3 km^, the area actually consisted
of four separate testing grids. The primary area was located in
the southern portion of the testing area and consisted of a 37 ha
instrumented grid. This was the first sampling grid and was in
operation in June 1962. It consisted of four intersecting
straight lines (flight paths) arranged in a circular pattern,
each path being at a 45° angle from those adjacent to it.
Although this grid was used from 1962 to 1964, this grid (called
Grid I) received 39,550 kg of 2,4-D and 39,550 kg 2,4,5-T as
the Herbicide Purple formulation (50 percent n-butyl 2,4-D,
30 percent n-butyl 2,4,5-T and 20 percent iso-butyl 2,4,5-T).
Two other testing grids were sprayed with Herbicide Orange.
Grid II was an area of 37 ha and located immediately north of
Grid I. Grid II received 15,890 kg 2,4-D and 15,890 kg 2,4,5-T
from 1964 through 1966. Grid IV was the largest and final
grid established on Test Area C-52A. It was approximately 97
ha and received 20,000 kg 2,4-D and 17,570 kg 2,4,5-T from
1968 through 1970. Grid III was an experimental circular grid
that received 1,300 kg 2,4-D from 1966 through 1970. Thus,
for the four spray equipment calibration grids, a total of
approximately 73,000 kg 2,4,5-T and 77,000 kg 2,4-D were aerially
disseminated during the period 1962-1970. These data are
summarized in Table I.

Table I. Approximate Amount of 2,4,5-T and 2,4-D Applied to Test
Area C-52A, Eglin AFB Reservation, Florida, 1962-1970

II

37

III

37

IV

97

17,570
(1968-1970)

2,4-Da
(fcg)
39,550
(1962-1964)
15,890
(1964-1966)
1,300
(1966-1970)
20,000
(1968-1970)

208

73,010

76,740

Test
Grid
I

Total
a

Grid
Area (ha)
37

2,4,5-Ta
(kg)
39,550
(1962-1964)^
15,890
(1964-1966)
-

Amount of 2,4,5-T and 2,4-D calculated on weight of active
ingredient in the military Herbicides Orange and Purple.
^Years when the specific grid received the herbicide.

�164

TREATMENT AND DISPOSAL OF PESTICIDE WASTES

Residue Studies. Despite excellent records as to the number of
missions and quantity of herbicide per mission, there was no way
to determine the exact quantity of herbicide deposited at any
point on the instrumented grids. The first residue studies of
Test Area C-52A involved analyses of soils for phenoxy herbicides
by both chemical and bioassay techniques. These studies,
published by Young (2) in 1974, showed that residues of the
phenoxy herbicides rapidly disappeared. However, problems were
encountered in these residue studies because of the heterogeneity
of the test grids. Not only were there small geologic differences
(soil types, contours, organic matter and pH), and differences
in vegetation density and locations of water, but most important
the herbicides had been sprayed on specific test arrays (i.e.,
along dictated flight paths) over a span of years. An obvious
disparity also existed between bioassay data and chemical
analyses because the latter analysis for 2,4-D and 2,4,5-T alone
could not account for all the biologically active phytotoxic
components. The last application of Agent Orange was applied
in December 1969 at a rate of 28 L/ha. Chemical analyses of
soil cores from the treated areas showed that levels of total
2,4-D and 2,4,5-T in the top 15 cm of soil averaged 2.82 ppm
in April 1970 and less than 8.7 ppb in December 1970.
In October 1973, soil samples collected from Grids 1 and
II were analyzed and found to contain significant levels of
TCDD. Highest TCDD residues (740-1,500 parts per trillion, ppt)
were found on Grid I, the area sprayed with Herbicide Purple
in 1962-1964. Subsequent soil samples confirmed TCDD
contamination throughout three of the four test grids. The
persistence of TCDD in the soils of Test Area C-52A has recently
been described by Young, 1983 (_4).
Vegetative Studies. To demonstrate the rapid dissappearance
of phenoxy herbicides from the environment of the test grids,
a vegetative succession study was conducted of the dicotyledonous
species. Nine months (June 1971) after the last defoliantequipment test mission, a detailed survey of the vegetation
was initiated. The 3.0 km^ area was divided into a grid of
169 sections (each 122 by 122 m), and within each section the
percentage vegetative coverage was visually ranked as Class 0,
0-5%; I, 5-20%; II, 20-40%; III, 40-60%; IV, 60-80%; and V
80-100%. Three sections within each class were selected at
random and surveyed for dicotyledonous plants. An unsprayed
area located 0.3 km northwest of the test area was also surveyed.
In June 1973, each of these areas was again surveyed, but in
addition in 15 sections, nine randomly selected areas, each
0.093 m, were analyzed for species composition and ground
cover density.
Vegetative coverage maps prepared in 1971 and 1973 (Figures
1 and 2 respectively) confirmed that rapid re-vegetation occurred
immediately after herbicide applications ceased. Table II

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Degradation Studies of Phenoxy Herbicides

165

shows the percent coverage that each vegetative class occupied
in June 1971 and in June 1973.

Table II. Percent of Vegetative Cover Occupied by Vegetative
Class for the 3 km2 Test Area
Vegetative Class
0 (0-5%)
I (5-20%)
II (20-40%)
III (40-60%)
IV (60-80%)
V (80-100%)

June 1971

June 1973

4
14
29
25
21
4

0
4
12
18
42
23

From June to September 1971, 74 dicotyledonous species were
collected on the 3 km2 Test Area, and 33 additional species were
found during the June 1973 survey. The most important
dicotyledonous plants found invading the test area were rough
buttonweed, Piodia teres Walt; poverty weed, Hypericum
gentianoides L.; and common polypremum, Polypremum procumbens L.
The studies of soil residues and vegetative succession
of Test Area C-52A confirmed that massive quantities of
phenoxy herbicides rapidly disappeared following the termination
of an aerial spray equipment testing program.

Soil Incorporation/Biodegradation Plots

One potential method proposed for the disposal of Herbicide
Orange was subsurface injection or soil incorporation of the
herbicide at massive concentrations. The premise for such
studies was that high concentrations of the herbicides and TCDD
would be degraded to innocuous products by the combined action
of soil microorganisms and soil hydrolysisv In order to field
test this conceptj biodegradation plots were established in
three climatically different areas of the United States;
Northwest Florida (Eglin Air Force Base), Western Kansas (Garden
City) and Northwestern Utah (Air Force Logistics Command Test
Range Complex). A comparison of the soils of the three sites
is given in Table III. The Utah site had a mean annual rainfall
of 15 cm, while the Kansas and Florida sites had 40 and 150 cm,
respectively. Table IV describes the experimental protocol for
the three sites to include when the plots were established, the
method of herbicide incorporation, the experimental design and
the initial calculated herbicide concentration, ppm, at the

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TREATMENT AND DISPOSAL OF PESTICIDE WASTES

80 to 100%

2

5 to 20%

60 to 80%
1

40 to 60%

20 to 40%

0 to 5%

3

4

5

6

7

8

9

1 0

1 1

1 2

1 3

1 4

Figure 1. The May 1971 Vegetation Density Map of the 169
sections (each 122 m x 122 m) that constituted the 2.5 km2
area that received more than 69,300 kg 2,4-D and 2,4,5-T
between June 1964 and December 1969, Test Area C-52A, Eglin
AFB, Florida.

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167

Degradation Studies of Phenoxy Herbicides

80 to 100 %

40 to 60%

5 to 20%

Figure 2. The June 1973 Vegetation Density Map of the 169
sections (each (122 m x 122 m) that constituted the 2.5 km2
area that received more than 69,300 kg 2,4-D and 2,4,5-T
between June 1964 and December 1969, Test Area C-52A, Eglin
AFB, Florida.

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TREATMENT AND DISPOSAL OF PESTICIDE WASTES

time the plots were established. Further details on
experimental protocol can be obtained from Young, et al
(_5), 1974, and Young et al ( ) 1976.
6,

Table III. Comparison of the Characteristics of the Top 15 cm
Layer From Each of the Soil Biodegradation Sites
Location

Organic
Sand
£E Matter (%) __(%_)_

Eglin AFB, PL*
Garden City,KSb
AFLC Test Range
Complex, UTC

5.6 0.5
7.0 1.7
7.8 1.4

91.6
37
27

Silt
4.0
42
53

Clay
4.4
21
20

Soil
Description
Sandy loam
Silt loam
Clay loam

a

Plots located on Test Area C-52A, Eglin AFB Reservation,
Florida,
kplots located on the Kansas Agricultural Experiment Station,
Garden City, Kansas.
c
Plots located 120 km west of Salt Lake City, Utah.
Table V compares the degradation of total 2,4-D and 2,4,5-T
(n-butyl esters and acids) over six years of observations in the
Kansas and Florida locations. Although the rates of application
were similar, the method of application, preplant incorporation
versus subsurface injection, resulted in significant differences
in the initial concentrations of herbicides in the plots. The
acid of 2,4,5-T comprised most of the total residue after the
first two years. Although some residues were recovered,
especially in later years, at depths below 15 cm, the majority
(90 percent) of residue was confined to the top 15 cm of soil
profile. The addition of soil amendments such as lime, organic
matter and fertilizer did not appreciably increase the overall
rate of disappearance of the herbicide. The addition of
activated coconut charcoal, however, significantly decreased
the rate of disappearance of herbicide. Six years after the
charcoal plots were established, residues (primarily 2,4,5-T
acid) were still present.
Microbial studies were conducted on the biodegradation plots
in Florida. Soil samples were taken from all plots in June
and August 1974 (2 years) and in April 1975 (3 years). Although
bacterial and fungal levels were similar for control plots or
plots receiving either herbicide or herbicide plus the soil
amendments lime, fertilizer, and organic matter, the levels
were significantly higher in the plots receiving the activated
charcoal. Microorganisms tended to be concentrated in the level
which contained the charcoal (0-15 cm), but greatly reduced in

�Table IV.

Descriptions of Three Soil Biodegradation Studies Involving Use of Herbicide Orange

Location
Eglin AFB,
Florida

Date
Established
4/'2/72

Method of
Incorporation
Simulated Subsurface Injection
(30cm band width)

§
z
o

Calculated Initial
Herbicide
Concentration (ppm)c
Treatment
4,480 kg Herbicide/haa
4,480 kg Herbicide/ha,
plus soil amendments*"
4,480 kg Herbicide/ha
plus soil amendments
and activated charcoal

5,000
5,000
5,000

I
I

§
Garden City,
Kansas

5/10/72

AFLC Test
Range Complex,
Utah

10/2/72

a

Preplant Incorporate (Rototiller)

2,240 kg Herbicide/ha
4.A80 kg Herbicide/ha

1,000
2,000

Simulated Subsurface Injection
( cm band width)
8

1,120 kg Herbicide/ha
2,240 kg Herbicide/ha
4,480 kg Herbicide/ha

5,000
10,000
20,000

Rate of herbicide calculated as active ingredient. Herbicide injected at 10-15 cm level
or preplant incorporated in the 0-15 cm level. All plots duplicated.
^The amendments included 4.5 kg lime, 13.5 kg organic matter, and 1.4 kg fertilizer
(12:4:8 for N,P,K, respectively) uniformly mixed within the top 0-30 cm of soil in the plot.
c
Contained in the top 0-15 cm layer.

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TREATMENT AND DISPOSAL OF PESTICIDE WASTES

Table V. Concentration (ppm) of Total 2,4-D and 2,4,5-T
(Herbicide Orange) Over a Six-Year Period in Field Plots in
Kansas and Florida
Florida1*
Herbicide
Time After
Application
(years)
Day 5
0.25
0.5
1
1.5
2.0
2.5
3.0
4.0
5.0
6.0

Kansas3

Herbicide

1,950
1,070
490
210
40
&lt;10

4,900
4,280
e
1,870

Herbicide
+
Amendments0
5700
5420

Amendments
+
Charcoal^
3,075
2,770

2015
2,660

508
440

184

52
30
12

8
3

120
360

a

Garden City, Kansas. Plots established 10 May 1972, 4,480 kg/ha
preplant Incorporated. Data are means of replicate plots,
0-15 cm soil increment.
b
Eglin AFB, Florida. Plots established 2 April 1972, 4,480 kg/ha
simulated subsurface injection. Data are means of replicate
plots, 0-15 cm soil increment.
c
The amendments included 4.5 kg lime, 13.5 kg organic matter,
and 1.4 kg fertilizer (12:4:8 for N,P,K, repectively) uniformly
mixed within the top 0-30 cm of soil in the plot.
^A 1 cm layer of activated coconut charcoal was applied to the
trench prior to application of the herbicide.
e
Not analyzed.
number at depths immediately below the charcoal. This effect
of increasing the number of microorganisms may have been due
to adsorption of growth promoting substances (e.g., nutrients
and water) on the surface of the charcoal particles. Although
the number of organisms were greater in these plots, the level
of herbicide residue was also greatest. Apparently, the binding
of the herbicide by the charcoal prevented it from being degraded
by the microorganisms.
Table VI shows the concentration of herbicide in two of the
three sets of field plots established in Utah in 1972. It was
only after the plots were established and the first soil samples
analyzed that it became apparent that the herbicide formulation

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Degradation Studies of Phenoxy Herbicides

171

placed in these plots was different than that used in Florida
or Kansas. Indeed, an analysis of the formulation confirmed
the presence of roughly a 50:50 mixture of the n-butyl and
isooctyl esters of both 2,4-D and 2,4,5-T. Note from Table VI
that the n-butyl ester of either 2,4-D or 2,4,5-T disappeared
more rapidly than the isooctyl ester. The hydrolysis of the
isooctyl ester to the acid, probably microbially mediated,
accounts for the presence of the acid.

Table VI. Concentrations (ppm) of the Acid and n-Butyl and
Isooctyl Esters of 2,4-D and 2,4,5-T Placed Subsurface in Utah
Plots
2,4^D

Rate/Date

n-Butyl

2,4,5-T

Acid Isooctyl

1,120 kg/ha
Initial (1972) 1280a &lt;10b
1975
&lt;10 440
1978
&lt;10 250
4,480 kg/ha
Initial (1972) 5900 &lt;10
1975
10 1970
1978
&lt;10 1060

n-Butyl

Acid

Isooctyl

560
&lt;10
&lt;10

770
&lt;10
&lt;10

&lt;10
930
900

1230
40
20

2640
470
95

3590
72
&lt;10

&lt;10
1740
2900

5790
3000
1080

a

Data are means of replicated plots.
^Detection limit was generally 10 ppm.
Microbial studies have also been conducted on the biodegradation plots in Utah and have been published by Stark et al,
1975 (_7_)« Samples were taken three times throughout the year
(summer, winter, and spring, 1973-1974), and microblal species
present (bacteria, actinomycetes and fungi) were determined.
Bacterial counts were higher for soils with greater moisture
content, but the herbicide, in any concentration, had no
significant effect on the microflora.
As with the studies on the herbicide spray equipment testing
grids at Eglin AFB, Florida, the studies of the biodegradation
plots confirmed the presence and persistence of TCDD. Analysis of
soil samples collected from the Utah plots in 1978 indicated
that 85 percent of the amount of TCDD originally extracted in
1972 could be recovered, suggesting that TCDD applied subsurface
was minimally disappearing.

�172

TREATMENT AND DISPOSAL OF PESTICIDE WASTES

Studies of Herbicide Storage Sites

During the summer of 1977 the USAF disposed of 8.4 million L
of Herbicide Orange by high temperature incineration at sea.
This operation, Project PACER HO, was accomplished under the
very stringent criteria set forth in an United States
Environmental Protection Agency (EPA) ocean dumping permit.
Among the numerous conditions of the EPA-approved disposal
operation was the requirement for the USAF to conduct extensive
environmental and occupational monitoring of the land-transfer/
loading operations, shipboard incineration operations and
subsequent storage site reclamation and environmental monitoring.
Details of the proposed site monitoring programs were prepared
and approved prior to the disposal of the herbicide. The plan
recommended that soil samples from the storage areas at both
the Naval Construction Battalion Center (NCBC), Gulfport,
Mississippi and Johnston Island, Pacific Ocean, be collected
and analyzed for Herbicide Orange after the completion of
transfer operations. These analyses were to aid in the
establishment of a schedule for future monitoring.
In July 1977, following the completion of Project PACER
HO dedruming and subsequent site clean-up operations at NCBC
and Johnston Island, Air force scientists initiated an extensive
site monitoring program. The objectives of this program were:
1. To determine the magnitude of Herbicide Orange
contamination on the storage areas.
2. To determine the soil persistence of the two phenoxy
herbicides contained in Herbicide Orange and the
dioxin contaminant.
3. To monitor for any movement of residues from the sites
into adjacent water, sediments and biological
organisms.
In July 1977, a preliminary sampling study was initiated.
This consisted of assessing the heterogenity of the soils on the
sites and the heterogenity of the herbicide concentrations. The
studies conducted on the biodegradation plots showed that
movement of the herbicide components and the TCDD was low; thus
surface sampling, e.g., the top 8 cm of soil, constituted the
primary sampling depth. Twelve sites were selected for sampling
at each location; six were in areas of obvious spills and six in
areas that showed no spill. Not only were the spills discernible
by sight but also by smell. Winston and Ritty (_8) had previously
found that the olfactory senses can detect a butyl ester
formulation of 2,4,5-T at levels of 0.4 ppb. The results of
this first sampling after Project PACER HO (1977) are shown
in Table VII. Significant concentrations of herbicides, phenols
and TCDD were detected in soils from spill sites. Variation
in concentrations and in the portion of acids to esters
suggested that the spills were from different time periods.

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Degradation Studies of Phenoxy Herbicides

173

Accordingly, a more extensive protocol was proposed for future
sampling.

Table VII. Concentration (ppm) of Total Herbicides, Total
Phenols, and TCDD in 12 Soil Samples Collected July 1977 from
the Herbicide Orange Storage Areas, Johnston Island and
Naval Construction Battalion Center, Gulfport, Mississippi

Location

Number
of Sites

Total
Herbicides3
(ppm)

Total
Phenolsb
(ppm)

TCDD
(ppm)

Spill Sites
8
Johnston Island
58,000+42,000 135+120
0.073+0.07
NCBC, Gulf port
6
78,000+42,000
152+ 90
0.24 +0.27
No Spill Sites
4
Johnston Island
26+15
NAC
3+2
14.2+12.4
NA
NCBC, Gulf port
6
a
Total herbicides refers to concentration of acid and all esters
detected of 2,4-D and 2,4,5-T herbicides. Samples consisted of
top 8 cm of soil.
blotal phenols refers to concentration of dichlorophenol and
trichlorophenol.
c
NA=Not Analyzed.

