Air & Waste

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Treatment of Pesticide-Contaminated Soils with

Thermal Desorption Technologies

William L. Troxler , Steven K. Goh & Lynton W.R. Dicks

To cite this article: William L. Troxler , Steven K. Goh & Lynton W.R. Dicks (1993) Treatment
of Pesticide-Contaminated Soils with Thermal Desorption Technologies, Air & Waste, 43:12,
1610-1617, DOI: 10.1080/1073161X.1993.10467230

To link to this article: https://doi.org/10.1080/1073161X.1993.10467230

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 CONTROL TECHNOLOGY
Treatment of Pesticide-Contaminated Soils
with Thermal Desorption Technologies
William L. Troxler and Steven K. Goh
Focus Environmental, Inc.
Knoxville, Tennessee
Both laboratory-scale and full-scale studies have shown that thermal desorption is an effective technology for treating soils
contaminated with a variety of organochlorine pesticides. Soil decontamination results are presented from six full-scale and nine
laboratory, bench and pilot-scale thermal desorption treatability studies. The impacts of several key factors that influence thermal
desorption kinetics, total pesticide removal efficiency, and achievable pesticide residual concentration are discussed. Conclusions are
presented regarding scale-up issues in predicting the performance of full-scale systems from laboratory, bench, or pilot-scale tests.
There are a number of sites on the CERCLA National Priorities
List that are contaminated with organochlorine (OCL) pesticides.
Many of these sites were used for manufacturing, blending, or
distributing agricultural chemicals. Contamination at these sites was
generally caused by leaks, spills, or disposal of residues from the
manufacturing or application processes.
Laboratory, bench, and pilot-scale treatability studies and full-
scale site remediation projects have shown that thermal desorption is
an effective technology for treating soils contaminated with a variety
of OCL pesticides. This paper presents conclusions that have been
drawn by analyzing a database of treatability data from six full-scale
and nine laboratory, bench, or pilot-scale studies on treatment of
pesticide-contaminated soils with thermal desorption technologies.
The studies cited include data both on residual concentrations of
contaminants in the soil after treatment and air emissions parameters.
This paper deals primarily with the capability of thermal desorption
processes to meet soil cleanup objectives, however, a limited amount
of data are presented on air emissions measured during full-scale
projects. The key objectives of this paper are to: (1) summarize results
from full-scale projects and treatability studies; (2) identify the key
parameters affecting the thermal desorption process; (3) summarize
the process operating conditions required for meeting soil cleanup
objectives; and (4) compare pesticide residual concentrations and
removal efficiencies achieved in full scale operations with results
predicted by treatability studies.
Pesticide Characteristics
The primary OCL pesticides addressed in this paper include DDT,
DDD, DDE, toxaphene, lindane, chlordane, aldrin, dieldrin, isodrin,
and endrin. These pesticides were selected for analysis from a much
larger group of compounds. Compounds addressed in this summary
were chosen because they have one or more of the following
characteristics: (1) they are regulated as Resource Conservation and
Recovery Act (RCRA) toxicity characteristic contaminants; (2) they
are common contaminants at a number of the sites included in this
study; and/or, (3) they have physical and chemical properties span-
ning the typical range for a larger group of OCL pesticides. A
summary of chemical and physical characteristics for the subject
group of OCL pesticides is presented in Table I. In general, OCL
1610 • December 1993 • Vol. 43 • AIR & WASTE
Lynton W.R. Dicks
Shell Development Company
Houston, Texas
pesticides have very low vapor pressures, typically in the range of 1O5
to KFmm of mercury at ambient temperature. OCL pesticides also
have relatively low boiling points or thermal decomposition tem-
peratures, typically in the range of 300 to 400°F. Because of these
characteristics, OCL pesticides can be removed from soils by thermal