&lt;r

1978 Protocol. The sites within the two storage areas for
monitoring of residue were determined by whether a spill had
occurred or not occurred at that specific location. The basis for
determining a spill was whether a herbicide stain was discernible
(heavy, light, absent) and whether a herbicide odor was detectable
(strong, mild, absent). Thus, within the storage area numerous
locations were found that had a heavy stain and strong odor
(labeled H/H, presumably representing a recent spill); a light
stain and mild odor (labeled L/L, presumably representing an
older spill); and no stain and no odor (labeled 0/0, presumably
representing an uncontaminated area). Fourteen replications of
each treatment were then randomly selected to represent the
storage area (thus a total of 42 permanently marked sampling
locations at both NCBC and Johnston Island). Twelve of these
locations had been tentatively located and marked in July 1977
with the remaining 30 located and marked in January 1978 with
sampling being conducted on these dates, as well as in November
1978. In collecting the soil samples, a 8 cm square was marked
15 cm away from the site marker pin. At each sampling time soil
was taken from a different "point of the compass" with reference
to the marker pin to insure a fresh and undisturbed profile. At

�174

TREATMENT AND DISPOSAL OF PESTICIDE WASTES

the designated site a 8X8X8 cm cube of soil was removed with a
ceramic spatula which was rinsed with acetone between uses to
prevent carry-over of residue and microorganisms. Wherever
possible, sediment samples were collected from the drainage
areas in a similar manner.
Results. A summary of the analytical results for the 42 sites
sampled in January and November 1978 for the storage area at
Gulfport, Mississippi is shown in Table VIII. A statistically
significant decrease in the levels of total herbicides and
total phenols was found to occur between the two dates. There
was also a downward trend in TCDD levels, but it was not
statistically different ( . 5 . This trend in decreasing
P0)
levels of TCDD (as well as in herbicides and phenols) is even
more pronounced when the July 1977 data for spill sites (Table
VII) are compared to the 1978 data. Unfortunately, because of
differences in site delineation between 1977 and 1978, data
for spill vs no spill between the 2 years cannot be "paired"
and statistically analyzed. Similar levels of herbicides,
phenols, and TCDD have been found in selected soils of the
Herbicide Orange Storage Area on Johnston Island. Table IX
compares the trends in these compounds over four sampling dates
(August 1977, January and October 1978, and August 1979) from
four sites heavily contaminated with phenoxy herbicide (new
spill sites in 1977). Although herbicide levels significantly
decreased over the periods of sampling, trends for disappearance
of TCDD were not as well defined. The data for these four sites
illustrate the inherent weakness of the sampling protocol. When
a spill occurred on a site, the concentration of chemicals
varied significantly within the spill perimeter. Although the
marker pin for permanently locating the site was placed as near
the center of the spill as possible, that did not necessarily
define the zone of greatest soil contamination. Soil samples
collected over time were collected at different "points-of-thecompass" around the marker pin. Nevertheless, data for samples
collected at the same site and between other spill sites are
generally of similar magnitude.
Studies on the penetration of the herbicides and on the
microbial content of the samples were conducted at both the
Naval Construction Battalion Center and Johnston Island. The
results of these studies have been described by Young, et. al.
in 1979 and 1983 ( , 0 . The data indicated that although
91)
penetration of herbicide and TCDD had occurred throughout the
soil profiles sampled (8 cm increments down to 32 cm), the
bulk of the chemicals remained near the surface. Data from the
microbial analyses of soil samples collected from the Herbicide
Storage Areas confirmed that proliferation of certain microflora
occurred under high levels of herbicide residue.

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175

Degradation Studies of Phenoxy Herbicides

Table VIII. Mean Concentrations (ppm) of Total Herbicides,
Phenols and TCDD in Soils Collected in January and
November 1978 from Selected Sites on the Herbicide
Orange Storage Area, Naval Construction Battalion
Center, Gulfport, Mississippi

Location

Number
Total
of Sites Herbicides
Sampled9
(ppm)b

Total
Phenols
(ppm)c

TCDD
(ppm)

"No" Spills ( / )
00d
14
32*e
ND(4)f
3.5*
January 1978
November 1978
1A
3t
NAS
0.4t
"Old" Spills (L/L)
14
1,202*
January 1978
86*
0.0364(3)
November 1978
14
492t
23t
0.0438(3)
"New" Spills (H/H)
January 1978
437*
14 51,285*
0.2064(10)*
November 1978
0.1444(11)*
14 30,005t
253t
a
Each soil sample consisted of a cube of soil (8X8X8 cm) removed
adjacent to a designated marker.
^Total herbicides refers to the concentration of acid and all
esters of both 2,4-D and 2,4,5-T.
c
Total phenols refers to total concentration of both
dichlorophenol and trichlorophenol.
d
The coding 0/0, L/L and H/H are described in the text.
e
Means within columns within subtitles followed by the same
symbols are not significantly different at the 0.05 probability
level.
For the statistical analysis, the Wilcoxon Paired-Sample Test was
used. A test for a one-tailed hypothesis with paired samples was
used in the procedure for nonparametric data since it could not
be assumed that the levels of residue detected were from a normal
distribution and it was expected that the residues would decrease
with time.
*ND=Not Detected; the number of samples analyzed is in
parentheses. The detection limit was generally 0.0002 ppm
(200 ppt).
SNA=Not Analyzed.

�176

TREATMENT AND DISPOSAL OF PESTICIDE WASTES

Table IX. Concentration (ppm) of Total Herbicides, Total Phenols
and TCDD in Soil Samples from Four Selected Spill
Sites for Four Dates from the Herbicide Orange Storage
Area, Johnston Island
Sample Date
and
Sample Site
25 August 1977
5C
9
10
12
8 January 1978
5
9
10
12
18 October 1978
5
9
10
12
8 August 1979
5
9
10
12

Total
Phenolsb
(ppm)

TCDD
(ppm)

38,000
52,270
135,250
76,080
75,400

93
205
460
172
233

0.0330
0.0417
0.1960
0.1780
0.1122

38,980
70,090
141,300
57,000
76,840

123
181
477
110
223

0.0340
0.0220
0.2300
0.0800
0.0915

31,440
60,530
159,700
42,840
73,630

34
111
456
47
T62

0.0191
0.0286
0.2350
0.1110
0.0984

Total
Herbicides3
(ppm)

ND
3,560
0.0410
149
003
.50
44,230
48,660
136
0.1300
54
0.0810
18,430
28,720
TT3(3)d
0.0763
^Total herbicides refers to concentrations of acid and all esters
detected of 2,4-D and 2,4,5-T.
^Total phenols refers to concentrations of dichlorophenol and
trichlorophenol.
c
The sample consisted of a cube (8X8X8 cm) of soil removed from
near the center of an area designated as a spill.
^Refers to number of samples included in obtaining the means.

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Degradation Studies of Phenoxy Herbicides

111

Discussion and Conclusions
The amount of phenoxy herbicides applied or spilled on a kg/ha
basis in the above studies can only be described as "massive."
Although Grid 1 on the Eglin AFB spray equipment testing grids
received the herbicides primarily during 1962 and 1963, the
total amount aerially applied was 2,140 kg/ha. Because the
herbicides in this situation were applied from an aircraft, the
time between repetitive applications and the environmental
factors greatly influenced the amount that was incorporated
into the soil profile. Thus, residues were continually disappearing and accumulation and persistence were minimal. However,
in the biodegradation plots and in the Herbicide Storage Areas,
high concentrations of herbicides were applied in a short time
period and incorporated immediately into the soil profile, and
hence, the long persistence time. Nevertheless, these studies
do show that the soil chemistry and the soil microbial populations
can effectively combine to degrade massive concentrations of the
phenoxy herbicides and that recovery of the sites occur as
documented by the re-establishment of the vegetative community.
The major conclusions from long-term degradation studies of
massive quantities of 2,4-D and 2,4,5-T in test grids, field
plots and herbicide storage areas are:
1. The method of application has significant impact on the
amount applied per unit area and hence on residue persistence:
spills &gt;^ soil incorporation &gt; aerial application.
2. The herbicide 2,4,5-T is more persistent in the soil than
2,4-D.
3. The formulation of the herbicide has significant impact
on its persistence:
isooctyl ester &gt; n-butyl ester &gt; acid
4. The addition of coconut charcoal increases persistence of
phenoxy herbicide residues, especially residues of 2,4,5-T.
5. The appearance of dichlorophenol and trichlorophenol in soils
treated with 2,4-D and 2,4,5-T suggests that they are
degradation products of the herbicides.
6. The massive concentration of herbicides found in these
studies do not sterilize the soils. Indeed, the data suggest
that microbial populations respond both quantitatively and
qualitatively to the presence of high concentrations of
herbicides and may play a major role in their degradation.
7. The contaminant 2,3,7,8-TCDD has a long persistence time
in soils (years) and may be a major consideration in the
use of soil biodegradation as a disposal option for
"unwanted" phenoxy herbicides or TCDD-contaminated chemical
wastes.

�178

TREATMENT AND DISPOSAL OF PESTICIDE WASTES

Acknowledgments

I am indebted to Drs. Eugene Arnold and Mason Hughes for the
analyses of the phenoxy herbicides, phenols and the TCDD
contaminant.

Literature Cited

Young, A. L., J. A. Calcagni, C. E. Thalken and J. W.
Tremblay, 1978. "The Toxicology, Environmental Fate and
Human Risk of Herbicide Orange and Its Associated Dioxin."
Air Force Technical Report OEHL-TR-78-92. 247p. Document
available from NTIS, 5285 Port Royal Road, Springfield, VA
22161.
Young, A. L., 1974. "Ecological Studies on a HerbicideEquipment Test Area (TA C-52A), Eglin AFB Reservation,
Florida." Air Force Technical Report AFATL-TR-74-12.
141p. Document AD-^80 517, available from NTIS, 5285 Port
Royal Road, Springfield, VA 22161.
Young, A. L., C. E. Thalken and W. E. Ward, 1975. "Studies
of the Ecological Impact of Repetitive Aerial Applications
of Herbicides on the Ecosystem of Test Area C-52A, Eglin,
AFB, Florida." Air Force Technical Report AFATL-TR-75-142.
127p. Document AD-A032 773, available from NTIS, 5285 Port
Royal Road, Springfield, VA 22161.
Young, A. L., 1983. "Long-Term Studies on the Persistence
and Movement of TCDD in a Natural Ecosystem." Environ.
Sci. Kes_. 26:173-190.
Young, A. L., E. L. Arnold, and A. M. Wachinski, 1974.
"Field Studies on the Soil-Persistence and Movement of
2,4-D 2,4,5-T, and TCDD." Appendix G. Disposition of
Orange Herbicide by Incineration. Final Environmental
Statement, November 1974. Department of the Air Force,
Washington, D.C.
Young, A. L., C. E. Thalken, E. L. Arnold, J. M. Cupello,
and L. G. Cockerham. 1976. "Fate of 2,3,7,8Tetrachlorodibenzo-p-dioxin (TCDD) in the Environment:
Summary and Decontamination Recommendations." Air Force
Technical Report USAFA-TR-76-18. 44p. Document AD-A033 491,
available from NTIS, 5285 Port Royal Road, Springfield, VA
22161.
Stark, H. E., J. K. McBride, and G. F. Orr, 1975. "Soil
Incorporation/Biodegradation of Herbicide Orange. Vol I.
Microbial and Baseline Ecological Study of the U.S. Air
Force Logistics Command Test Range, Hill AFB, Utah."
Document No. DPG-FR-C615F, US Army Dugway Proving Ground,
Dugway, Utah 84022, February 1975.

�10. YOUNG

Degradation Studies of Phenoxy Herbicides

179

8. Winston, A. W. and R. M. Ritty, 1971. "What Happens to
Phenoxy Herbicides When Applied to a Watershed Area."
Ind. Vegetation Manage. 4(1):12-14.
9. Young, A. L., C. E. Thalken, and W. J. Cairney, 1979.
"Herbicide Orange Site Treatment an Environmental Monitoring:
Summary Report and Recommendations for Naval Construction
Battalion Center, Gulfport, Mississippi." Air Force
Technical Report OEHL-TR-79-169. 36p. Document AD-A062
143, available from NTIS, 5285 Port Royal Road, Springfield,
VA 22161.
10. Young, A. L., W. J. Cairney and C. E. Thalken, 1983.
"Persistence, Movement and Decontamination Studies of
TCDD in Storage Sites Massively Contaminated with Phenoxy
Herbicides." Chemosphere 12(4/5): 713-726.
RECEIVED May 1, 1984

Reprinted from ACS SYMPOSIUM SERIES, No. 259
TREATMENT &amp; DISPOSAL OF PESTICIDE WASTES
Raymond F. Krueger and James N. Seiber, Editors

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                    <text>Item D Number

°4133

Author

Young, Alvin L.

D fjnt scanned

Corporate Author
Report/Article Title ^ate °f 2,3,7,8-TCDD in an Ecosystem Treated with
Massive Quantities of 2,4-D and 2,4,5-T Herbicides

Journal/Book Title
Year

1982

Month/Day

January 21

Color
Number of Images

D

7

Descriptor! Notes

Wednesday, January 16, 2002

Page 4136 of 4258

�FATE OF 2,3,7,8-TCDD IN AN ECOSYSTEM TREATED WITH MASSIVE
QUANTITIES OF 2,4-D AND 2,4,5-T HERBICIDES

by
Alvin L. Young*

PRESENTATION TO THE
CALIFORNIA WEED CONFERENCE
Town and Country Convention Center
San Diego, California
21 January 1982

Address Inquiry to: Major Alvin L. Young, USAF, Ph.D.
Office of Environmental Medicine (102)
Veterans Administration
810 Vermont Avenue, N.W.
Washington, D.C. 20420
Phone: (202) 389-5411

�FATE OF 2,3,7,8-TCDD IN AN ECOSYSTEM TREATED WITH MASSIVE
QUANTITIES OF 2,4-D AND 2,4,5-T HERBICIDES

A. L. Young, Veterans Administration,
Washington, D.C.*

Since 1970 hundreds of laboratory studies have been conducted on the toxic
contaminant 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD) found in trichlorophenol.
Although numerous commerical products are made from trichlorophenol, including
the herbicide 2,4,5-trichlorophenoxyacetic acid (2,4,5,-T), controversy remains
as to what extent the TCDD found in these products has impacted humans or their
environment.
Laboratory data for rodents strongly suggest a correlation between
histological lesions in the liver and lymphatic system and the amount of TCDD
ingested. Unfortunately, data relating to any actual effects on wild populations
or their natural habitat are lacking•

The problem of finding a field site where

a wide population of animals has been exposed to significant quantitites of TCDD
is improbable because of (1) low levels of TCDD (&lt; 0.1 ppm) found in currently
produced phenoxy herbicide, and (2) low rates of 2,4,5,-T applied for brush
control on rangeland or for reforestation ( . to 2.2 kilogram (kg)/hectare
11
(ha)). This presentation summarizes the effects of residual TCDD on the ecology
of a unique test site: a site previously treated with massive quantities of
2,4,5-T and 2,4-D herbicides and located on the Eglin Air Force Base
Reservation, Florida.
The Eglin Reservation has served various military uses, one of them having
been the development and testing of aerial dissemination equipment in support of

*0ffice of Environmental Medicine (102), 810 Vermont Avenue, N.W.
Washington, D.C. 20420

�military defoliation operations in Southeast Asia. It was necessary for this
equipment to be tested under controlled situations that would simulate actual
use conditions as near as possible. For this purpose an elaborate testing
installation, designed to measure deposition parameters, was established on the
Eglin Reservation with the place of direct aerial application restricted to an
2
area of approximately 3 square kilometers (km ) within Test Area C-52A in the
southeastern part of the reservation.

Massive quantities of herbicide, used in

the testing of aerial defoliation spray equipment from 1962 through 1970, were
released and fell within the instrumented test area.
has prompted continued ecological surveys since 1967.

The uniqueness of the area
As a result, few

ecosystems have been so well studied and documented.
Description of Field - Test Area C-52A (TA C-52A) covers an area of

2
approximately 8 km

and

is a grassy plain surrounded by a forest stand that is

dominated by longleaf pine (Pinus palustris), sand pine (Pinus clausa), and

turkey oak (Quercus laevis). The actual area for test operations occupies an
2
area of approximately 3 km and is a cleared area occupied mainly by
broomsedge (Andropogon virginicus), switchgrass (panicum virgatum), woolly
panicum (Panicum lanuginosum) and low growing grasses and herbs. Much of the
center of the range was established prior to 1960, but the open range as it
presently exists was developed in 1961 and 1962. The test grid is approximately
28 m above sea level with a water table at 1.5 to 3 m. The major portion of
this test area is drained by five small creeks whose flow rates are influenced
by an average rainfall of 150 cm.

The mean annual temperature for the test area

is 19.7C while the mean annual relative humidity is 70.8 percent.

For the most

part, the soil of the test grid is a fine white sand on the surface, changing to
yellow beneath. The soils of the range are predominantly well drained, acid

2.

�sands of the Lakeland Association with a 0 to 3 percent slope. A typical
one-meter soil core contained approximately 92 percent sand, 3.8 percent silt,
and 4.2 percent clay with an organic matter content of 0.17 percent an average
pH of 5.6, and a cation exchange capacity of 0.8.
Although the total area for testing aerial dissemination equipment was
2
approximately 3.0 km f the area actually consisted of four separate testing
grids.

The primary area was located in the southern portion of the testing area

and consisted of a 37 ha instrumented grid. This was the first sampling grid
and was in operation in June 1962.

It consisted of four intersecting straight

lines in a circular pattern, each being at a 45 angle from those adjacent to
it. Although this grid was discontinued after 2 years, it received the most
intense testing program. From 1962 to 1964, this grid (called Grid I received
39,550 kg 2,4-D and 39,550 kg of 2,4,5-T as the Herbicide Purple formulation (50
percent n-butyl 2,4~D, 30 percent n-butyl 2,4,5-T and 20 percent iso-butyl
2,4,5-T). Two other testing grids were sprayed with Herbicide Orange (50
percent n-butyl 2,4-D and 50 percent n-butyl 2,4,5-T). Grid II was an area of
37 ha and located immediately north of Grid I. Grid II received 15,890 kg 2,4-D
and 15,890 kg 2,4,5-T from 1964 through 1966.

Grid IV was the largest and final

Grid established on Test Area C-52A. It was approximately 97 ha and received
20,000 kg 2,4-D and 17,570 kg 2,4,5-T from 1968 through 1970.

Grid III was an

experimental circular grid that received 1,300 kg 2,4-D from 1966 through 1970.
Thus, for the four spray equipment calibration grids, a total of 73,000 kg
2,4,5-T and 77,000 kg 2,4-D were aerially disseminated during the period
1962-1970. No residues of 2,4,5-T or 2,4-D were detected (detection limit of 10
ppb) in any soil samples collected during 1971-72.
Results - Analysis of archived samples of the formulations sprayed on the
calibration grids indicated that approximately 2.8 kg 2,3,7,8-TCDD were applied

3.

�as a contaminant of the herbicide.

However, 2.6 kg of this TCDD were applied to

a 37 ha test grid (Grid I) from June 1962 through July 1964.

Levels of &lt; 10 to

1,500 parts per trillion (ppt) could be found in the top 15 cm of soil 14 years
after the last application of herbicide on this site. Nevertheless, analysis of
61 soil samples suggested that less than 1 percent of the TCDD remained on the
test area. Photodegradation at the time of and immediately after aerial
application probably accounted for much of the disappearance of TCDD, although
wind and water erosion and biological removal may have also contributed to its
disappearance. Probably, the most startling observation about Test Area C-52A,
is that biological organisms are abundant. The composition of species is
diverse and the distribution extensive. In February 1969, a "list of species"
was initiated for the test grids. Whenever a species was observed on or
associated with the grids, that species was recorded. Over the years of
observation, approximately 341 species or organisms have been observed and
identified as associated with the test area. The sheer number of species
testifies to the extensiveness of the ecological studies that have been
conducted on this unique area.

To date 290 biological samples (plants and

animals) have been analyzed for TCDD.

TCDD residues have now been found in a

wide spectrum of animals collected from the test area. Approximately one-third
(21) of the different species examined for TCDD residue have been positive. In
general, the levels of TCDD in the organisms appeared to be close to the mean
levels of TCDD found in the soils.
The ecological survey extending over a 5-year period (1973-1978) documented
the presence of at least 123 different plant species, 77 bird species, 71 insect
families, 20 species of fish, 18 species of reptiles, 18 species of mammals, 12
species of amphibians and 2 species of mollusks. No TCDD was found in any of
the seeds of the plant species examined.

However, TCDD was found in nine

4.

�species of animals including two rodent species: beachmouse (300-2,900 ppt,
liver) and hispid cotton rat ( 10-210 ppt, liver); three species of birds:
(
meadowlark (100-1,020 ppt, liver), mourning dove (50 ppt, liver), and Savannah
sparrows (69 ppt, liver); three species of fish: spotted sunfish (85 ppt,
liver), mosquito fish (12 ppt, whole body) and sailfin shinner (12 ppt, whole
body); two reptiles: six-lined racerunner (360-430 ppt, muscle), and the Eastern
coachwhip (150 ppt, fat); and one amphibian (Southern toad, 1,360 ppt, whole
body) . In addition ground-borne spiders ere positive for TCDD (115 ppt) as were
crickets (18-25 ppt) and insect grubs (240 ppt). These data verify that both
bioaccumulation and bioconcentration of TCDD occurs. Indeed, in a special
examination of liver tissue from 36 individual beachraice, a close relationship
between soil and liver levels of TCDD was observed, i.e., high liver levels of
TCDD were consistent with high soil levels of TCDD. Moreover, for beachmice
bioconcentration factors (mean liver concentrations divided by mean soil
concentrations) ranged from 6 for females to 18 for males. Whole body analysis
of fetuses from test area females indicated apparent placental transport of
TCDD. Histopathological examinations were performed on 255 adult or fetal
beachmice from the test area and a control area. Examinations were performed on
the heart, lungs, trachea, salivary glands, thymus, liver, kidneys, stomach,
pancreas, adrenals, large and small intestine, spleen, genital organs, bone,
bone marrow, skin and brain.

Initially the tissues were examined on a blind

study basis. All microscopic changes were recorded including those interpreted
as minor or insignificant. The issues were then re-examined on a control versus
test basis, which demonstrated that the test and control mice could not be
distinguished histopathologically. The mean number of fetuses per observed
pregnancy was 3.1 and 3.4 for the test area and a control area, respectively. A
single female beachmouse is capable of producing a litter every 26 days. At

5.

�this frequency, the animals collected in 1978 could have been 50 generations
removed from the population studies in 1973.

A two-factor (treatment and year)

disproportional analysis of covariance of organ weights revealed that liver
weights for pregnant beachmice from the test area were significantly heavier
(P ( 0 ) than liver weights of pregnant females from the control area, and these
.1
differences were consistent over the 5 years of observation. These studies
suggest that long-term, low level exposure to TCDD under field conditions has
had minimal effect upon the health and reproduction of the beachmouse.

6.

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&lt;p&gt;For more about this collection, &lt;a href="/exhibits/speccoll/exhibits/show/alvin-l--young-collection-on-a"&gt;view the Agent Orange Exhibit.&lt;/a&gt;&lt;/p&gt;</text>
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ows

Author

D

Young, Alvin L.

Corporate Author
Report/Article Title

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Herbicides in South Vietnam, 1961 -1971,
Presentation/Proceedings

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198

Month/Day

May 28-30

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°

D

18

Descripton Notes

Wednesday, January 16, 2002

Page 4078 of 4258

�USE OF HERBICIDES IN SOUTH VIETNAM, 1961-1971

ALVIN L. YOUNG*
MAJOR, USAF, PHD
Epidemiology Division
USAF School of Aerospace Medicine
Brooks AFB, San Antonio, TX 78235

PRESENTATION/PROCEEDINGS

EDUCATIONAL CONFERENCE ON HERBICIDE ORANGE
United States Veterans Administration
Silver Springs, Maryland
28-30 May 1980

*Address Inquiry: Major Alvin L. Young, USAF, Ph.D.
Environmental Sciences Consultant
Epidemiology Division
USAF School of Aerospace Medicine
Brooks AFB, San Antonio, TX 78235
Phone: (512) 536-3309/2604

�USE OF HERBICIDES IN
SOUTH VIETNAM,1961-1971*
ALVIN L. YOUNG
MAJOR, USAF, PHD

Epidemiology Division
USAF School of Aerospace Medicine
Brooks AFB, San Antonio, TX 78235

Herbicides used in support of tactical military operations in South Vietnam
from 1961 to 1971 are today, ten years after the last herbicide mission, the
center of intense scientific debate involving not only medical but also legal,
political and ecological issues. This paper reviews the historical and operational concepts and some potential human exposure considerations involving
the military use of herbicides in the Southeast Asian Conflict.
Herbicides Used in South Vietnam
Synthesis technology, efficacy data, and field application techniques were
developed for the two major phenoxy herbicides, 2,4-dichlorophenoxyacetic acid
(2,4-D) and 2,4,5-trichlorophenoxyacetic acid (24,5-T) during World War II
at Fort Detrick, Frederick, Maryland. Following World War II, the commercial
use of these two "synthetic" organic herbicides revolutionized American agriculture.

In 1950, more than 10 m i l l i o n pounds of these materials were used

annually for weed and brush control in the United States.

By 1960, in excess

of 36 million pounds were used.

*A synopsis of Information from Chapters I and III of The Toxicology, Environmental Fate, and Human Risk of Herbicide Orange and Its Associated Dioxin,
Air Force Technical Report OEHL-TR-78-92, USAF Occupational and Environmental
Health Laboratory, Brooks Air Force Base, Texas. (Authors: A. L. Young,
J. A. Calcagni, C. E. Thalken, and J. W. Tremblay). 1978.

�In May 1961, the Office of the Secretary of Defense requested the Fort
Detrick personnel to determine the technical feasibility of defoliating
jungle vegetation in the Republic of Vietnam. By early fall, 1961, 18 different aerial spray tests (defoliation and anticrop) had been conducted
with various formulations of commercially-available herbicides.

The choice

of these herbicides was based upon the chemicals that had had considerable
research, proven performance, and practical background at that period in
time.

Also, such factors as availability in large quantity, costs and

known or accepted safety in regard to their toxicity to humans and animals
were, considered. The results of these tests were that significant defoliation and anticrop effects could be obtained with two different mixtures of
herbicides. The first was a mixture of the n-butyl esters of 2,4-D and
2,4,5-T and the iso-butyl ester of 2,4,5-T. This mixture was code-named
"Purple." The second "military" herbicide was code-named "Blue" and consisted of the acid and sodium salt of cacodylic acid. The colored bands
which were painted around the center of the 55-gallon drums served as aid
to the identification by support personnel.

The first shipment of Herbicides Purple and Blue was received at Tan Son Nhut
Air Base, Republic of Vietnam, on 9 January 1962.

These were the first m i l i -

tary herbicides used in Operation RANCH HAND, the tactical military project
for the aerial spraying of herbicides in South Vietnam. Two additional phenoxy
herbicide formulations were received in limited quantities in South Vietnam
and evaluated during the first two years of Operation RANCH HAND. These were
code-named Pink and Green.

By January 1965, two additional military herbicides,

�code-named Orange and White, had been evaluated and brought into the
Spray program.

Herbicide Orange replaced all uses of Purple, Pink, or

Green, and eventually became the most widely used military herbicide in
South Vietnam.

The composition of the three major herbicides used in

South Vietnam were as follows:
1. Herbicide Orange
Orange was a reddish-brown to tan colored liquid soluble in
diesel fuel and organic solvents, but insoluble in water.

One gallon

of Orange theoretically contained 4.21 pounds of the active ingredient
of 2,4-D and 4.41 pounds of the active ingredient of 2,4,5-T.

Orange

was formulated to contain a 50:50 mixture of the n-butyl esters of
2,4-D and 2,4,5-T.

The percentages of the formulation typically were:

n-butyl ester of 2,4-D
free acid of 2,4-D

n-butyl ester of 2,4,5-T
Free acid of 2,4,5-T
inert ingredients (e.g., butyl
alcohol and ester moieties)

49.49
0.13

48.75
1.00
0.62

2. Herbicide White
White was a dark brown viscous liquid that was soluble in
water but insoluble in organic solvents and diesel fuel. One gallon of
White contained 0.54 pounds of the active ingredient of 4-amino-3,5,6trichloropicolinic acid (picloram) and 2.00 pounds of the active ingredient
of 2,4-D. White was formulated to contain a 1:4 mixture of the triisopropanoamine salts of picloram and 2,4-D. The percentages of the formulation were:

�triisopropanolamine salt of picloram

10.2

triisopropanolamine salt of 2,4-D

39.6

inert ingredient (primarily the
solvent triisopropanolamine)

50.2

3. Herbicide Blue
Blue was a clear yellowish-tan liquid that was soluble in
water, but insoluble in organic solvents and diesel fuel. One gallon of
Blue contained 3.10 pounds of the active ingredient hydroxydimethyarsine
oxide (cacodylic acid). Blue was formulated to contain cacodylic acid
(as the free acid) and the sodium salt of cacodylic acid (sodium cacodylate).
The percentages of the formulation were:
cacodylic acid

4.7

sodium cacodylate

26.4

surfactant

3.4

sodium chloride

5.5

water

59.5

antifoam agent

0.5

As previously noted, not all of the herbicides used in South Vietnam were
used throughout the entire 10 years (1962-1971) encompassed by the Department of Defense defoliation program.

In addition, 2,4,5-T formulations used

early in the program are believed to have contained higher levels of the
toxic contaminant TCDD (2,3,7,8-tetrachlorodibenzo-p-dioxin or "dioxin")
than did the formulations used in the later years. The three time periods

�shown in Table 1 can be differentiated on the basis of specific herbicides
used and the mean dioxin content.

TABLE 1. THE DIFFERENTIATION OF THREE TIME PERIODS DURING THE US MILITARY
DEFOLIATION PROGRAM IN SOUTH VIETNAM AND MEAN DIOXIN CONTENT

Herbicides Used
(Code Names)

Period

Mean Dioxin Content
(parts per million)*

January 1962-

Purple, Pink, Green

June 1965

Blue

^32**

July 1965June 1970

Orange
White, Blue

^ 2+
0

July 1970October 1971

White, Blue

0

0

*Found only in 2,4,5-T containing formulations.
**Value based on analyses of five samples.
+Value based on the analyses of 488 samples.

Herbicide Orange was the most extensively used herbicide in South Vietnam.
Orange accounted for approximately 10.7 million gallons of the total 17.7
million gallons of herbicide used (Table 2). It was used from mid-1965 to
June 1970.

However, as noted in Table 2, Orange was not the only 2,4,5-T

containing herbicide used in the defoliation program. Small quantities of
Purple, Pink, and Green, all containing 2,4,5-T were used from 1962 through
mid-1965.

In subsequent sections of this document, the term "Herbicide

Orange" will refer to all of the 2,4,5-T containing herbicides used in
Vietnam (Purple, Pink, Green, and Orange).

�TABLE 2. NUMBER OF GALLONS OF MILITARY HERBICIDE PROCURED BY THE US
DEPARTMENT OF DEFENSE AND DISSEMINATED IN SOUTH VIETNAM
DURING JANUARY 1962 - OCTOBER 1971

Code Name

Herbicide

Quantity

Period of Use

Orange

2,4-D; 2,4,5-T

10,646,000

1965-1970*

White

2,4-D; Picloram

5,633,000

1965-1971**

Blue

Cacodylic Acid

1 ,150,000

1962-1971**

Purple

2,4-D; 2,4,5-T

145,000

1962-1965

Pink

2,4,5-T

123,000

1962-1965

Green

2,4,5-T

8,200
17,705,200

1962-1965

Total

*Last fixed-wing mission of Orange 16 April 1970; last helicopter mission of
Orange 6 June 1970.
**Last fixed-wing mission 9 January 1971; all herbicides under US control
stopped 31 October 1971.

Use Patterns of Individual Herbicides
Each of the three major herbicides (Orange, White, and Blue) had specific
uses. Ninety-nine percent of Herbicide White was applied in defoliation
missions. It was not recommended for use on crops because of the persistence
of Picloram in soils. Because the herbicidal action on woody plants was
usually slow, full defoliation did not occur for several months after spray
application. Thus, it was an ideal herbicide for use in the inland forests
in areas where defoliation was not immediately required, but where it did
occur it would persist longer than if the area were sprayed with Orange
or Blue.

�Herbicide Blue was the herbicide of choice for crop destruction missions
involving cereal or grain crops. Approximately 50 percent of all Blue
was used in crop destruction missions in remote or enemy controlled areas
with the remainder being used as a contact herbicide for control of grasses
around base perimeters.

Ninety percent of all Herbicide Orange was used for forest defoliation and
it was especially effective in defoliating mangrove forests.

Eight percent

of Herbicide Orange was used in the destruction of broadleaf crops (beans,
peanuts, ramie, and root or tuber crops). The remaining 2 percent was used
around base perimeters, cache sites, waterways, and communication lines.

Table 3 shows the number of acres sprayed with herbicides in South Vietnam
within the three major vegetational categories.
TABLE 3. THE NUMBER OF ACRES TREATED IN SOUTH VIETNAM, 1962-1971, WITH
MILITARY HERBICIDES WITHIN THE THREE MAJOR VEGETATIONAL
CATEGORIES
Vegetational Category

Areas Treated*

Inland forest

2,670,000

Mangrove forests

318,000

Cultivated crops

260,000

Total

*Areas receiving single or multiple coverage.

3,248,000

�Certain portions of South Vietnam were more likely to have been subjected
to defoliation. Herbicide expenditures for the four Combat Tactical Zones
Of South Vietnam are shown in Table 4. These data were obtained from the
HERBS tape (a computer listing of all herbicide missions in South Vietnam
from 1965 through 1971). Total volume is in close agreement with the
actual procurement data shown in Table 4.
TABLE 4.

US HERBICIDES EXPENDITURES IN SOUTH VIETNAM, 1962-1971:
A BREAKDOWN BY COMBAT TACTICAL ZONE*

Herbicide Expenditure
(gallons)
Orange
White
Blue

Combat Tactical Zones
CTZ I

2,250,000

363,000

298,000

CTZ II

2,519,000

729,000

473,000

CT2 III
(includes Saigon)

5,309,000

3,719,000

294,000

CTZ IV

1,227,000

435.000

62,000

Subtotals

11,305,000

17.678.000

Grand total

*Source:

5,246,000 1,127,000

HERBS tape

In addition to the herbicides, numerous other chemicals were shipped to
South Vietnam in 55-gallon drums.

THese included selected fuel additives,

cleaning solvents, cooking oils, and a variety of other pesticides. The
insecticide Malathion was widely used for control of mosquitoes and at least
400,000 gallons of it were used from 1966 through 1970.

In addition, much

smaller quantities of Lindane and DDT were used in ground operations

8

�throughout the war in Southeast Asia, The distribution of the herbicides
within Vietnam after their arrival did not occur randomly. About 65 percent
was shipped to the 20th Ordnance Storage Depot, Saigon, and 36 percent was
shipped to the 511th Ordnance Depot, Da Nang.
Military Aircraft and Vehicles Used in the Dissemination of Herbicides
Numerous aircraft were used in the air war in Vietnam, but only a few of these
aircraft were used for aerial dissemination of herbicides. The "work horse" of
Operation RANCH HAND was the two-engine aircraft C-123/UC-123 called the "Provider." This cargo aircraft was adapted to receive a modular spray system for
internal carriage. The module (the A/A 45 Y-l) consisted of a 1,000-gallon
tank, punp, and engine which were all mounted on a frame pallet. An operator's
console was an integral part of the unit, but was not mounted on the pallet. Wing
bo.oms (1.5 inches in diameter, 22 feet long) extended from the outboard engine
nacelles toward the wing tips. A short tail boom (3 inches in diameter, 20 feet
long) was positioned centrally near the aft cargo door.

Each aircraft normally

had a crew of three men: the pilot, co-pilot (navigator), and flight engineer
.(console operator). During the peak activity of RANCH HAND operations (19681969), 33 UC-123K aircraft were employed. The "U" designated modification for
aerial spraying and the "K" designated modification with jet boosters.

However,

many other squadrons of non-RANCH HAND C-123 aircraft were routinely used throughout South Vietnam in transport operations.,
The control of malaria and other mosquito-borne diseases in South Vietnam
necessitated an extensive aerial insecticide application program in order to
Control these vector insects. From 1967 through 1972, three UC-123K aircraft
were used to spray Malathion, an organophosphate insecticide. These aircraft
could be distinguished from the Herbicide-spraying aircraft because they were

�not camouflaged. These aircraft routinely sprayed insecticide adjacent to
military and civilian installations, as well as in areas where military
operations were in progress, or about to commence.
Approximately 10 to 12 percent of all herbicides used in South Vietnam
was disseminated by helicopter or ground application equipment. Generally,
helicopter crews were not assigned to herbicide spray duties on a full-time
basis and rotated the spraying duties with other mission requirements. The
military UH-1 series of helicopters, deployed by the Air Force, the Army,
and Navy units, generally sprayed the herbicides. The most common spray
system used was the AGRINAUTICS unit. This unit was installed in or removed
from the aircraft in a matter of minutes because it was "tied down" to installed cargo shackles and aircraft modifications were not required for its
use. The unit consisted of a 200-gallon tank and a collapsible 32-foot spray
boom. The unit was operated by manual controls to control the flow valve and
a windmill brake.

Generally, each helicopter had three crew members.

A summary of the aircraft used in herbicide and insecticide operations is
shown in Table 5.
TABLE 5. US MILITARY AIRCRAFT USED IN THE DISSEMINATION OF HERBICIDES
AND INSECTICIDES IN SOUTH VIETNAM

Aircraft

Camouflaged

Chemical Disseminated

UC-123K

Yes

All Herbicides

UC-123K

No

Malathion

Yes

Orange, Blue

Helicopter
Air Force UH-1
Army UH-1B/UH-1D
Navy UH-1E

10

�Various ground delivery systems were also used in South Vietnam for
control of vegetation in limited areas. Most of these units were towed
or mounted on vehicles. One unit that was routinely used was the Buffalo
turbine. It developed a wind blast with a velocity up to 150 mph at 10,000
ft /minute volume. When the herbicide was injected into the air blast, it
was essentially "shot" at the foliage. The buffalo turbine was useful for
roadside spraying and applications of perimeter defenses.

The herbicides

of choice in these operations were Blue and Orange.
Exposure Considerations:

Applications and Environmental Parameters

There were relatively few military operations that involved the handling
of herbicides by military personnel. A review of operations involving
Herbicide Orange in South Vietnam from January 1962 to April 1970 revealed
that there were essentially three groups of US military personnel potentially exposed to Herbicide Orange and its associated dioxin contaminant.
These three groups were:
1. "Operation RANCH HAND" personnel actively involved in the
defoliation program.