desorption technologies operating at relatively low soil treatment
temperatures.
Thermal Desorption Overview
Thermal desorption is defined as "heating in an enclosed chamber
under either oxidizing or non-oxidizing atmospheres at sufficient
temperature and treatment time to vaporize hazardous contaminants
from contaminated surfaces and surface pores and to remove the
contaminants from the heating chamber in a gaseous exhaust gas." 1
Types of commercially available thermal desorption systems include
rotary dryers, thermal screws, and indirectly-heated calciners. Or-
ganic contaminants in the exhaust gas from the thermal desorber may
be destroyed in a thermal oxidizer, collected by condensation,
adsorbed onto granular activated carbon, or treated by a combination
of these technologies.
Thermal desorbers generally operate at relatively low soil dis-
charge temperatures, typically in the range of 300 to 1,000°F.
However, the upper part of this temperature range exceeds the boiling
points for the OCL pesticides. Pesticide boiling point temperatures
versus potential soil discharge temperatures for several types of
thermal desorption systems are shown in Figure 1.
Operating at relatively low soil discharge temperatures mini-
mizes thermal desorption treatment costs. While treatment costs vary
depending upon the size of the site, reported treatment costs for
thermal desorption systems treating pesticide-contaminated soils are
in the range of $150 to $225 per ton of soil*
Full-Scale Treatment Results
Thermal desorption has been used for remediating pesticide-
contaminated soils at four CERCLA sites in the U.S.2 In addition to
the U.S. experience, two remediation contractors in the Netherlands,
Ecotechniek and NBM, have reported results from the full-scale
Copyright 1993 - Air & Waste Management Association
 treatment of pesticide-contaminated soils with stationary thermal nated soils. Brief case histories for each of these projects are pre-
desorption systems. Table II lists sites where full-scale thermal sented in the following.
desorption systems have been used for treating pesticide-contami-
Old Marsh Aviation Site
The U.S. EPA conducted a Superfund Innovative Technology
Evaluation (SITE) study at the Old Marsh Aviation site in Litchfield
Pestickle Boiling Points or Decomposition Temperatures
Park, Arizona in September 1992. 34 The remediation project was
conducted by Canonie Environmental Services using its low tem-
Endrln perature thermal aeration (LTTA) system. The LTTA consists of a
• materials pretreatment and handling system, rotary dryer, pug mill
4-4'-D0D for cooling treated soils, air pollution control system, and liquid-
4-4'-DDT
phase granular activated carbon system for treating condensed water.
The air pollution control system was a physical/chemical treatment
Chlordana system including dual cyclones, baghouse, wet venturi scrubber, two
Undane vapor-phase granular activated carbon beds in parallel, induced draft
Toxaphene fan, and stack. Organic compounds were volatilized from the soil and
• collected on the activated carbon and disposed of off site. During the
Aldrin
•
SITE demonstration, an LTTA feed rate of 34 to 38 tons per hour of
soil was achieved at a rotary dryer soil discharge temperature of 730
Thermal Dmorher Soil Discharge Temperature Range
op
Approximately 52,000 tons of soil at the site which had been
mwmal Screw (a) contaminated with toxaphene, DDT, DDD, DDE, and other OCL
mm Dryerfcartwnstool) pesticides from a crop spraying operation were treated using the
iwllfoctlyHBatBdOalcliiar ' "j
LTTA system. Average total concentrations of OCL pesticides at the
site were in the range of 200 to 500 mg/kg, however, hot spots were
f T ] identified with total OCL pesticide concentrations as high as 2,500
mg/kg. Pesticide removal efficiencies from soil measured during the
Legend: SITE demonstration test are as follows (in percents):
Boiling Point (sea Table 1)
Decomposition Temperature 4,4'-DDT 99.97 Dieldrin 99.27
Typioal Soil Discharge Temperature Range 4,4'-DDD > 99.97 Toxaphene > 99.83
(a) Hot oil heated
(b) Molten salt heated 4,4'-DDE 90.26 Endosulfan I 99.98
Endrin > 99.85 Endosulfan II 99.34
200 400 600 800 1 ,000 Endrin aldehyde 97.43
Temperature (°F)