This group included aircrew members and maintenance

and support personnel directly assigned to the RANCH HAND squadrons.
2. Personnel assigned to selected support functions that may have
resulted in exposure to Herbicide Orange. This group included, for example,
personnel who sprayed herbicides, using helicopters or ground application
equipment; personnel who may have delivered the herbicides to the units
performing the defoliation missions; aircraft mechanics who were specialized
and occasionally provided support to RANCH HAND aircraft; or, personnel who

11

�may have flown contaminated,C-l23 aircraft, but were not assigned to RANCH
HAND (e.g., during the Tet Offensive, all RANCH HAND aircraft were reconfigured to transport supplies and equipment, and were assigned to non-RANCH
HAND squadrons).
3. Ground personnel who may have been inadvertently sprayed by
defoliation aircraft or who, during combat operations, may have entered an
area previously sprayed with Herbicide Orange.
The total number of US military personnel exposed to Herbicide Orange is
not known. Approximately 1,200 RANCH HAND personnel were exposed in direct
support of the defoliation operations; however, there are no data on the
number of non-RANCH HAND personnel who may have been exposed. The actual
number of people may be in the thousands since at least 100 helicopter spray
equipment units were used in South Vietnam, and most military bases had
vehicle-mounted and backpack spray units available for use in routine vegetation control programs.

The number of military ground personnel who may

have inadvertently been sprayed by RANCH HAND aircraft, or who may have
entered areas recently sprayed with Herbicide Orange during combat operations
is not known. Approximately 10 percent of South Vietnam was sprayed with
herbicides, and most of this area was contested and/or controlled by enemy
forces. Most areas sprayed were remote, unpopulated and forested. Because
of the dense canopy cover, the target of the defoliation operation, the amount
of herbicide penetrating to the forest floor would have been small. The
exposure of personnel could have occurred by essentially three routes:

12

�1. Percutaneous absorption and inhalation of vapors/aerosols by
direct exposure to sprays.
2. Percutaneous absorption and inhalation of vapors by exposure to
treated areas following spray application, and
3. Ingestion of foods contaminated with the material.
The chemical and physical characteristics of Herbicide Orange and the
spray, as it would have occurred following dissemination from a UC-123K, are
important factors in assessing relative exposures to the Herbicides and TCDD.
Table 6 reviews the pertinent chemical and physical characteristics of
Herbicide Orange. Table 7 reviews both the application parameters of the
spray system used in the UC-123K aircraft and the characteristics" of the
spray itself. Generally, herbicides were sprayed in the early morning or
late afternoon, so as to minimize the effects of air movement on particle
dispersion.
TABLE 6. PERTINENT CHEMICAL AND PHYSICAL CHARACTERISTICS OF HERBICIDE ORANGE

Formulation Concentrated
Water Insoluble

(8.6 Ib ai/gal)*
Density = 1.28

Vapor Pressure

-4
3.6 x 10 mm Hg at 30°C

NBE** 2,4-D

: 1.2 x 10"4

NBE 2,4,5-T
TCDD

: 0.4 x 10"4
:
1 x 10"4

Viscous
Noncorrosive to metal
Deleterious to paints, rubber, neoprene
: Long shelf 1ife

40 centipoises at 20°C

*Pounds active ingredient (2,4-D and 2,4,5-T) per gallon.
**NBE - Normal Butyl ester
13

�TABLE 7. APPLICATION PARAMETERS AND SPRAY CHARACTERISTICS OF THE UC-123K/
AA 45 Y-] INTERNAL SPRAY SYSTEM

Aircraft speed

130 KIAS*

Aircraft altitude

150 feet

Tank volume

1,000 gallons

Spray time

3.5-4 minutes

Particle size:
&lt;100 microns: 1.9%
100-500 microns: 76.2%
&gt;500 microns : 21.9%
87% impacted within 1 min
13% drifted or volatilized
Mean particle volume

0.61 microliters

Spray swath

260 + 20 feet

Mean deposition

3 gallons/acre

Total area/tank

340 acrea

*Knots indicated air speed

Ground combat forces normally would not have been expected to have entered
a previously treated area for several weeks after treatment, during which
time numerous environmental factors would have reduced the potential for
exposure to military personnel. An indepth review of the environmental
fate of Herbicide Orange and TCDD concluded the the vast majority of the
phenoxy herbicides would have impacted forest canopy, the intended target.
14

�Rapid uptake (e.g., within a few hours) of the ester formulations of
2»4-D and 2,4,5-T would have occurred.

Most of the herbicide probably

would have undergone rapid degradation (weeks) within the cellular
matrix of the vegetation. However, some of the herbicide may have
remained unmetabolized and would have been deposited on the forest
floor at the time of leaf fall. Soil microbial and/or chemical action
would likely have completed the degradation process.

Herbicide droplets

that impacted directly on soil or water would have probably hydrolyzed
rapidly (within hours). Biological and nonbiological degradative processes
would have further occurred to significantly reduce these residues.

Some

violatilization of the esters of 2,4-D and 2,4,5-T would have occurred
during and immediately after application. The volatile material most likely
would have dissipated within the foliage of the target area.

Photodecompo-

sition of TCDD would have minimized the amount of biologically active volatile residues moving downwind of the target area.
Accumulation of phenoxy herbicides in animals may have occurred following
irigestion of treated vegetation.

The magnitude of this accumulation would

have likely been at nontoxic levels. Herbicide residues in animals would
have rapidly declined after withdrawal from treated feed.
Most TCDD sprayed into the environment during defoliation operations would
have probably photodegraded within 24 hours of application. Moreover,
recent studies suggest that even within the shaded forest canopy, volatilization and subsequent photodecomposition of TCDD can occur. Since translocation into vegetation would be minimal, most TCDD that escaped

15

�photodegradation would probably have entered the soil-organic complex
on.the forest floor following leaf fall. Soil chemical and microbial
processes would have further reduced TCDD residues. Bioconcentration
of the remaining minute levels of TCDD may have occurred in liver and
fat of animals ingesting contaminated vegetation or soil. However,
there are no field data available that indicate that the levels of TCDD
likely to have accumulated in these animals would have had a biological
effect.
The environmental generation of TCDD from 2,4,5-T residues, through thermal
or photolytic processes, would have been highly unlikely and of no consequence.
SUMMARY
The choice of herbicides used in South Vietnam in Operation RANCH HAND,
1962-1971, was based upon those herbicides that had been widely used in
world agriculture, shown to be effective in controlling a broad spectrum
of vegetation, and proven safe to humans and animals. The major herbicides
used in South Vietnam were the phenoxy herbicides 2,4-D and 2,4,5-T. These
two herbicides were formulated as the water insoluble esters and code-named
by the military as Purple, Orange, Pink and Green. A water soluble amine
formulation of 2,4-D was used in Herbicide White. Two other herbicides
were extensively used by the military, picloram (in White) and cacodylic
acid (in Blue).
An estimated 107 million pounds of herbicides were aerially-disseminated
oh 3 million acres in South Vietnam from January 1962 through October 1971.

16

�Approximately 94 percent of all herbicides sprayed in Vietnam were
2,4-D (56 million pounds or 53 percent of total) or 2,4,5-T (44 million
pounds or 41 percent of total). The 44 million pounds of 2,4,5-T contained
an estimated 368 pounds of the toxic contaminant, 2,3,7,8-tetrachlorodibenzop-dioxin (TCDD or dioxin). Ninety-six percent of all 2,4,5-T was contained
in Herbicide Orange; the remaining 4 percent in Herbicides Green, Pink and
Purple. However, Herbicides Green, Pink and Purple contained approximately
40 percent of the estimated amount of TCDD disseminated in South Vietnam.
Green, Pink and Purple were sprayed as defoliants on less than 90,000
acres from 1962 through 1964, a period when only a small force of US
military personnel were in South Vietnam. Ninety percent of all the
Herbicide Orange (containing 38.3 million pounds of 2,4,5-T and 203 pounds
of TCDD) were used in defoliation operations on 2.9 million acres of inland
forests and mangrove forests of South Vietnam.
The handling, transport and storage procedures employed for the herbicide
generally precluded physical contact with the herbicides by most military
personnel. However, personnel assigned to the RANCH HAND squadron and to
individual helicopters responsible for the dissemination of herbicides
were the most likely military personnel exposed to the herbicides.
The methods employed in spraying the herbicides, the geographical areas
designated for dissemination of the herbicides, and the action of the
environment on the herbicides generally precluded direct physical contact
with the herbicide by military personnel assigned to other military programs,

17

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&lt;p&gt;For more about this collection, &lt;a href="/exhibits/speccoll/exhibits/show/alvin-l--young-collection-on-a"&gt;view the Agent Orange Exhibit.&lt;/a&gt;&lt;/p&gt;</text>
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                <text>May 28-30 1980</text>
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                    <text>item B Number

°4039

Author

Young, Alvin L.

CorDOratB Author

USAF Occupational and Environmental Health Laborato

D Not Scanned

Report/Article TitlB Typescript: Preliminary Draft for Summary: Herbicide
Orange Site Treatment and Environmental Monitoring:
Summary Report and Reccommendations for the Naval
Construction Battalion Center, Gulfport, MS

Journal/Book Title
Year

1979

Month/Day

November

Color

D

Number of Images

6

DOSCrlptOn NOtOS

Note on reP°rt "F°r Official Use Only". See Item 187 for final
version

Wednesday, January 16, 2002

Page 4039 of 4258

�PRELIMINARY DRAFT
SUMMARY

HERBICIDE ORANGE SITE TREATMENT AND ENVIRONMENTAL MONITORING:
SUMMARY REPORT AND RECOMMENDATIONS FOR THE
NAVAL CONSTRUCTION BATTALION CENTER, GULFPORT MS

Prepared For
AIR FORCE LOGISTICS COMMAND
WRIGHT-PATTERSON AFB OH

Major Alvin L. Young, Ph.D.
Major William J. Cairney, Ph.D.
Lt Col Charles E. Thalken, DVM

November 1979

USAF OCCUPATIONAL AND ENVIRONMENTAL HEALTH LABORATORY
AEROSPACE MEDICAL DIVISION (AFSC)
BROOKS AFB TX 78235

"FOR OFFICIAL USE ONLY"

�SUMMARY

This report was prepared by members of the Aerospace Medical Division
(AFSC) and the United States Air Force Academy for the Air Force Logistics
Command (AFLC). The purpose of the report is to document the past and
present interest and concern in environmental monitoring studies of a
storage area on the Naval Construction Battalion Center (NCBC), Gulfport MS.
The area of concern had been used for the long-term storage of 840,000
gallons of Herbicide Orange from mid-1968 to mid-1977.
Since 1970, various Air Force laboratories have been conducting
environmental surveys of the soils, plants, and aquatic system in and
around the Herbicide Orange Storage Area. As the drums of herbicide began
to deteriorate, and as more information became available on the toxic
contaminant 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD) contained in the
herbicide, more extensive monitoring programs were conducted.

In the

summer of 1977, the entire inventory was dedrummed at NCBC, transferred
to a specially equipped ship and destroyed by at-sea incineration during
Project PACER HO.

The AFLC programming plan and the EPA permits for the

disposal of the herbicide, committed the USAF to a subsequent storage site
reclamation and environmental monitoring program. The major objectives of
this program were to (1) determine the magnitude of Herbicide Orange contamination on the Storage Area; (2) determine fate of the phenoxy herbicides
2,4-D and 2,4,5-T, their phenolic degradation products and TCDD in soils
of the Storage Area; (3) monitor movements of residues from the Storage
Area into adjacent water, sediments and biological organisms; and (4)
recommend managerial techniques for minimizing the impact of the herbicides
and TCDD residues on the ecology and human populations adjacent or near
the Storage Area.

�The basic protocol used in the present study consisted of selecting
42 sites within the Storage Area and sampling the soil.

Previous studies

had shown that the residue did not appreciably move within the acid soil
and, in addition, an impervious concrete-stabilized hardpan is located
approximately 6 inches below the soil surface. The sites selected for
monitoring of herbicides, phenol and TCDD residues were determined by
whether a spill had occurred or not occurred at a specific location.

In

addition to residue analyses, each soil sample was analyzed for microorganisms. The results of these on-site soil studies indicated that
approximately 1-2 acres of the 12 acre area are significantly contaminated
with Herbicide Orange and TCDD.

Levels of 2,4-D and 2,4,5-T herbicides in

selected samples were greater than 100,000 ppm (mean 78,040 ppm) in July 1977, but
rapidly decreased to one-third that level in 18 months. No accurate estimate of
the persistence time of TCDD are obtained from these studies. However,
data from spill sites monitored for 18 months suggested that TCDD levels
are decreasing. The soil penetration of the herbicides was low while
penetration of TCDD was very low but measurable. Soil sterilization of the soil did
not occur; indeed, certain microflora proliferated under high levels of
herbicides.
As data became available indicating that high levels of TCDD (e.g.,
100-200 ppb) were associated with spill sites on the Herbicide Storage Area,
studies on the fate of TCDD into the drainage system were initiated.

Frozen

archived biological samples, collected and frozen from the stream adjacent
to the Storage Area, were analyzed and reported January 1979 and found positive
for TCDD residues (0.14-3.5 ppb TCDD). Thereafter, additional environmental
ii

�samples were collected in January, February and June 1979. Sediment and
biological samples collected in 1979 from the stream immediately adjacent
to the Storage Area confirmed that movement of TCDD from the Storage Area
occurred through erosion of the soil into the stream (sediment levels of
2.7 to 3.6 ppb and biological levels of 0.14 to 7.2 ppb). Water samples
collected in the same area were negative for TCDD at a detection level
of 0.02 ppb. Samples taken progressively downstream at 3,000, 7,000,
9,000 and 12,000 feet indicated that significant reductions in residue
occurred.

Only two off-base samples (samples collected in February 1979

beyond the 7,000-foot station) were positive for TCDD and then at levels
of only 20 parts per trillion. Although these samples are considered
positive, they are so near the detection limit of the present "state-of-theart" instrumentation (gas chromatography-mass spectrometry).
The specific recommendations for the 12 acre Herbicide Orange Storage
Area are (1) continue to leave the area undisturbed and restricted to vehicular
traffic; (2) prevent movement of soil and silt from the area by stabilizing
the ditch bank, constructing silt catchments within the ditches, and
constructing a silt-retaining pond prior to the stream leaving the NCBC;
and initiate a research effort to:
a. decontminate TCDD-laden soils.
b. increase TCDD degradation rates.
c. characterize the uptake and distrubution of TCDD in the
aquatic environment.

iii

�SECURITY CLASSIFICATION OF THIS

/&gt;«!« fin

READ INSTRUCTIONS
BEFORE COMPLETING FORM

REPORT DOCUMENTATION PAGE
1. REPOST NUMDER

2. OOVT ACCESSION NO

3, RECIP'FMT'S CATALOG NUMBER

OEHL-TR-79
4. TITLE (end Subtitle)

5. TYPE OF REPORT ft PERIOD COVERED

Herbicide Orange Site Treatment and Environmental
Monitoring: Summary Report and Recommendations
for Naval Construction Battalion Center,
Gulfport MS

Final
6. PERFORMING ORG. REPORT NUMBER
8. CONTRACT Ofl GRANT NUMBERfa)

7. AUTHORfs)

Alvin L. Young, Major, USAF
Charles E. Thalken, Lieutenant Colonel, USAF, VC
William J. Cairney, Major, USAF, BSC
10. PPOGPAM ELEMENT, PROJECT, TASK
APE* ft'WORK UNIT NUMBERS

9. PERFORMING ORGANIZATION NAME AND ADDRESS

USAF Occupational and Environmental Health
Laboratory
Brooks Air Force Base, Texas 78235
It. CONTROLLING OFFICE NAME AND ADDRESS

U, REPORT PATE

USAF Occupational and Environmental Health
Laboratory
Brooks Air Force Base, Texas 78235

November 1979
13. NUMBER OF PAGES

14. MONITORING AGENCY NAME &amp; ADDRESSfU dlllerent from Controlling Office)

15. SECURITY CLASS, (at this report)

Unclassified
15a. OECLASSIFICATION/ DOWNGRADING
SCHEDULE
16. DISTRIBUTION STATEMENT (o[ this Report)

Approved for public release; distribution unlimited

17. D I S T R I B U T I O N S T A T E M E N T (of the abstract entered In Block 20, It dlllerent from Report)

CV^"

J^.
18.

/e&gt;

Xl

9. KEY WORDS (Continue on reverse side II necessary and Identify by block number)

aquatic studies
bioaccumulation
Mode gradation of herbicides
biodegradation of TCDD
chlorinated phenols

ecological effects
Herbicide Orange
2,4-dichlorophenoxyacetic acid (2,4-D)
dioxin
Orange
environmental monitoring
phenoxy herbicides
herbicides
PACER HO

20. A B S T R A C T (Continue on reverse aide It necessary and Identity by block number)

Environmental surveys of the soils, plants and the aquatic system in and around
a 12-acre Herbicide Orange Storage-$urea at Gulfport MS were conducted from 1970
through 1979./^The major objectives of the surveys were to (1) determine the
magnitude of Herbicide Orange contamination on the storage area (2) determine
the fate of the phenoxy herbicides 2,4-D and 2,4,5-T, their phenolic degradation products and TCDD in soils of the storage area (3) monitor movements of
residues from the storage area into adjacent water, sediments and biological
organisms; and (4) recommend managerial techniques for minimizing the impact

DD ,

1473

EDITION OF 1 NOV 65 IS OBSOLETE

Unclassified
SECURITY CLASSIFICATION OF THIS PAGE (Whan Data Entered)

�Sh'CURITv C L A S S I F I C A T I O N OF THIS PAGEflfhan Data Entnr'jd)
.
_
_
.
.
,
.

...'.

soil microbial studies
TCDD
2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD)
2,4,5-trichlorophenoxyacetic acid (2,4,5-T)
20.
.
of the herbicides and TCDD residues on the ecology and human populations adjacent or near the storage area. High levels of TCDD (e.g., 100-200 parts per
billion [ p ] were associated with spill sites on the herbicide storage area.
pb)
Sediment samples from the storage area contained 2.7 to 3.6 ppb TCDD and
biological organisms closely associated with the sediment contained 0.14 to 7.2
,,ppb TCDD. Water samples collected in the same area were negative for TCDD at a
detection level of 0.02 ppb. Two of five off-base samples were positive for
TCDD (a crayfish and a sediment sample both contained 0.02 ppb TCDD). The
primary recommendation is that the 12-acre Herbicide Orange storage area be
left undisturbed permitting the continuation of "natural" degradation of the
herbicides and TCDD. If the area remains undisturbed, it is recommended that
the area be restricted and that efforts be immediately undertaken to minimize
future erosion of contaminated soil into the ditches. The prevention of soil
and silt movement from the area may be accomplished by stabilizing the ditch
banks, constructing silt catchments within the ditches and constructing a silt'^
retaining pond prior to the stream leaving the NCBC.

Unclassified
S E C U R I T Y C L A S S I F I C A T I O N OF T H I S P AGF.fWion fata

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&lt;p&gt;For more about this collection, &lt;a href="/exhibits/speccoll/exhibits/show/alvin-l--young-collection-on-a"&gt;view the Agent Orange Exhibit.&lt;/a&gt;&lt;/p&gt;</text>
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                <text>Charles E. Thalken</text>
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          </element>
          <element elementId="41">
            <name>Description</name>
            <description>An account of the resource</description>
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                <text>&lt;strong&gt;Corporate Author: &lt;/strong&gt;USAF Occupational and Environmental Health Laboratory, Aerospace Medical Division (AFSC), Brooks AFB, Texas</text>
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                <text>1979-11-01</text>
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                <text>Typescript: Preliminary Draft for Summary: Herbicide Orange Site Treatment and Environmental Monitoring: Summary Report and Reccommendations for the Naval Construction Battalion Center, Gulfport, MS</text>
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AUthOP

Young, Alvin L.

D (jot Scanned

Corporate Author
Report/Article Title Memorandum: from Alvin L. Young to USAF OEHUSU,
with subject Statement of Work for Project Order to
USAF Academy, dated 26 October 1979

Journal/Book Title
Year

000

°

Month/Day
Color
Number of Images

D

1

Descripton Notes

Wednesday, January 16, 2002

Page 4031 of 4258

�DEPARTMENT OF THE AIR FORCE
USAF SCHOOL OF AEROSPACE MEDICINE (AFSC)
BROOKS AIR FORCE BASE, TEXAS
78235

ATTN'O™

E

SUBJECT:

Statement of Work for Project Order to USAF Academy

•TO-.

K

26 October 1979

USAF OEHL/SU (Ms Dennis)
1. The following statement of work is recommended for the Project Order
to the USAF Academy (USAFA/DFCBS) in support of the Herbicide Orange
Site Monitoring Project:
USAFA/DFCBS shall during the period of this Project Order conduct
an ecological monitoring program of the storage sites previously
used iftotf. the storage of Herbicide Orange at the Naval Construction
Battalion Center (NCBC), Gulfport MS, and Johnston Island (JI),
Pacific Ocean. The monitoring program will include but not be
limited to the following work:
1.
2.

The chemical analysis of selected soil and biological
samples for TCDD.

3.

The chemical analyses of selected soil and biological
samples for isomers of the tetrachlorodibenzo-p-dioxin
and tetrachlorodibenzo-p-furans.

4.

The microbial analyses of selected soil samples for
qualitative and quantitative data on soil fungi,
actinomycetes and bacteria.

5.
2.

The chemical analyses of selected soil samples for
residues of 2,4-D, 2,4,5-T and associated phenols,

Prepare an interim and final report for submission
to USAF OEHL by 1 Jul and 1 Oct 80, respectively.

If I may be of assistance in clarification or revision of the
above statement, please contact me at 3471.

r•••

«

^

ALVIN L. YOUNG, MAJOR, USAF, P h . D .
Environmental Sciences Consultant

�</text>
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                  <text>&lt;p style="margin-top: -1em; line-height: 1.2em;"&gt;The Alvin L. Young Collection on Agent Orange comprises 120 linear feet and spans the late 1800s to 2005; however, the bulk of the coverage is from the 1960s to the 1980s and there are many undated items. The collection was donated to Special Collections of the National Agricultural Library in 1985 by Dr. Alvin L. Young (1942- ). Dr. Young developed the collection as he conducted extensive research on the military defoliant Agent Orange. The collection is in good condition and includes letters, memoranda, books, reports, press releases, journal and newspaper clippings, field logs and notebooks, newsletters, maps, booklets and pamphlets, photographs, memorabilia, and audiotapes of an interview with Dr. Young.&lt;/p&gt;&#13;
&lt;p&gt;For more about this collection, &lt;a href="/exhibits/speccoll/exhibits/show/alvin-l--young-collection-on-a"&gt;view the Agent Orange Exhibit.&lt;/a&gt;&lt;/p&gt;</text>
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                    <text>itBmDNumbur

04016

Author

a Not Scanned

Young, Alvin L.

Corporate Author
RBDOrt/ArtiClB TltlO Notes on the Herbicide Orange Storage Site, Naval
Construction Battalion Center, Gulfport, Mississippi,
June 13-14, 1979

Journal/Book Title
Yoar

000

°

Month/Day
Color
Number of Images

D

8

Items were filed together in folder labeled, "TOY, NCBC,
Gulfport, MS, 13-14 June 1979, Herbicide Orange Site
Monitoring Project."

Wednesday, January 16, 2002

Page 4016 of 4258

�7

i
jstjc.

^^jL-^- .^?J*=?. J^-rL^??^?

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/^

_^£jZ&lt;?L££
"
1

�TDY SCHEDULE
MAJOR A. L. YOUNG &amp; CAPTAIN J.M. LIVINGSTON
NCBD, GULFPORT MS
13-14 JUNE 79
PROJECT 78-8
13 June 79
Depart SAT 0700

EA 521

Arrive New Orleans

0820
Rental Car:

Arrive NCBC, Gulf port Ms

Airways
504-721-9321

1100 Hr
Contact:
QITRS:

Mr. Claude Anderson
AV 363-2412
NCBC OFFicers Closed Mess

14- June 79
0800

Brief NCBC Commander

Depart NCBC 1300 Hr
Arrive New Orleans 1530
Depart New Orleans

1730

EA 532

Arrive SAT 1900 Hr
MISSION COMPLETE

I

&lt;*

�!Xc—Ji&lt;
JO--

J[ „

W ..-

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.% _.
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�N-!

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i-w

Location of H.O.
Inventory
&gt;- 1 r

;
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'-2.

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Ave
Herbicide Orange Storage Site
Naval Construction Battalion Center
Gulfportffi
.

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Inventory

,• \ \
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Seventh Ave
Herbicide Orange Storage Site
Naval Construction Battalion Center
Gulfport MS

�Location of H.O
Inventory

Ave
Herbicide Orange Storage Site
Naval Construction Battalion Center
Gulfport MS

��</text>
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                  <text>&lt;p style="margin-top: -1em; line-height: 1.2em;"&gt;The Alvin L. Young Collection on Agent Orange comprises 120 linear feet and spans the late 1800s to 2005; however, the bulk of the coverage is from the 1960s to the 1980s and there are many undated items. The collection was donated to Special Collections of the National Agricultural Library in 1985 by Dr. Alvin L. Young (1942- ). Dr. Young developed the collection as he conducted extensive research on the military defoliant Agent Orange. The collection is in good condition and includes letters, memoranda, books, reports, press releases, journal and newspaper clippings, field logs and notebooks, newsletters, maps, booklets and pamphlets, photographs, memorabilia, and audiotapes of an interview with Dr. Young.&lt;/p&gt;&#13;
&lt;p&gt;For more about this collection, &lt;a href="/exhibits/speccoll/exhibits/show/alvin-l--young-collection-on-a"&gt;view the Agent Orange Exhibit.&lt;/a&gt;&lt;/p&gt;</text>
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                  <elementText elementTextId="63891">
                    <text>Item D Number

°4014

AuthOP

Young, Alvin L.

D Not Scanned

Corporate Author
Report/Article TitlB Manuscript Notes Regarding Incineration, 20 June 1978

Journal/Book Title
Year

°00°

Month/Day
Color
Number of Images

D

2

Doscrlpton Notes

Wednesday, January 16, 2002

Page 4014 of 4258

�* •

J*

rs

fc-

n

�EPA-600/2-78-086
April 1978

Environmental Protection Technology Series

ifF

ft %*

jse&gt; sr^
jflk
HI

O

%
^ PRO^°

^

�</text>
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&lt;p&gt;For more about this collection, &lt;a href="/exhibits/speccoll/exhibits/show/alvin-l--young-collection-on-a"&gt;view the Agent Orange Exhibit.&lt;/a&gt;&lt;/p&gt;</text>
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                  <elementText elementTextId="63871">
                    <text>Item D Number

°3947

Author

Young, Alvin L.

D ^ot Scanned

Corporate Author
RBpOPt/ArtiCiO Title

Notes

&gt; Data. and Photographs: Ecological
Studies/Gulfport, Mississippi, 1-2 July 1974

Journal/Book Title
0000

Month/Day
Color
Number of Images
DOSCrlptOn NOtOS

D

60

A items were filed

"
together in a folder labeled, "Ecological
Studies/Gulfport, Mississippi, 1-2 July 1974."

Tuesday, January 08, 2002

Page 3947 of 4009

�D E P A R T M E N T OF THE AIR F O R C E
THE DEAN OF THE F A C U L T Y
U S A F A C A D E M Y , C O L O R A D O 80840

1 July 1977

Mr John Davidson
Ag-Organics Department
Dow Chemical USA
P.O. Box 1706
Midland, MI 48640
Dear John
Under separate cover, I have sent Mr Don Ervick, 24 soil sample for TCDD
analysis (see attached) . As you will note these samples are from our
biodegradation plots or from Test Area C-52A. They were carefully
selected to provide the maximum amount of data on (1) the soil persistance and/or degradation rate of TCDD in three soil types, (2) the
leaching of TCDD in soil profiles, (3) an assessment of degradation
potential of samples in storage in the absence or presence of phenoxy
herbicides, and (4) the confirmation of analysis by another laboratory.
I sincerely appreciated your assistance in providing for the analysis of
these samples. I will provide a brief report to you on the results.
As of 15 July 1977, I will be affiliated with the USAF Occupational and
Environmental Health Laboratory, Brooks AFB, TX 78235. I will call you
when I get settled on station. Again, my thanks to you for all your
assistance to me during my tenure at the Air Force Academy.
Sincerely
x
ALVIN L. YOUNG/ Capt, -USAF, PhD
Associate Professor of Biological Science
Dept of Chemistry and Biological Sciences
(

1 Atch
List of Samples

�USAFA
TCDD BIODEGRADATION STUDY
SOIL SAMPLES
SUBMITTED TO DOW CIJEMICAL USA
15 JUNE 1977
USAFA
SAMPLE #

DESCRIPTION

Garden City, KS, 22 Mar 74, 4000 Ib/A, 0-6
Garden City, KS, 14 Jan 75, 4000 Ib/A, 0-6
•H1-A^
TCDD, Kansas soil, formulated 22 Jan 75
.G3V.20.qg)4
1.5 ppm TCDD plus 10,000 ppm Orange, Kansas
formulated 22 Jan 75
H-13, AFLC Test Range, UT, 5 Nov 76, 1000 Ib/A, Rep I,
Hole 3, 6-12
6 / 50pfrtr H-14, AFLC Test Range, UT, 5 Nov 76, 1000 Ib/A, Rep I,
V
Hole 3, 0-6
7
H-25, AFLC Test Range, UT, 5 Nov 76, 2000 Ih/A, Rep I,
Hole 2, 6-12
8
H-26, AFLC Test Range, UT, 5 Nov 76, 2000 Ib/A, Rep I,
^
Hole 2, 0-6
9
H-37, AFLC Test Range, UT, 5 Nov 76, 4000 Ib/A, Rep I, -;
Hole 4, 12-18
H-38, AFLC Test Range, UT, 5 Nov 76, 4000 Ib/A, Rep I, 5 ^ m p i
10
Hole 4, 6-12
'
H-39, AFLC Test Range, UT, 5 Nov_76, 4000 Ib/A, Rep I,
Hole 4, Q-,6
12.
H-44, AFLC Test Range, UT, 5 Nov 76, 4000 Ib/A, Rep I,
.f-HolG 2, ,0.-6
13
H-54, AFLC Test Range, UT, 5 Nov 76, 4000 Ib/A, Rep II,
Hole 1, Or6
CMS" Soil Core, Site 0-7,'Eglin AFB, FL, collected 31 Mar 73
3-p 14
Plot #6, 0-6", Herbicide and plowed, Eglin AFB, EL, 21 May 73
'•ii'f- '&gt;
15
Plot tflO, 0-6", Herbicide and amendments plus charcoal,
Eglin AFB, FL,' 21 toy 73
E-10, Eglin AFB, FL, 18 Nov 76, plot_5, hole 2, 12-18 \Q ppjb ••;
E-ll, Eglin AFB, FL, 18 Nov 76, plot. 5, hole 2, 6-12 | PfW
E-12, Eglin AFB, FL, 18 Nov 76, plot, 5, hole 2, 0-6Vy\^ 0^ 4f3&gt;ff

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E-41,
E-44,
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Eglin AFB, FL, 18 Nov 76, plot 7, hole 3, 0 6 &lt; ' ' " ^
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Eglin AFB, FL, 18 Nov 76, plot 9, hole 2, 0-6
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Eglin AFB, Ft,, 18 Nov 76, plot. 10, hole 2, 6-12 ';• ,
Eglin AFB, FL, 18 Nov 76, plot 10, hole .2, 0-6, ,••/"'•''.';

�UNITED STATES AIR FORCE ACADEMY

�Date

ROUTING AND TRANSMITTAL SUP

DO NOT use this form as 4 RECORD of
clearances, and similar
FROM: (Name, org. symbol, Agency/Post)

concurrences, disposals,
Room No.— Bldg.
Phone No.

5041-102
•• GPO : 1977 O - 241-530 (3157)

OPTIONAL FORM 41 (Rev.
Prescribed by GSA
FPMR (41 CFR) 101-11.206

7-76)

�TCDD ANALYSIS, LIQUID ORANGE SAMPLES
Analysis Performed by ARL/LJ, WPAFB, Ohio
Samples submitted: 1 February 1975
Data Received:

11 March 1975
Sample
Number

Date
Sampled

TCDD
PPM

1

1 Aug 74

&lt; 0.25

(a)

2

1.3

(a)

n

3

0.3

(a)

n

4

"

&lt; 0.07

„

5

"

&lt; 0.07

„

6

0.07

Sample Source
*Johnston Island
n
n

n

n

7

4.6

n

a

8

4.6

9

5.3

10

0.28

„
„
•*Eglin AFB

1

*Eglin AFB

2

1 Jan 70

&lt; 0.04
&lt; 0.04

(a) TCDD peak appeared on top of large interference peak.
*

Samples collected from Drums that were to be re-barrelled.

**

Sample routinely used at USAFA for laboratory experiments.

***

Samples used in Biodegradation Plots, Eglin AFB, Florida, April, 1972.

�UNITED STATES AIR FORCE ACADEMY

f'

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�Data from Plots Sampled
August 1974
Data from Plots Sampled
January 1978
10,000

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o

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Q
O

C
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O
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10
1974

4-

1975

1976

4-

1977

1978

1979

Time (Years)
FIGURE 1. Semi-logarithmic Plot of Soil Concentration (0-15 cm) of
TCDD in a Field Site Aerially-treated with 40,000 Kg
2,4,5-T, 1962-1964. Data for Each Date Represent Analysis
of Five 1m2 Plots Established August 1974. (Unpublished
Data, A. L. Young, USAF Occupational and Environmental
Health Laboratory, Brooks AFB, Texas 78235.)

7 years

�S*AJ

78

�A-c.

�DEPARTMENT OF THE AIR FORCE
USAF ENVIRONMENTAL HEALTH LABORATORY (AFLC)
KELLY AIR FORCE BASE. TEXAS
78241

REPLY TO
ATTN OF:

SUBJECT.
TO:

Trip Report - USAF Academy CO and Pullman WA
Chief, OL AA USAF OEHL
Commander, USAF OEHL
IN TURN
1. Place: Department of Chemistry and Biological Sciences,
USAF Academy CO and Department of Soils and Agronomy, Washington State
University, Pullman WA.
2. Inclusive dates of travel: 25-30 Sep 1977.
3. Person making trip: Capt Alvin L. Young.
4. Primary mode of transportation: Commercial air.
5. Purpose of trip: To attend Herbicide Orange Conference at
USAF Academy and review Herbicide Orange biodegradation contract at
Washington State University.
6. Persons contacted: (See attached list).
7. Comments and Observations:
a. The objectives of the Air Force Academy Conference on Herbicide
Orange were to (1) review recent laboratory and field data on the fate
of TCDD and 2,4-0/2,4, 5-T herbicides and to (2) define the direction of
FY78 research. Recent data on TCDD and the phenoxy herbicides from USAF
studies suggest the following:
(1) The degradation of TCDD within a soil profile (i,,e., not
on the soil surface) in a field environment is apparently a first order
reaction, contrary to our earlier opinions (USAFA-TR-76-18). This means
that at any time, the rate of TCDD loss is proportional to its concentration in the soil .

�TCDD, the most favorable conditions for its activity will be defined.
Attempts will then be made to culture the species in sufficient quantity
to use for enriching field soil samples. The Department of Chemistry and
Biological Science have on hand an excellent research staff, facilities, and
equipment for this project. It is estimated that in addition -to the. $12, 000
programmed for FY78 for the microbe study, an additional $8,000 would be
necessary for labeled compounds and technician support.' The Academy team
is submitting a proposal for our evaluation and support.
c. From 28 - 30 September, I visited with Dr H. H. Cheng, Dr T. J. Mizuk
and Mr J. T. Makja, Department of Agronomy and Soils, Washington State
University, Pullman, WA. Dr Cheng is currently completing Phase II of an
Orange Biodegradation Study (see Atch 1). Much of the chemical analyses
of 2,4-D, 2,4,5-T and phenols is being done by a graduate study, Mr Makja
in support of his Ph.D. program (Atch 2). Discussions were held on a
proposed continuation of the project (Atch 3) for FY78. Details of this
entire program were discussed in a previous trip report outlining FY78
Herbicide Orange Research (26 Aug 77). While at WSU, I was invited to
lecture to Dr Cheng ' s CEnvi ronmentalScTence^Course and to Dr Muzik's
D x-ience^Course. Both lectures were on the "Dilemma for Disposal
of Herbicide Orange." With the exception of a few final remarks on the
actual incineration (e.g., efficiency, dates of incineration) the presentations were from a paper, same title, cleared by SOFOI and given in Helena,
Montana, 16 Sep 75 at a conference on "Advancements in Pesticides."
J-*_^_-. , , . I , -C r ^ | . |
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d. This TOY gave me an opportunity to oversee the herbicide work by
both the USAF Academy and Washington State University. Although, Orange
has been incinerated, the projects by these two universities will provide
valuable data in support of the reclamation of the Gulfport (NCBC) and
Johnston Island storage sites. I recommend continuation of both projects
during FY78.
ALVIN L. YOUNG, CAPT, USAF, Ph.D.
Chemist/Biologist Consultant

Atchs
1. Phase II Report
2. Rsch Report for HO
3. Phase III &amp; IV
4. List of Persons Contacted

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�(2) Concentrations of TCDD in soils from field plots treated
with a 3.7 ppm TCDD formulation of Herbicide Orange degraded five
half-lives during a four year period (1972 - 1976). Therefore, the T%
for TCDD in alkaline desert soils was approximately 290 days.
(3) Soils from field plots exposed to TCDD were brought
into the laboratory, dried thoroughly at 30°C and treated to contain
1.5 ppm TCDD. Half of the soil was spiked with 10,000 ppm Herbicide
Orange. Both samples were maintained for two years in the open at a
constant temperature of 24°C and with no water. Less than 15%
herbicide degradation occurred and no appreciable TCDD degradation
occurred in either sample.
(4) Aspergillus leoporis^isolated from herbicide biodegradation
plots in Utah, was evaluated for ^ ability to degrade • C-TCDD.
its
Although the organism rapidly removed the TCDD from the media, no apparent
metabolism occurred. Recovery of the C-TCDD required disruption of the
cellular membrane and exhaustive chloroform extraction. Thin-layer
chromatographic separation suggested that the recovered C-compound was
the parent molecule.
(5) Analysis of Gulfport and Johnston Island soils for actinomycetes, fungi and bacteria indicated increased populations of microbes
with increasing concentrations of herbicide. In soils from areas of
herbicide spills, the populations of microbes were frequently two orders
2
of magnitude (10 ) greater than in control soils.
(6) The movement of TCDD in a soil profile is negligible. Note
that in Table 1, 98% of all TCDD detected is in the 0 - 15 cm increment
of soil. The herbicide was originally subsurface injected in an 8 cm
band at the 10 - 15 cm level. Thus, even in the 4,480 kg/ha plots, the
TCDD detected in the 15 - 30 cm increment may have been there because of
the mass movement of the herbicide at the time of application. Notice
also in Table 1 the close association between rate of herbicide application