The LTTA met the soil cleanup level of 3.52 mg/kg of total DDT
Figure 1. Pesticide thermal properties versus thermal desorber temperature. family compounds (DDT, DDE, DDD) and 1.09 mg/kg of tox-

Table I. Chemical and physical properties of organochlorine pesticides

Vapor

Parameter Service Mo. Formula Weight CD (mm Hi)

4,4'*DDD 72-54-6 WiA 320.0 36S 1.0x10^@30wG

4,4'-D0l 72-554 MA mo Uth 6.5xt(H025*C

M'-ODT 50-29-3 WA 3S4.S 365 @ 0.05 mm Hg 1.5 x 10' @ 20"C

Chlordane 57-74-9 4090 347 0 1 mm H0 1.0 x 10^ % 2S*C

Undane W« 290 3 DfiO,#$5S 9.4xf(H02O*C

Aldrin 300-00-? WA 364.9 293@2rnmHg 6.6x10*@25"C

Dieldrin 60-S7-1 WAP 380.9 N/A 1.8 x tO*7 % 25°C

Endrin 72-20*1 VW 380.9 Dec, @ 473 2 x 10* 0 25°C

Toxaphene 8001-30-2 WA 413.8 0fi0> ® 311 3.3 x 10* 41259C

AIR & WASTE • Vol. 43 • December 1993 • 1611

 CONTROL TECHNOLOGY

Table II. Full-scale pesticide thermal desorption projects.
Contractor S)ts Name/Loeatioii
Canonie Environmental Old Marsh Aviation/
Services, inc. t.itchtield Park, AZ
Williams Environmental! TH Agriculture and Nuitrition/
Services, Inc. Albany, GA
Envirotecn S&S Flying, Marianna, IFt
Envlrotach Malone.FL
Ecotechniek Rozenburg.theNetrierl,ands
aphene. No dioxins were detected in the stack gas, the treated soil, the
liquid condensate, or the granular activated carbon systems during
the demonstration. The analytical detection limit for 2,3,7,8-
tetrachlodibenzo-para-dioxin in the stack gas ranged from < 0.0019
ng/dscm to < 0.0022 ng/dscm. Low concentrations of thermal
degradation products were detected in the scrubber liquor, vapor
phase granular activated carbon beds, and the stack gas. Specific
thermal degradation products that were detected included acetone,
acrylonitrile, benzoic acid, benzyl alcohol, benzaldehyde,
dihydrofuranone, phenol, and methyl phenol. The average emission
rate for compounds detected at quantifiable levels in the stack gas
included 4,4-DDE at 0.000043 lb/hr, chloromethane at 0.020 lb/
hour, benzene at 0.053 lb/hr, toluene at 0.008 lb/hr, acetonitrile at
0.126 lb/hr, and acrylonitrile at 0.078 lb/hr.
T H Agriculture and Nutrition
Williams Environmental Services treated 4,000 tons of pesticide-
contaminated soil at the T H Agriculture and Nutrition site in Albany,
Georgia in 1993.5 The soil was treated with a thermal desorption
system consisting of a materials pretreatment and handling system,
rotary dryer, treated soil cooling auger, air pollution control (APC)
system, and liquid-phase granular activated carbon system for treat-
ing APC system purge water. The air pollution control system was a
physical/chemical treatment system including a baghouse, induced
draft fan, quench, demister, two vapor-phase granular activated
carbon beds in parallel, and a stack. Organic compounds were
volatilized from the soil and collected on the activated carbon and
disposed of off site.
During the performance test for the project, a soil feed rate of 7.2
to 9.5 tons per hour of soil was achieved at a rotary dryer soil
discharge temperature ranging from 833 to l,082°F. Average total
The average removal efficiency for
DDE was skewed by one low value re-
Equipment I corded during the performance test run
with the lowest soil treatment tempera-
Rotary Dryer 3,4 ture. However, data from subsequent full-
scale production operations indicated that
DDE was consistenly removed from soil
Rotary Dryer 0 at an efficiency of greater than 95 per-
cent.
Pesticides in the stack gas were
fmmt>w a sampled using Modified Method 5. Con-
centrations of all fifteen pesticides were
Rotary Dryer 7 below detection levels in the stack gas
during all test runs. Summa canisters
Rotary Dryer 8 were also used to collect stack gas
samples. Summa canisters were analyzed
to determine concentrations of 27 poten-
tial volatile thermal degradation prod-
ucts. Concentrations of 23 of the com-
pounds were below quantitation limits.
Compounds which were detected at low concentrations included
chloromethane (41.3 to 92.5 ppb), chloroethane (11.6 to 21.1 ppb),
methylene chloride (4.1 to 4.6 ppb), and benzene (1.9 ppb).
One composite treated soil sample was analyzed for every two
hundred tons of material processed during production operations.
Figures 2 and 3 illustrate the distribution of residual concentrations
of DDT and toxaphene that were measured during the performance
test and during production operations. Ninety percent of the DDT
samples had residual concentrations of < 0.13 mg/kg and ninety
percent of the toxaphene samples had residual concentrations of < 6.8
mg/kg. The concentration of toxaphene in all treated soil samples was
below analytical detection limits and the concentration of DDT in 75
percent of the treated soil samples was below analytical detection
limits. However, matrix interferences resulted in high detection
limits for the two samples with the highest concentrations of tox-
aphene and one of the two samples with the highest concentrations
of DDT.
S&S Flying/Malone
In 1989, the U.S. EPA awarded a contract to Envirotech to treat
5,500 tons of toxaphene contaminated soil at the S&S Flying site in
Marianna, Florida.6-7 Contamination at the site was caused by dis-
posal of chemical rinsates from mixing vats in the formulation area
100
90
80 • /u
70

concentrations of OCL pesticides at the site were in the range of 400 Cumulative 60
to 500 mg/kg. Average pesticide removal efficiencies from soil Percentage
measured during the four performance test runs are as follows (in of Data
percents): Points 40