�and the level of TCDD found four years after treatment. This is another
indication that the rate of degradation is probably a first-order reaction.
(7) A question that has remained unanswered until recently
was "How long can soil samples remain in a freezer without significantly
affecting TCDD concentration?" Two soil samples have been reanalyzed
after being stored for four years in a freezer in glass jars having
aluminum cap liners. Table.2 give the results of the analysis.
Recognizing that at this level of detection, an error of 20% is acceptable,
the data support the conclusion that soil samples can be stored for at
least four years with no appreciable loss of TCDD.
(8) Biodegradation plots that were treated with activated coconut
charcoal prior to subsurface injection of Herbicide Orange still have
significant herbicide and TCDD levels four years after treatment when
compared with non-charcoal containing plots. Chemical recovery studies in
the laboratory have shown that soils containing charcoal must be extracted
for eight hours with benzene rather than the usual procedure of a 30 minute
extraction with hexane/acetone in order to recover the TCDD.
b. The Air Force Academy Herbicide Staff have indicated their interest
in continuing the|F program on Herbicide Orange through FY78. They propose
supporting the Gulfport ~ Johnston Island Storage Site Study through the
analyses of all soil samples for microorganisms. In addition they are very
interested in a program to determine the feasibility of enriching selected
field sites with microbes capable of degrading TCDD. Captain Cairney is a
microbiologist and is currently the project leader. Under his direction a
preliminary study of microorganisms in the soil of Gulfport and Johnston
Island has been completed. He has isolated a number of species that could
be evaluated for their ability to degrade TCDD. LtCol Bainter and
Maj Bomar.both Ph.D. radiation biologists, are interested in examining
TCDD degradation by these organisms (using tritium labeled TCDD and
C-labeled herbicides). When an organism is identified that can degrade

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21 October 1977

Trip Report ~ USAF Academy CO and Pullman MA
Chief, OL M USAF OEHL
Commander, USAF OEHL

JUOffiE
1. Place: Department of Chemistry and Biological Sciences9
USAF Academy CO and Department of Soils and Agronomy, Washington State
University* Pullman WA.
2. Inclusive dates of travel: 25-30 Sep 1977.
3. Person making trip: Capt Alvln L. Young,
4. Primary mode of transportation: Commercial air.
5- Purpose of trip: To attend Herbicide Orange Conference at
USAF AcaderHiy and review Herbicide Orange blodegradatlon contract at
Washington State University.
6. Persons contacted; (See attached 11st).
7. Comments and Observations:
a. The objectives of the A1r Force Academy Conference on Herbicide
Orange were to (1) review recent laboratory and field data on the fate
of TCDO and 2,4-0/2,4,5-T herbicides and to (2) define the direction of
FY78 research. Rectnt data on TCDD and the phcnoxy herbicides from USAF
studies suggest the following:
(1) The degradation of TCDD within a soil profile (I.e., not
on the soil surface) In a field environment Is apparently a first order
reaction, contrary to our earlier opinions (USAFA-TR-76-18), This means
that at any time, the rate of TCDD loss 1s proportional to Its concentration 1n the soil.

�(2) Concentrations of TCOD 1n soils from field plots treated
with a 3.7 ppw TCDD formulation of Herbicide Oranqe degraded five
half-lives during a four year period (W2 - 1976), Therefore, the Pa!
for TCDD In alkaline desert soils was approximately 290 days.
(3) Soils from field plots exposed to TCOD were brought
Into the laboratory, dried thoroughly at 30 C and treated to contain
1.5 ppm TCDO. Half of the soil was spiked with 10,000 ppw Herbicide
Orange. Both samples were maintained for two years 1n the open at a
constant temperature of 24 C and with- no water. Less than 15%
herbicide degradation occurred and no appreciable TCOD degradation
occurred 1n either sarople.
(4) Asperqlllp leoporis, Isolated from herbicide biodegradatlon
plots in Utah, was evaluated for Its ability to degrade C-TCDD.
Although the organism rapidly removed t e TCOD from the media, no apparent
|
metabolism occurred, Recovery of the C-TCDO required disruption of the
cellularraerobraneand exhaustive chloroform extraction. , Thin-layer
chroraatographic separation suggested that the recovered C-compound was
the parent molecule.
{5} Analysis of Gulfport and Johnston Island soils for actinof^yeetes, fungi and bacteria indicated increased populations of microbes
with increasing concentrations of herbicide. In soils from areas of
herbicide spills, the populations of ralcrobes were frequently two orders
of magnitude (10*) greater than in control soils.
(6) The movement of TCDD in a soil prof11© is negligible. Note
that in Table 1 » 98S of all TCDO detected 1s 1n the 0 - 15 era increment
of soil , "Hie herbicide was originally subsurface Injected in an 8 era
band at the 10 - 15 era level. Thus, even in the 4»48Q kg/ha plots, the
TCDD detected in the 15 - 30 cm Increment may have been there because of
the mass movement of the herbicide at the time of application. Notice
also in Table 1 the close association between rate of herbicide application
and the level of TCDD found four years after treatment. This 1s another
Indication that the rate of degradation is probably a first-order reaction.
(7) A question that has remained unanswered until recently
was "How long can soil samples remain 1n a freezer without significantly
affecting TCDO concentration?" Two soil samples have been reanalyzed
after being stored for four years in a freezer 1n glass jars having
aluminum cap liners. Table 2 give the results of the analysis.
Recognizing that at this level of detection* an error of 201 1s acceptable,
the data support the conclusion that soil samples can be stored for at
least four years with no appreciable loss of TCOD.

�(8) B1odegradat1on plots that were treated with activated coconut
charcoal prior to subsurface Injection of Herbicide Orange still have
significant herbicide and TCOD levels four years after treatment when
compared with non-charcoal containing plots. Chemical recovery studies in
the laboratory have shown that soils containing charcoal must be extracted
for eight hours with benzene rather than the usual procedure of a 30 minute
extraction with hexane/acetOM 1n order to recover the TCDD.
to. The. A1r Force Acade»?y Herbicide Staff have Indicated their Interest
1rt continuing the program on Herbicide Orange through FY78. They propose
supporting the Gulfport - Johnston Island Storage Site Study through the
analyses of all soil samples for microorganisms^ In addition they are very
Interested 1n a program to determine the feasibility of enriching selected
field sites with microbes capable of degrading TCDD. Captain Calrney 1s a
m1crob1olog1st and 1s currently the project leader. Under his direction a
preliminary study of microorganisms 1n the soil of Gulfport and Johnston
Island has been completed. He has Isolated a number of species that could
be evaluated for their ability to degrade TCDD. LtCol Balnter and
f'iaj Boraar* both Ph.D. radiation biologists* are Interested In examining
TCDD degradation by these organisms (using tritium labeled TCOD and
i^c-labeled herbicides). When an organism Is Identified that can degrade
TC09a the most favorable conditions for Its activity will be defined.
Attempts will then be made to culture the species 1n sufficient quantity
to use for enriching field soil samples. The Department of Chemistry and
Biological Science have on hand an excellent research staff, facilities, and
equipment for this project. It Is estimated that 1rs addition to the $12,000
programmed for FY78 for the microbe study, an additional $83000 would be
necessary for labeled compounds and technician support. The Academy team
1s submitting a proposal for our evaluation and support.
c. From 28 - 30 September, I visited with Or H, H. Cheng, Or T. J. Mlzuk
and Mr J. T. Hakja, Department of Agronomy and So1ls» Washington State
University, Pullman, WA. Dr Cheng 1s currently completing Phase II of an
Orange Rlodegradatlon Study (see Atch 1), Much of the chemical analyses
of 2,4-D, 2,4,5-T and phenols 1s being done by a graduate study, Mr Matcja
1n support of his Ph.D. program (Ateh 2). Discussions were held on a
proposed continuation of tha project (Atch 3) for FY78, Details of this
entire program were discussed 1n a previous trip report outlining FY78
Herbicide Oranp Research (26 Aug 77). While at MSU, I was Invited to
lecture to Or Cheng's ENVIRONMENTAL' SCIENCE Course and to Dr fluzlk's
WEED SCIENCE Course. Both lectures were on the "Dilemma for Disposal
of Herbicide Orange." With the exception of a few final remarks on the
actual Incineration (e.g., efficiency* dates of Incineration) the presentations were from a paper, same title, cleared by SOFOI and given 1n Helena,
Montana» 16 Sep 75 at a conference on "Advancements 1n Pesticides."

�d. This TOY gave me ah opportunity to oversee the herbicide work by
Loth the USAF Academy and Washington State University. Although, Orange
has been Incinerated^ the projects by these two universities villl provide
valuable data In support of the reclamation of the Gulfport (rCBC) and
Johnston Island storage sites, ! recommend continuation of both projects
during FY78.
AlVIM I. YOUNG, CAPT, USAF, Ph.D.
Chemist/Biologist Consultant

C Atchs
1. Phase II Report
2. Rsch Report for S10
3. Phase III .&amp; IV
4. List of Persons Contacted
5. .Table 1
6. Table 2

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��FATE OF HERBICIDE ORANGE IN THE SOIL
Interim Report-Phase II

May, 1977
Most of the research activities during the past, six months have been in
the laboratory, with the initiation of experiments on the adsorptiondesorption, leaching, and degradation of 2,^,5-T in the soil. There was,
on the other hand, very little action related to the field lysimeter.
study. Because of the prolonged dry period over the winter months, plus
the lack of severe weather, little had happened in the field. We delayed
the sampling of the lysimeters until April and decided to postpone the
initiation of the summer series of lysimeters until August in order to
characterize the seasonal factors better. Reason for this modification
of research plan will become obvious from the discussion of the laboratorydata.
The purpose of the initial series of laboratory studies was to become
acquainted with the various research techniques, to compare our findings
with existing literature values for verification of our procedures, and
to discover any discrepancies or gaps in the existing information. Since
we already have a wealth of background information on 2,k-D, most of the
experiments in this initial series were conducted with 2,4,5-T at normal
to low levels of treatment concentration. Several reports by O'Connor et
al. (Soil Sci. Soc. Am. Proc. 38:^33, 1971!-; J. Environ. Qual. 5:375, 1976}
have been particularly pertinent in our comparison studies, since they used,
the Palouse soil in their studies. The Freundlich k adsorption constants
we obtained for the Glendale soil were comparable to those by O'Connor et
al., but those for the Palouse soil were higher than theirs. Whereas 2,^-,5-T
was desorbed readily from the Glendale soil (with 67, 7^, 100,and 1 0 de0$
sorbed at 0.2, 0,75 10.2, and ^5.2 ppm after 5 desorptions), desorption
was much less reversible in the Palouse soil (with 21, 20, §2, and 33$ desorbed at the same concentrations). The predictive model by O'Connor et al.
worked well for the Glendale soil, we were interested in the applicability
of this model to a soil with very different desorption pattern. Preliminary,
leaching study on the mobility of 2,U,5-T in a column of Palouse soil under
saturated conditions showed that more than 50$ of the 2,^,5-T in the soil,
after leaching of 10 pore volumes of water, remained in the top 3 cm of
the soil column. Even though unsaturated flow may improve the leaching
efficiency, the mobility of 2,^,5-T in the Palouse soil appears to be limited.
We will be developing more data to test the validity of the model used by
O'Connor et al.

We have also been conducting an incubation experiment to determine'the degradatioi
of 2,U,5-T in the soil at two concentrations under saturated or field capacity conditions. The pattern of 2,U,5-T degradation appeared to differ front
that of 2,H-D in that there was no exponential take-off of the degradation,
rate of the former. Whereas it was almost indistinguishable between the
degradation rates of chain-labeled vs. ring-labeled 2,^-D, the side-chain
of 2,*»-,5-T appeared to degrade faster than the ring. Also more 2,^,5-T degradation occurred in soil at field capacity than at saturation.

�The preliminary data from the laboratory already indicate that seme modification of our research plan may be necessary. We will need to obtain more
data on the adsorption-desorption of both 2,U,5~T and 2,*l-D in all three
soils, particularly at high rates of application. Similarly, we need to
characterize the mobility of these two herbicides in the three soils under
study. Particular focus of our attention will be the mobility of 2,^-D and
the persistence of 2,U,5-T.
On our agenda for research this summer include the following activities:
1. Continued verification and improvement of procedures- for extraction and
analysis of HERBICIDE ORANGE in the soil.
2. Periodical sampling of the lysimeter soils and determination of the herbicide
contents .
3. Preparation of
bation studies.

lU

,

C-labeled butylesters of 2,U-D and 2,^,5-T for the incu-

h. Assess the degradation of HERBICIDE ORANGE in the three soils under laboratoryconditions using ^C tracer technique.
5. Conduct additional experiments on the adsorption-desorption and mobility
of HERBICIDE ORANGE in the three soils.
6. Initiate the summer series of outdoor minilysimeters in Augu^st.
7. Initiate studies on the extractability and identification of herbicide
metabolites -- e.g., 2,if,5~trichlorophenol. to^t1 *•'••'-'
It is the goal of Phase II to develop the methodology and to define the research
emphasis. We anticipate that much of this goal will be realized T?y September,
1977.

�H

3/3

(20

�RESEARCH REPORT FOR HERBICIDE ORANGE

Most of the summer work was devoted toward developing a reliable and
sensitive chemical analysis for Herbicide Orange. The present status may be
evaluated in terms of the analytical technique itself.
Extraction,:

We have been experimenting with a Sephadex anion exchange gel for

extracting herbicide Orange from both water and soil from a 0.2 N NaOH water
or soil extract.

Presently, extraction efficiencies for both 2,4-D and

2,4,5-T have been greater than 70% for the Palouse silt loam, although
we believe improved extraction efficiencies are still possible.

To monitor

the efficacy of the Sephadex before anion exchange, 2,4-D and 2,4,5-T can be
spectrophotoraetrically characterized via ultra-violet light absorption in
both acid and alkali media. Results presently indicate that a cleanup step
before esterification will probably not be necessary as in most chemical
analyses.
Esterification;

To esterify the acid forms of 2,4-D and 2,4,5-T to the

n-butyl ester form for determination on the gas chromatograph, two techniques
were tested, diazoalkylation and boron trifluoride/n-butyl alcohol. At this
time, diazoalkylation appears to be better adapted for routine analyses,
although both techniques appear to give approximately equal yields. Within
a few weeks we plan to esterify our stock solutions of C-14 labelled 2,4~D
and 2,4,5-T for use in a laboratory incubation study scheduled for November.
Thirty four individual incubation apparatuses have been constructed for
the above experiment.
Gas-liquid chromatographic determinations: GLC analyses were performed on

�Orange research report, page 2.

columns packed with 5% SE-30 on Chromosorb W/DMCS, which gave satisfactory
separations of the 2,4-D and 2,4,5-T butyl esters from our supply of Orange.
Due to difficulties experienced with our tritium GLC detector, we are in
the process of upgrading our system by installing a $2000 Ni-63 electron
capture detector, which has the advantages of an enhanced linear range
and resistance to herbicide overloading.

This addition should improve

our GLC capabilities considerably.
Field experiments;

We are continuing our field studies as last reported.

A third soil sampling was recently taken from the Palouse-Wyoming
mini-lysemeters installed last winter, while a summer set of 12 minilysemeters for the Palouse-Mississippi soils were installed and herbicides
applied.

Soil samples were collected from these plots two days later,

and stored.

We are also preparing the water extraction equipment for the

mini-lysemeters.

Hopefully, there will be sufficient moisture in the

early spring for water samples after winter precipitation.

Joseph T. Majka
H. H. Cheng
September, 1977.

�Phase III - 1 October, 1977 to 31 July, 1978.
Work plan:

.

.

1. Complete the second year raihilysimeter study of the fate of Herbicide
Orange under field conditions.
2. Complete the laboratory degradation study using ring2,k-D or 2,U,5-T butyl esters in the three soils.

C or chain- C

3. Initiate a. new series of degradation study under controlled environment
on Mississippi soil only with emphasis on metabolite identification and
possibly the rate of metabolite degradation.

Phase IV - 1 August, 1978 to 30 June, 1979.
1. Complete all analyses for the various degradation studies.
2. Conclude the metabolite identification and degradation study.
3. Complete a Ph. D. dissertation.

3.

�PERSONS CONTACTED

LtCol Hugh Bainter, DFCBS, USAF Academy
LtCol Orwyn Sampson, DFCBS, USAF Academy
Maj John Bomar, DFCBS, USAF Academy
Capt William Cairney, DFCBS, USAF Academy
Capt Randall Gaseor, DFCBS, USAF Academy
Dr H.
Dr T.
Mr J.
State

H. Cheng, Professor of Soils, Washington State University
J. Muzik, Professor of Agronomy, Washington State University
T. Makja, Graduate Student, Dept of Agronomy and Soils, Washington
University.

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                  <text>&lt;p style="margin-top: -1em; line-height: 1.2em;"&gt;The Alvin L. Young Collection on Agent Orange comprises 120 linear feet and spans the late 1800s to 2005; however, the bulk of the coverage is from the 1960s to the 1980s and there are many undated items. The collection was donated to Special Collections of the National Agricultural Library in 1985 by Dr. Alvin L. Young (1942- ). Dr. Young developed the collection as he conducted extensive research on the military defoliant Agent Orange. The collection is in good condition and includes letters, memoranda, books, reports, press releases, journal and newspaper clippings, field logs and notebooks, newsletters, maps, booklets and pamphlets, photographs, memorabilia, and audiotapes of an interview with Dr. Young.&lt;/p&gt;&#13;
&lt;p&gt;For more about this collection, &lt;a href="/exhibits/speccoll/exhibits/show/alvin-l--young-collection-on-a"&gt;view the Agent Orange Exhibit.&lt;/a&gt;&lt;/p&gt;</text>
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03399,

Author

D

Young, Alvin L.

MotScannBfl

Corporate Author
Report/Article TitlB Typescript: Dilemma for Disposal of Herbicide Orange

Journal/Book Title
Year

1975

Month/Day

September 16

Color
Number of Images

D

30

Presentation to a seminar on "Advancements in Pesticides"
Helena, Montana, September 16, 1975.

Friday, January 04, 2002

Page 3899 of 3927

�DILEMMA FOR DISPOSAL OF HERBICIDE ORANGE*

Captain Alvin L&gt;i&gt;Jf5auji&lt;g,, Ph.D.
Associate Professor of Physiology
Department of Chemistry and Physiology
United States Air Force Academy, CO 80840

Presentation to a seminar on "Advancements in Pesticides",
Helena, Montana, September 16, 1975. Sponsored by the
Solid Waste Management Bureau, Montana Department of Health
and Environmental Sciences, Helena, Montana and by Region
VIII, Environmental Protection Agency, Denver, Colorado.

* The information on disposal options from Final Environmental'
Impact Statement on "Disposition of Herbicide Orange by
Incineration, November, 1974".

�DILEMMA FOR DISPOSAL OF HERBICIDE ORANGE
Captain Alvin L. Young, Ph.D.
Associate Professor of Physiology
Department of Chemistry and Physiology
United States Air Force Academy, CO 80840
In 1962 vegetation control systems using herbicides were
introduced by the military into the Southeast Asia Conflict.
Their use was to remove dense vegetation along highways, canals,
lines of communication, and around base perimeter camps; thereby
reducing

•enemy ambush.

The herbicide formulation of choice was

an equal mixture of the n-butyl esters of 2,4-D and 2,4,5-T.
This formulation was labelled Orange because of the orange band
around the centers of the 55-gallon drums in which it was
transported.
Although severe criticism of the defoliation program was
voiced as early as 1964, it was five years later before the
program (Operation Ranch Hand) was suspended by the Department
of Defense.

Initial criticism was directed at Orange as a

chemical warfare agent used against crops and the environment
of South Vietnam.

However, the termination of the program was

not based on the above criticism but rather on reports by
South Vietnamese newspapers of an increased occurrence of
birth defects during June and July 1969 from areas defoliated
with Orange Herbicide.

These reports elicited far-reaching

reactions from governmental agencies, segments of the scientific
community, lay groups concerned with environmental problems,

�and from the communication media.

Government sponsored panels

of experts, special commissions established by scientific
organizations, hearings before subcommittees, of the U. S.
Congress, and Conferences attended by representatives from
industry, government, and universities examined available data
and were not able to provide a generally acceptable answer,to
the central question of whether 2,4,5-T as produced and used
constituted a risk for human

pregnancy.

In mid-October 1969&gt; a report was released to the press of
the findings of a study by Bionetics Research Laboratories,
Litton Industries Incorporated.

The report documented the

presence of defective offsprings from mice and rats treated
during early pregnancy with large doses of 2,4,5-T,
subsequently announced on October 29, 1969,

It wa.s

that a series of

coordinated actions were being taken by several governmental
agencies to restrict.the use of the herbicide 2,4,5-T.

Addi-

tional animal experiments performed early in 1970 confirmed
that pregnant mice did deliver some malformed offspring.

The

question then was one of whether or to what extent, such animal
data could be extrapolated to man.

On April 14, 1970, the

Secretary of Health, Education and Welfare (HEW) advised the
Secretary of Agriculture that:

"In spite of these uncertainties,

the Surgeon General feels that a prudent course of action must
be based on the decision that exposure to this herbicide may
present an imminent hazard to women of child-bearing

age."

�Accordingly, on the following day, the Secretaries of Agriculture,
HEW, and Interior jointly announced the suspension of 2,4,5-T for
"all uses around the home, recreation areas, and similar sites"
and "all uses on crops intended for human consumption".

Immedi-

ately thereafter, the Department of Defense suspended the use of
Orange Herbicide in South Vietnam.
The suspension of the use of Orange Herbicide left the
Department of Defense with 1.5 million gallons in Vietnam and
860,000 gallons at the Naval Construction Battalion Center,
Gulfport, Mississippi.

In September 1971, the Secretary of

Defense directed the Joint Chiefs of Staff to dispose of the
surplus inventories of herbicide in both the Continental United
States and Vietnam.

The Air Force was assigned the responsibility

of finding a disposal method(s) that was (were) ecologically safe
and economically feasible.

In April 1972, the 1.5 million gallons

of herbicide in Vietnam was placed in 55-gallon drums and transported to Johnston Island, Pacific Ocean.

The total Orange

Herbicide inventory was 2.3 million gallons stored in approximately 40,000 55-gallon drums.

Thus, not only is there herbicide

to be disposed but also the drums.
The initial method proposed for disposal was incineration
at a commercial facility in the United States.

The details of

this proposed course of action were documented in a draft
environmental statement which was filed with the Council on
Environmental Quality and the Public in January 1972.
draft statement discussed the studies that were being

3

The •

�accomplished but not completed when the statement was filed.
Based on the fact that studies were still in progress and the
interest evidenced in comments received on the draft statement,
the Air Force decided to conduct additional studies on incineration as well as additional investigations of alternative
disposal methods.
In April 1972, the Air Force Logistics Command (AFLC)
began an indepth investigation into the feasibility of use,
incineration, soil biodegradation, factionation, chlorinolysis
and

reprocessing as major disposal options.

Data to be

collected on each method included the parameters of time, cost,
and effectiveness of the disposal process.

In addition, the

physical, biological,managerial and social-political factors
for potential sites of disposal were to be assessed.

Reports

of progress and/or problems encountered were periodically
presented to an Ad hoc Committee on the Disposal of Herbicide
Orange of the Air Force Scientific Advisory Board.

Other

disposal options reviewed and discussed with the Ad_ hoc.
Committee were return of the herbicide to the manufacturer,
deep well disposal, burial in an underground nuclear cavity,
sludge burial, microbial reduction, and no disposal action.
The last option was to be selected only if the other options
were not ecologically acceptable, technology not sufficiently
developed for their employment, if excessive capital investment
was required, if unacceptable time delay was imminant, or if the

�socio-political opposition prevented any course of action.
The option of "no action" would mean that Orange would be placed
into seal storage tanks for permanent storage at both Johnston
Island and Gulfport, Mississippi.
In the formulation of an environmental impact statement on
the disposal of Orange the following description of action for
each option was prepared.

1.

Use
Orange Herbicide is not an Environmental Protection

Agency (EPA) registered pesticide and cannot be domestically
used or sold.

The Orange Herbicide stock to be disposed rep-

resents a resource of considerable monetary
estimate is $80-100 million).

value (a recent

Orange Herbicide has a potential

use on Federal lands as well as on privately owned lands; however,
any use would require registration.

The prudent disposition of

Orange Herbicide for use on privately owned or governmentally
owned lands may have a tremendous impact on increasing

the avail-

ability of certain natural resources, e.g., rangelands and
forests.
Undesirable weed and brush species are widespread in every
region of the United States.

Their combined impact on range-

lands and production of commercial timber is enormous.

Approx-

imately half o£ the total land area of the United States is used
for pasture and grazing purposes, and weeds and brush are a
problem on nearly all these forage lands.

Economic losses from

�weeds on forage lands are virtually incalculable and include
low yield of forage and animal products per unit area, reduced
livestock gains, and livestock poisoning.

Although herbaceous

weeds are found on all rangelands in the United States and
result in forage losses, brush is the primary problem.

Various

brush species dominate an estimated 320 million acres of
rangelands.

More than 80% of 107 million acres of grazing land

in Texas alone is infested to some extent with brush.
established, woody plants such as mesquite (Prosopis
juniper

Once
spp.)

(Juniperus spp.) oak (Quercus spp.}, and sagebrush

(Artemisia spp.) cannot be eliminated by good grazing practices
alone.

Measures must be taken to convert brush dominated

rangeland to more productive types of vegetation.

Brush control

and striking improvements in the grazing capacity of rangeland
may be obtained most economically by low-rate and low-volume
applications of phenoxy herbicides.
Commercial forest land in the United States is estimated
at 509 million acres.

Although much of this land is not under

any form of planned management for production of forest products,
management for an increased productivity will soon become
essential to meet the needs of the United States population.

It

is estimated that the total area of forest lands supporting
important amounts of undesirable vegetation is approximately
300 million acres, or a land area of potentially commercial
timberland equal to roughly the combined areas of Texas, California,
and Washington.

There are some 4.7 million acres of commercial

�forest land in western Oregon and Washington on which the land
is occupied by vegetation whose presence precludes reestablishment of conifers.

Much of the area is in the highest productivity

class for growth of forest products.
Concepts of selective brush control have been developed for
reforestation with the aid of commercial formulations of 2,4-D
and 2,4,5-T.

There are presently some 100,000 acres being

treated each year with various formulations
all as the low-volatile esters.
in operations

of these materials,

Success has been good, especially

on the slower-growing brush

species.

Thus the purpose for using herbicide Orange on rangelands
and reforestation would be to reduce the amount of undesirable
vegetation that dominates in selected regions of the United
States bec'ause of past disturbances and improper grazing and/or
timber practices.

With the use of herbicide Orange, a more

diversified and desirable variety of plant species would
become established.

This in turn would have a substantial

impact on increasing productivity of these regions.
The environmental impact of using herbicide Orange for
chemical brush control will vary from region to region and
whether it is for range or forest use.

However, regardless of

the region of use, or for rangeland or reforestation, critical
assessments of effects on vegetation, wildlife, domestic
livestock, soil microorganism, aquatic life, rangeland or forest
waters, and man must be evaluated.
2.

RETURN TO MANUFACTURERS
In March 1972, seven manufacturers of herbicide Orange

7

�were contacted regarding the possibility of chemically reprocessing
Orange Herbicide whereby all impurities, including dioxin, would
be extracted or destroyed.

Results from all manufacturers were

essentially the same; i.e., they did not feel that they were
capable of reprocessing the product without extensive investment
in equipment and/or development of new processes.

Lead time

for this type of action would require in excess of 18 months
before large scale reprocessing could begin.

As a result of

EPA's action on 24 June 1974 to cancel the hearings on the
possible further restriction of 2,4,5-T, the manufacturers
were again contacted (August 1974) via letter to determine if
their position may have changed.

Manufacturers

again indicated

that they did not want to reprocess Orange.
3.

DEEP (INJECTION) WELL DISPOSAL.
This process would involve injection of the herbicide

into a deep subsurface formation.

The well hole down into the

formation would be lined with casing which has been cemented
into place to prevent fluids from rising to the surface outside
the casing to a permeable geologic formation.

The herbicide

drums would be emptied into tanks or vats on the surface where
the Orange Herbicide would be diluted and then pumped down the
tubing to the permeable formation.

The packer tool prevents

fluid from returning to the surface inside the casing and
impermeable upper and lower formations adjacent to the permeable
formation restrict verticle movement.

This process has not been

�approved by state agencies, or the EPA, as deep well injection
is not considered environmentally safe or desirable disposal
method for waste m a t e r i a l s .

The p o l i c y is to oppose all

storage or disposal of wastes in deep wells without strict
controls and a clear demonstration that such disposal will not:
a) interfere with present or potential use of subsurface

water

supplies, b) contaminate interconnected surface waters, or
c) otherwise damage the environment.

Little concrete information

is available on what degradation of the Orange would occur at
the depths, temperatures, and pressures encountered in deep
wells.

This coupled with the possibility of subsurface

disturbances at a later date which might allow Orange to migrate
into formations leading to water supplies or other valuable
formations, has prevented any of the firms interested in
disposing of Orange in deep wells from obtaining

state or

Federal permits.
4.

BURIAL IN UNDERGROUND NUCLEAR TEST CAVITIES
The Atomic Energy Commission was contacted regarding

the possibility of disposing of the Orange by burying it in an
earth cavity formed during underground

nuclear testing.

They

advised that a major research, development, and experimentation
effort would be required to prove the practicality of this
alternative.

In view of the time required for this effort,

it is not considered a fesible alternative.
5.

SLUDGE BURIAL
This technique offered definite promise, but there was

9

�a lack of interested and q u a l i f i e d i n d u s t r i e s to undertake ('lie
necessary preliminary investigations.

This process involves

one concept of destroying the Orange through bacterial action.
The proposal envisioned constructing trenches in geologically
suited formations on isolated government land.

The type of

formations picked for the trenches would preclude vertical and
lateral movement of the Orange.

The trenches would be filled

with drums containing the Orange and would then be surrounded
by secondary sewage plant sludge, which would provide a growth
medium for the bacteria.

The tops of the drums would then be

mounded with dirt fill and aggragate.

Depending upon the type

of bacteria selected to decompose the Orange, vents might be
required.

This process is not considered acceptable because'of

the time to completely destroy the herbicide is quite lengthy,
possibly as long as 10 to 25 years, and because a system of
monitoring would be required throughout this time period.

The

earth covering would require maintenance and additional time
might also be required to develop a strain of bacteria that
would tolerate high concentrations of Orange.
6.

MICROBIAL REDUCTION
This process involves the biological degradation of

the herbicide through fermentation.

It requires the development

of a microorganism to "feed" on the herbicide.

From the

literature, it seems apparent that microorganisms have developed
unbelievable capabilities for handling organic compounds.

10

�However, two factors severely complicate the biological degradation
of this refractive material:

1) its insolubility in water and

2) its chemical structure (specifically the number and position
of

chlorine atoms attached to the aromatic ring).

Many

investigators have showed that 2,4-D is rapidly decomposed in
the soils and that high concentrations have no depreciable
effect on the soil population of bacteria, fungi, and
actinomycetes.

The persistence of 2,4,5-T is usually two to

three times longer than 2,4-D and very few microorganisms have
been identified as having the ability to break down the 2,4,5-T
molecules.

Data are available that indicate that mixtures of

2,4,5-T are more rapidly degraded than are single compounds.
Very little work has been done on the microbial degradation
of TCDD; however, initial data indicate that it is degradable,
but with an estimated half life of one year (as a single
compound).
The environmental impact of a microbial reducation method
is dependent upon the fate of TCDD in a biological treatment
facility.

It must be established that no TCDD is remaining in

the effluent, or a problem of

enormous consequences can occur.

Thus far no data are available on the fate of TCDD in a
biological reduction system.

All other, aspects of such an

alternative can be controlled and minimized to an acceptable
level.

Monitoring methodology and a failsafe system would be

required.

Until more data are developed the particular

11

�environmental aspects cannot be evaluated.

More specific infor-

mation concerning the process, size of facility, land acreage
required, and effluent parameters are needed.
7.

FRACTIONATION
Fractionation is the process of converting Orange into

its acid ingredients

by means of distillation.

This would

separate the normal butyl esters of 2,4-D and 2,4,5-T and its
contaminant TCDD.
for commercial use.

The 2,4-D and 2,4,5-T would be reformulated
TCDD would then be destroyed by chemical,

biological or incineration

techniques.

Actual distillation

efficiencies theoretically could approach 90-95%.

One

investigator stated that any TCDD residue could be destroyed
by splitting the ether bonds of the molecule.

In the process

of fractionation, the dioxin would be isolated or destroyed.
A small scale study was funded, but the results were inconclusive
Fractionation is not acceptable because : a) the fate of the
dioxin has not been demonstrated, b) in the process, 3% of the
Orange processed could not be accounted for, c) standards to
control and monitor vapor and fluid emmissions into the
environment have not been identified.
8.

SOIL BIODEGRADATION
Soil biodegradation is a soil incorporation technique ,

based on the premise that high concentrations of the Orange
Herbicide and the contaminant TCDD will be degraded to innocuous
products by the combined action of soil microorganisms and soil

12

�chemical hydrolysis.

The rationale for soil incorporation of

herbicide as an ecologically-safe disposal method comes from
pertinent laboratory and field studies.
It seems apparent from laboratory studies that microorganisms have developed extensive capabilities for handling
organic compounds.

Moreover, most organisms seem to have a

latent ability for decomposition of halogenated hydrocarbons.
However, the amount of active herbicide applied to soil may
diminish by means other than biological decomposition; e.g.,
chemical degradation, absorption, volatilization, leaching, and
photodecomposition.
Until recently there was very little information

concerning

the breakdown of 2,4-D or 2,4,5-T in a soil incorporation site.
However, field experiments on the use of soil incorporation
a method of disposing of massive quantities

as

(approximately

1-1/4 million gallons) of 2,4-D and waste by-products has been
carried on in eastern Oregon.
to simulate subsurface
2,4-D

A trenching technique was employed

injection.

A concentration

of 500 Ib/A

(plus waste) was placed at a depth of 10 inches

bands on two-foot centers).

(5-inch

With this placement the actual

concentration of herbicide within these bands was approximately
1250 ppm.

Samples taken between trenches and in soil profile

segments from the surface down through the point of application
indicated minimal vertical and horizontal movement of the
herbicide (or phenolic waste) from the site of initial deposition,
13

�Results from this experiment indicated little differences in
rates of degradation in the trenched plots or a surface application of 500 Ib/A: 95% degradation in 540 days.
Our project group at the United States Air Force Academy
has studied the persistence and movement of herbicide Orange
and TCDD following soil incorporation at rates of 1,000, 2,000
and 4,000 pounds active ingredient 2,4-D and 2,4,5-T/acre (Ib
ai/A) in a remote site in western Utah.

The precent loss of

herbicide over a 330 day sampling period was 78.2%, 75.2% and
60.8%

for the 1,000, 2,000 and 4,000 Ib ai/A plots, respectively.

The calculated half-life of herbicide Orange in alkaline

(pH=

8.1) desert soils was approximately 150 days at these massive
rates.

Data on soil penetration indicated that less than 3.7%

of the herbicide was found at depths greater than 18 inches
282 days after soil incorporation of 4,000 Ib ai/A.

Preliminary

data based on levels of TCDD in the formulation (3.7 ppm) and
those encountered in the soil profile 265 days following soil
incorporation suggested that under these environmental conditions
that half-life of TCDD was 88 days.

Our USAF Academy team also

established biodegradation plots in Garden City, Kansas and
Eglin AFB, Florida.

Data from these incorporation studies are

in agreement with the Utah plots: degradation of 2,4-D, 2,4,5-T
and TCDD when applied at massive rates, rapidly occurs and
movement of the herbicide in fact is minimal.
It is important that the criteria for selection of a site
for soil biodegradation include certain physical, biological,

14

�and managerial factors.
(1) Physical Factors:

From the standpoint of just

p h y s i c a l consideration, the s o i l incorporation technique
provides an array of alternative as to the selection of site.
In general:
(a) A minimum of 2,000 acres must be available.

(b) The site must be remote. It cannot be adjacent
to land currently in agronomic production.
(c) The land must have a low-use potential, i.e,
it should be marginal land. Moreover, the land
should not be considered land that will be
significantly productive in the foreseeable
future.
(d) Water resources must be sufficiently far away
so as not to be contaminated.
(e) The topography of the land must be relatively
flat with a uniform surface.
(f) The texture of the soil should be sandy-loam
or silty-loam with a pH of approximately 8.0.
(g) The area should not be characterized by rock
outcrops or areas of marked deflation or dunes.
The area should also have minimal surface
erosion.
(h) Data should be available on subsurface geology
and hydrology.
(2) Biological Factors:

The vegetation that characterizes

the particular

site must be uniform with a ground cover of at

least 10-15%.

Such a plant community will provide the organic

matter and microclimate that supports the growth and maintenance
of microflora (e.g., fungi and bacteria).

Ideally, the

vegetation should be low-growing shrubs, forbs and grasses to
facilitate the incorporation equipment.
(3) Management Factors:

The management factors that

will influence the selection of the site are:
15

�(a) The requirement for established all weather
roadbeds to and within the disposal site.
(b) The distance to the disposal site from an
off-loading station (e.g., Tail to truck).
(c) The requirement for security of the disposal
site.
(d) Availability of personnel facilities.
(e) Adequate storage space at the disposal site.
A subsurface injection system would be used to incorporate
the herbicide into the soil at a depth of 6-10 inches.

The

injection would be done by using a conventional agricultural
subsoiler, drawn by a heavy industrial tractor.