30

I
Aldrin > 98.64 4,4'DDD > 98.50 20
Initial DDT Concantratlon
alpha-BHC > 97.85 4,4'DDE 58.76 170 to 212 mg/kg
101
beta-BHC 97.88 4,4'-DDT 99.89
delta-BHC > 98.28 Endosulfan > 99.73 n
0.1 0.2 0.3 0.4 O.B 0.6 0.7 0.8
gamma-BHC > 98.50 Endosulfan II > 98.64 Residual DDT Concentration In Treated Soil (mg/kg)
alpha-Chlordane > 98.50 Endrin > 98.64
gamma-Chlordane > 98.50 Toxaphene > 98.99
Dieldrin > 98.34 Figure 2. Distribution of residual DDT concentration.

1612 • December 1993 • Vol. 43 • AIR & WASTE

 and residues from aircraft spraying systems. After the soil was
remediated at the S&S site, approximately 2,500 tons of waste from 100

a similar site in Malone, Florida was transported to the S&S site and 90
treated. 80
The contaminated soil was treated in a system consisting of a
70
materials pretreatment sub-system, rotary dryer, dual cyclones, after-
burner, venturi scrubber, ID fan, and stack. The rotary dryer was Cumulative 60

operated at a feed rate of 10 tons per hour, soil total treatment time of
30 minutes, and soil discharge temperature of 700°F. The afterburner
Percentage
o f Data
SO
i
was operated at a gas temperature of l,850°F and residence time of
0.6 seconds.
Points 40

30
I
Performance test results indicated that the system removed tox- 20I
aphene from an initial concentration in soil of 634 mg/kg to below the [| Initial Toxaphene Concentration:
101 \ 190 to 2S8 mg/kg
site cleanup level of 1.5 mg/kg, resulting in a removal efficiency of ]
> 99.76 percent. Stack test results from three test runs indicated that n
6 10 IS 20 20 30 3S
average destruction and removal efficiencies of > 99.998 and 99.989
Residual Toxaphene Concentration in Treated Soil Img/kg)
percent were achieved for toxaphene and trichlorobenzene, respec-
tively. An average hydrogen chloride removal efficiency of > 99.5
percent was achieved and average particulate emissions were 0.008 Figure 3. Distribution of residual toxaphene concentration.
gr/dscf corrected to 7 percent oxygen.

Ecotechniek 700

In April of 1991, Ecotechniek conducted a test to treat soils

600
contaminated with aldrin, dieldrin, and endrin with a rotary dryer
system.8 Two tests were conducted at soil discharge temperatures in SOO
/
the range of 1,112 to l,130°F. A summary of treatment results are
presented in the following: 400 /
Bon
Feed Soil Treated Soil Removal Temperature
(oR 300
Concentration Concentration Efficiency /

Pesticide (mg/kg) (mg/kg) (percent) 200

h —_y
Aldrin 44-70 <2.0 >95.45-98.82 / A - Total Treatment Tlma
Dieldrin 130-20 <2.0 >98.46-99.78 / B • Tlma at Temperature

Endrin 450-20 <2.0 >99.56-99.61 0 i i > i i i i i i i

C O.1 0.2 0.3 0.4 OB 0.6 0.7 0.8 O.S 1 11

Fraction of Solids Residence Time
NBM
In September of 1991, NBM conducted a thermal desorption test
on soils contaminated with aldrin, dieldrin, endrin and lindane.9 The Figure 4. Soil treatment time/temperature curve.
soils were treated in an indirectly heated calciner operated at a soil
discharge temperature of 1,242°F. Concentrations of pesticides in the achieved by full-scale equipment. The types of treatability test
untreated and treated soils and pesticide removal efficiencies were as equipment that have been most commonly used for thermal desorp-
follows: tion studies are: (1) thermogravimetric analyzers, (2) static quartz
Feed Soil Treated Soil Removal tube furnace; (3) static tray, and (4) rotary tube apparatus (RTA). A
Concentration Concentration Efficiency brief description of each of the three major types of treatability test
Pesticide (mg/kg) (mg/kg) (percent) equipment is presented in the following.