The subsoiler

would consist of a verticle blade on which a chisel, or foot,
is mounted at an angle of approximately 15° from horizontal.
A piece of metal tubing will be attached to the blade (and
terminating at the base of the chisel) in such a manner that a
piece of hose from the injection pump could be inserted to
permit disposition of the herbicide immediately behind the
chisel.

The equipment, with eight injectors

be calibrated to apply 4000 Ib/A of Orange.
should be on 20-inch centers.

(shanks), should
The eight shanks

During the process of application

the overlying vegetative structures will be damaged.

To prevent

the loss of soil moisture and to reseal the soil (thus minimizing
volatility and damage from wind) a soil compactor

(cultipacker)

will be required and a drought resistant, salt tolerant grass
will be planted.
The environmental impact of soil biodegradation would be
expressed in two major areas; the most significant of which is
the denial of a 1,000 - 2,000 acre tract of land for reclamation
or recreation use for a 3-5 year period during biodegradation.
16

�The proposed site would require continuous monitoring during
the lifetime of the project.

Also occurring will be damage

and/or kill of the overlying vegetative structure in the immediate
disposal area, drastic alteration of the soil structure, and
disturbance and/or temporary destruction of local ecosystems.
Adherence to the above site criteria and incorporation

method

will optimize the soil biodegradation procedure and minimize
adverse environmental impact.
9.

CHLORINOLYSIS

From the theoretical engineering point of view, chlorinolysis offers an efficient, controlled, and safe method for
disposal of the herbicide, as well as other hydrocarbon
lations.

formu-

Chlorinolysis is a process that breaks down the mole-

cule and adds a chlorine molecule to produce carbon tetrachloride,
phosgene, and anhydrous hydrogen chloride, all of which have
established commercial value.
Chlorinolysis as a means to dispose of Orange Herbicide was
evaluated over a period of almost two years.

In July of 1972,

discussions and correspondence with the Environmental Protection
Agency (EPA) committed the Air Force to pursue the testing and
research program necessary to determine the feasibility of
converting Orange to salable products by Chlorinolysis.

In

September 1972, a Memorandum of Agreement between the EPA and
the Air Force was initiated.

The objective of the agreement

was the development of a laboratory program to evaluate the
practicality of the application of Chlorinolysis for the
disposal of Orange.

The investigation was also to determine
17

�the extent of destruction of the impurity dioxin.

The

information

and data obtained in this research was to be utilized by the Air
Force to determine whether the proposed concept could be applied
and used to dispose of Orange and by the Environmental Protection
Agency to determine if it could contribute toward solving the
disposal problems of the petrochemical industry.

It was agreed

that the EPA would manage the research and provide a report
containing all data collected, together with conclusions and
recommendations'.

The Air Force agreed to fund the effort in

the amount of $35,000.
analysis of dioxin.

An additional $10,000 was provided for

Three drums of Orange containging

14ppm

dioxin (analysis by Dow Chemical Company) were provided by the
Air Force.
The EPA report, "Study of Feasibility of Herbicide Orange
Chlorinolysis" (EPA-600/2-74-006, July 1974), covering only
the work of Diamond Shamrock Company was delivered on 2 October
1974.

The report covered the results of bench scale tests and

concluded, based on these bench scale tests, that

chlorinolysis

under the proper conditions effectively converts Orange Herbicide
and its TCDD contaminant to carbon tetrachloride, carbonyl
chloride and hydrogen chloride.

Destruction of the TCDD was

complete, and preliminary toxicology tests of the recovered carbon
tetrachloride on rabbits showed no evidence of TCDD contamination.
The report also contained cost estimates which included credit
for the sale of chemicals from a 25 ton/day plant.

The cost

in the worst case was shown to be $11 million and in the best
$4 million.
18

�Owing to the uncertainties associated with developing
this technique to a full scale plant capable of processing
2.3 million gallons of Orange in a timely and economical
manner.

Partial or total chlorinolysis was not selected as

the method of disposal even though it is satisfactory from an
environmental point of view.
10.

INCINERATION AT SEA
One of the most viable options for the destruction

of Orange Herbicide is via incineration on a ship at sea.

Since

September 1972, a ship the "Vulcanus" (registered in Rotterdam,
Netherlands) has been equipped to carry certain hazardous liquid
chemical cargoes from northern European ports and approved by
participating countries to incinerate the waste cargo in prescribed
areas of the North Sea.

Additionally, U. S. Companies have

suggested shipboard incineration and have indicated a willingness
to investigate it.
The ship is a "double hulled and double bottom tanker with
an overall length of 331.4 feet, a beam of 47.2 feet and a
draft of 22.9 feet.

Her construction

complies with the latest

Inter-Governmental Maritime Consultative Organization (IMCO)
regulations of bulk carriage of dangerous chemicals at sea.
Because of her size, the vessel is able to operate and
continuously man the incineration process.

Two diesel engines

drive the single propeller to give service cruising speeds of
10-13 knots.

19

�The vessel's cargo tank capacity of 3,503 cubic meters
(CBM)

(925,493 gallons) is divided into 15 cargo tanks ranging

in volume from 115 cbm to 574 cbm.

None of these tanks are in

contact with the vessel's hull and/or bottom.

The engine room

is separated from the cargo tanks by double bulkheads, the
pump room and generator room being situated in between.
The incineration

system consists of two combustion chambers

installed right aft of the upper deck.

Each of the bricklined

incinerators has a maximum outer diameter of 5.50 meters (m),
and inside diameter of 4.80 m and a total height, including the
stack, of 10.45 m.

The volume of each combustion chamber is

calculated to be 87.9

cmb.

Each chamber has three burners

with rotating cup fuel injection systems which provide vortex
turbulence and distribution of fuel feed throughout the whole
chamber.
Incineration could be conducted in a designated area
50-60 miles clear of normal shipping lanes and on the open tropical
sea downwind of Johnston

Island.

Gas or diesel oil would be used

to bring the chambers to the required combustion temperature,
normally 1400°C (2552°F); the maximum operating temperature
is reported as 1650°C.

Only when the required temperature is

reached would the feed pumps allow waste to enter the combustion
chambers.

Waste feed flow and air would be carefully

to insure complete combustion.

controlled

Once the required temperature

was obtained, the chambers would be fed solely by the undiluted
Orange.

The Orange could be pumped to each of two chambers at
20

�a rate of 10-12 tons per hour for a total daily pump rate of
about 576 tons.

Therefore, about 22-26 days of continuous

incineration would be required to burn the entire Orange stock
(2.3 million gallons).

The vessel's capacity of about 925,000

gallons of Orange would require three voyages; 925,000 gallons
of Orange would be burned during each of the first two voyages,
and the remaining 380,000 gallons of Orange plus any solvents
used in drum cleaning would be burned during the third voyage.
The data accumulated, together with theoretical considerations
and applied thermochemistry, clearly indicate that the production
of incomplete combustion products can be minimized to insignificant levels.

Destruction, efficiencies of 99.9%

appear feasible for this incinerator project.

or better

This would result

in a total discharge of 0.05 pounds or less of TCDD via the
exhaust streams over the duration of the project.

(The average

concentration of TCDD in the herbicide is about 2 mg/kg and the
total amount of TCDD in the entire Orange stock is approximately
50 pounds.)

The commercial incinerator test program

indicates

that if any TCDD were present in the exhaust stream, it was
analytically nondetectable.

Incineration would convert the

Orange herbicide to its combustion products of carbon dioxide,
hydrogen chloride, and water which will be released to the
atmosphere.

In addition, a relatively small amount of

elemental carbon and carbon monoxide would be generated in the
incineration process and discharged to the atmosphere.

With

proper concern for the environment in which such incineration
would take place, incineration is an environmentally safe
21

�method of disposal of Orange Herbicide.
Ecological monitoring is neither required nor feasible
for the following reasons:

a)

the ship will complete the

project within a month and always be moving and operating over
a large area of the open tropical sea; and b) the predicted
impact will be very minimal and transient for this incineration
option.

A dispersion zone model utilizing "worst case"

analyses techniques was used to estimate mass

concentrations

of unburned Orange and Hydrogen chloride in the air and water
environment in the vicinity of the discharge, and a meteorological model was applied to predict the atmospheric

concentra-

tion of unburned Orange and hydrogen chloride at sea level
downwind of the discharge location.

Predicted results from

these models revealed that there would be no significant
environmental impact upon either the air or ocean environment.
11.

INCINERATION ON JOHNSTON ISLAND
If incineration at sea is not approved by EPA (e.g.,

if a permit for incineration

at sea were not approved) then an

alternate incineration option would be the construction of
an incinerator facility on Johnston Island.
Johnston

Incineration on

Island would require a higher efficiency

ecology of the Atoll.

owing to the

( A complete ecological survey was

conducted of Johnston Island by the Smithsonian
in order to document the areas of concern.)

Institution

The facility on

Johnston Island would probably be designed to incinerate about
206 drums of herbicide per day.

At this rate, approximately

200 burn days would be required to incinerate all 2.3 million
22

�gallons of the Orange stocks.
Thermal decomposition research using differential thermal
analysis was conducted to determine the temperatures required
for complete combustion of Orange Herbicide and a test program
was conducted in a commercial incinerator to document the
feasibility of destroying undiluted Orange Herbicide by means
V

of combustion.

Particular emphasis was placed on the ability

to destroy the low quantity of TCDD (low miligram per kilogram
concentration, mg/kg) present in the herbicide.

Extensive

sampling, utilizing time-weighted and concentration
was conducted to evaluate the unscrubbed

techniques,

combustion gases, the

scrubbing liquid used to cool and scrub the combustion gases,
scrubbed effluent gases, and any solid residues deposited in
the system.

Program objectives were outlined to determine,

among other things, engineering data relative to controlling and
monitoring the incineration process, the composition of the
combustion products, and the toxicity of discharged
water to several aquatic

scrubber

organisms.

For a system operating at combustion chamber temperatures
of 2400-2800°F; dwell time equal to or greater than

0.14

seconds; fuel to air mass ratio of about 0.1; and excess air
greater than 30%, it can be stated that: a) combustion gas
and scrubbed effluent gases are free to undetectable levels.
3

(^0.20xlO~

yg/1 for each compound) of herbicide esters, acids,

and TCDD; b) about 10% of the carbon dioxide and greater than
99.9% of both the hydrogen chloride and carbon particulates
are removed from the combustion gases via an alkaline scrubber;
23

�c)

combustion pyrolyzates are unchlorinated hydrocarbons whose

total concentrations

average less than 0.50 yg/1; d) alkali

scrubbing removes a small fraction of the pyrolyzates from the
combustion gases, and with gaseous condensation in presence of
chlorine, converts some of the pyrolyzates into chlorinated
hydrolyzates; e) total unchlorinated pyrolyzates average less
than 13.0 yg/1 and total chlorinated hydrolyzates average less
than 3.0 yg/1 in the spent scrubber water; f) carbon particulates
contain no detectable levels of any type of hydrocarbon and
the mass of these particulates was less than 0.5% of the carbon
in the herbicide; g) carbon dioxide, carbon monoxide, and heat
of combustion gases are not environmentally significant; and
h) dispersions of scrubbed effluent gases into the atmosphere
have no effect on tomato plant bioassays and attest to the lack
of phytotoxicity of the gases.
12.

INCINERATION IN THE CONTINENTAL UNITED STATES (CONUS)
ROCKY MOUNTAIN ARSENAL, COLORADO
An incineration system has been constructed, installed,

and operated at the U. S. Army Rocky Mountain Arsenel (RMA) in
Colorado which, by technical investigation, appears to be
capable of incinerating the Orange in an environmentally safe
manner.

The RMA incinerator is used to destroy mustard

agent and many of the problems associated with the incineration
of mustard and Orange are similar.

The problems arise from

the similarity between mustard and Orange as regards certain
physical and chemical properties and environmental impact.
These problems include:

fuel conditioning, high

temperature

incineration, acceptable effluents, real time monitoring and
24

�drum disposal.

The problems are handled at RMA; but, the

facility is necessarily of considerable value, and the waste
feed rate of ^2 gallons per minute (gpm) requires considerable
time to incinerate a given quantity of material.

The informa-

tion below regarding the RMA facility has not been reviewed
by the U. S. Army, nor has any action been taken to contract
the RMA facility for Orange incineration.

Incineration

of

2,3 million gallons would require approximately 27 months.
The RMA system can operate at &gt;2,000°F with a stay time of 2-6
seconds.

Although no actual Orange incineration data is

available, it is felt that such operating conditions will
adequately destroy the herbicide and TCDD.

In addition a

caustic scrubber installed on the system will provide additional
treatment of the combustion gas.

The elimination of the liquid

discharge, the slow rate of incineration, the cumbustion gas
treatment, the monitoring systems installed, and the drum
cleaning capability make this option extremely attractive.
Based on technical and environmental considerations,
incineration in the CONUS in units such as the RMA facility
could be safely accomplished.

Unfortunately incineration

units of sufficient capacity are located near centers of
populationsand industry, and these areas are already marginally
acceptable from a polution viewpoint because of presently
occurring degrees of air pollution.

Furthermore, local and

state governments are generally opposed to the importation
waste for disposal within their areas of jurisdiction.
25

For

of

�1

*

the above reasons, incineration in the CONUS is not considered
a viable alternative.
13.

REPROCESSING
Repro"ce~i&gt;i&gt;-in"g"~ of Herbicide Orange would convert it

into commercial products (n-butyl esters of 2,4-D and 2,4,5-T)
containing acceptable levels of TCDD.

The process would

differentially destroy the TCDD or concentrate it into a readily
disposable waste.

To date (September 1975) three chemical

companies have submitted process descriptions in support of
bids to reprocess the herbicide.

The basic processes proposed

all basically attempt to selectively separate the valuable
components of Herbicide Orange from the TCDD contaminant.
Classical chemical methods, i.e., solvent extraction,
distillation or absorption, would be employed to concentrate
the TCDD.

The TCDD impurity would then be disposed of by

incineration.

The process descriptions have been evaluated by

EPA and the Army Environmental Hygene Agency.

The processes

appear promising with respect to 2,4-D and 2,4,5-T recovery as
well as satisfactory destruction of the dioxin contaminant.
However, sufficient processing questions have been raised (e.g.,
disposal of dioxin wastes and in-process destruction) to warrant
a mandate for pilot studies (up to 150 gallon capacity).

The

objectives of the pilot study would include: (1) confirmation
of process claims, (2) determination of impact of scale-up
unit on process efficiencies, (3) evaluation of dioxin
destruction and disposal, (4) estimation of possible dioxin
contamination of the environment.

-26-

�The Scientific Advisory Board's Ad hoc Committee on
Disposal of Herbicide Orange met for a final assessment of
all research data and a discussion of options in March

1974.

Rough estimates for the cost of each major viable option were
presented.
TREATMENT

ESTIMATED COST
($ MillionT"

Complete Incineration

3.657

Complete Biodegradation

2.235

Fractionation and Incineration

4.031

Fractionation and Biodegradation

2.754

Complete Chlorinolysis

11.462

Fractionation and Chlorinolysis

9.033

Reprocessing/Hemogenous Mixing/Sale

2.153

Although these data suggested that the reprocessing option
was most viable, there were no assurances given by EPA that once
selected, registration of appropriate inventory would follow.
The use option (as Orange Herbicide) was not considered in
the final analysis for two reasons

(3.) no registration existed

for the n-butyl ester of 2,4-D and 2,4,5-T and (2) the market
for a n-butyl ester formulation was thought to be minimal.
Moreover, field tests with Orange Herbicide in western Oregon
in 1973 drew an unusually and controversial reaction from the
public.

Newspapers in the area (and throughout the Country)

generally carried a very derogitory view of the use of this
chemical (as Orange) in reforestation programs.
Biodegradation of the herbicide in an isolated area in
27

�western Utah appeared feasible.

However, newspaper coverage in

the Fall of 1973, also made this option "politically" sensitive.
The suggestion in the newspapers that the Air Force was seeking a
site to "dump" 2.3 million gallons of toxic surplus herbicide
from Vietnam made the selection of an appropriate location
impossible.

For similar reasons, the incineration of Orange

within the Continental United States (CONUS) appeared unrealistic.
The obvious option was considered to be incineration outside
the CONUS.

Since some of the European Countries had used

specially designed ships for incineration at sea, this option
was considered the "most likely to succeed".

As a consequence,

the Environmental Health Laboratory at Kelly AFB, Texas, was
tasked with preparing an environmental impact statement for the
incineration of Herbicide Orange.

The final statement

"Disposition of Orange Herbicide by Incineration" was released
in November 1974.
Destruction of Herbicide Orange is pending final evaluation
of reprocessing and a review of the status of 2,4,5-T Herbicide
by the Environmental Protection Agency.

If the latter two actions

are negative, then the Air Force will seek a permit for ocean
incineration of Orange.

Destruction of the herbicide by

incineration could begin in the Spring of 1976.
It is ironic that such large quantity of herbicide, so
widely used in the United States, and so critical in World
Agriculture, will be destroyed because it was used in a highly
controversial military conflict.

When given the option of

whether to use it for the benefit of mankind or destroy it as
28

�a symbol of protest against war and the abuse of our environment,
the American public has choosen the latter.

29

�</text>
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                  <text>&lt;p style="margin-top: -1em; line-height: 1.2em;"&gt;The Alvin L. Young Collection on Agent Orange comprises 120 linear feet and spans the late 1800s to 2005; however, the bulk of the coverage is from the 1960s to the 1980s and there are many undated items. The collection was donated to Special Collections of the National Agricultural Library in 1985 by Dr. Alvin L. Young (1942- ). Dr. Young developed the collection as he conducted extensive research on the military defoliant Agent Orange. The collection is in good condition and includes letters, memoranda, books, reports, press releases, journal and newspaper clippings, field logs and notebooks, newsletters, maps, booklets and pamphlets, photographs, memorabilia, and audiotapes of an interview with Dr. Young.&lt;/p&gt;&#13;
&lt;p&gt;For more about this collection, &lt;a href="/exhibits/speccoll/exhibits/show/alvin-l--young-collection-on-a"&gt;view the Agent Orange Exhibit.&lt;/a&gt;&lt;/p&gt;</text>
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                <text>Typescript: Dilemma for Disposal of Herbicide Orange</text>
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                  <text>&lt;p style="margin-top: -1em; line-height: 1.2em;"&gt;The Alvin L. Young Collection on Agent Orange comprises 120 linear feet and spans the late 1800s to 2005; however, the bulk of the coverage is from the 1960s to the 1980s and there are many undated items. The collection was donated to Special Collections of the National Agricultural Library in 1985 by Dr. Alvin L. Young (1942- ). Dr. Young developed the collection as he conducted extensive research on the military defoliant Agent Orange. The collection is in good condition and includes letters, memoranda, books, reports, press releases, journal and newspaper clippings, field logs and notebooks, newsletters, maps, booklets and pamphlets, photographs, memorabilia, and audiotapes of an interview with Dr. Young.&lt;/p&gt;&#13;
&lt;p&gt;For more about this collection, &lt;a href="/exhibits/speccoll/exhibits/show/alvin-l--young-collection-on-a"&gt;view the Agent Orange Exhibit.&lt;/a&gt;&lt;/p&gt;</text>
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                <text>Young, Alvin L.</text>
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                <text>W. J. Cairney</text>
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                <text>Typescript: The Ecological Consequences of Massive Quantities of 2,4 -D and 2,4,5 -T Herbicides: Summary of a Five Year Field Study</text>
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