Aldrin 34 <0.01 >99.97 Thermogravimetric Analyzers

Dieldrin 88 <0.01 >99.98 Thermogravimetric analyzers consist of a weighing mechanism
Endrin 710 <0.01 >99.99 mounted inside of furnace. The data from the device are reported as
Lindane 1.8 <0.01 >99.44 weight loss from a sample versus treatment time. Thermogravimetric
analyzers can therefore be used to develop kinetic data for thermal
Treatability Test Equipment desorption applications. However, they require that samples contain
Treatability tests are commonly used to determine the soil dis- relatively high concentrations of contaminants in order to produce
charge temperature and treatment time requirements to achieve discernible weight losses.
target residual pesticide concentrations. Treatment protocols may
report the soil treatment time either as the "total treatment time" that Quartz Tube Furnace
the soil sample is in the thermal device or the "time at temperature" A quartz tube furnace consists of a small quartz tube (typically 1
that the soil sample is at or above the target test temperature. Figure inch in diameter by 6 inches long) which is enclosed in an electrically
4 presents a typical time/temperature curve for a thermal desorption heated furnace. The tube may be oriented either vertically or horizon-
treatability test that demonstrates how "total treatment time" and tally. The tube is packed with a soil sample, which may be supported
"time at temperature" are measured. on a glass frit or may be contained by plugging each end of the tube
An objective of a well designed treatability test is to yield data that with glass wool. The test is then initiated by purging the tube with a
can be scaled up to predict residual concentrations which can be preheated sweep gas. The soil sample is analyzed before and after the

AIR & WASTE • Vol. 43 • December 1993 • 1613

 CONTROL TECHNOLOGY
test to determine the removal efficiency for the test organic com-
pounds. The exhaust gas from the tube furnace may also be sampled
to obtain kinetic data to indicate the rate at which organic contami-
nants are desorbed.
Static Tray
Static tray tests are conducted by heating shallow trays of con-
taminated soil in a muffle furnace to a setpoint soil temperature.
Analytical data from the feed soil and the treated soil are compared
to evaluate if thermal desorption can meet treatment objectives.
Static tray tests are relatively inexpensive to conduct. Therefore, they
are commonly used as screening tests to identify optimum soil
treatment temperature and total treatment time or time at temperature
conditions before conducting bench or pilot-scale tests.
Rotary Tube Apparatus
There are several organizations that provide bench-scale RTA
testing equipment (Hazen Research, Golden, CO; IT Corporation,
Knoxville, TN; Clemson Technical Center, Clemson, SC) Typical
test equipment consists of an indirectly heated rotating metal cylinder
and air pollution control equipment. Bench-scale systems generally
operate in a batch mode while larger pilot scale equipment typically
operates in a continuous mode. A diagram of a typical RTA is
presented as Figure 5.
Bench-scale tests are normally conducted in a batch mode by
partially filling the cylinder with contaminated soil at the beginning
of the test. The cylinder is heated indirectly and the temperature of the
soil is monitored and controlled to achieve a target soil temperature
and treatment time at temperature. In pilot scale equipment, continu-
ous feed systems are used and the cylinder rotation speed and slope
are used to control the soil temperature. The soil temperature is
controlled by adjusting the heat input to the system, which may be
supplied by electrical heating elements or by a natural gas or propane
burner.
Air pollution control equipment is usually configured for the
particular application, and may include afterburners, particulate
filters, water-filled impingers, wet scrubbers, and activated carbon
adsorption systems. Gas sampling systems may also be used to
sample exit gases from the process.
Treatability Study Case Histories
Laboratory and bench-scale treatability studies that have been
performed on pesticide contaminated soils are listed in Table III. A
brief discussion of selected tests, testing methods, cleanup goals, and
reported pesticide removal efficiencies from soils is presented in the
following.
BACK PURGE GAS
.FRONT PURGE GAS
SOIL
TEMPERATURE
ELECTRIC FURNACE
"b?7?»gyxp7?yyr
J?
THERMOCOUPLE
Figure 5. Schematic of rotary tube apparatus test equipment.
1614 • December 1993 • Vol. 43 • AIR & WASTE
Old Marsh Aviation
Canonie performed bench-scale treatability testing on soils from
the Old Marsh Aviation site using an RTA followed by a series of
condensers and an activated carbon adsorption system.10 The objec-
tives of the test were to determine if the use of the full-scale system
was technically feasible for the application and to determine required
operating parameters. Six tests were conducted with 1,500 gram
samples of soil. Each test was conducted at a soil total treatment time
of eight minutes and a cylinder rotational speed of six rpm. One test
per temperature condition was conducted at soil temperatures of 500,
550, and 600°F. Three tests were conducted at a soil temperature of
650°F. The average total concentration of the eight OCL pesticides
in the feed sample was 2,404 mg/kg. Toxaphene and DDT were the
major contaminants, with average concentrations of 1,505 and 272
mg/kg respectively. The test results showed that at soil temperatures
in the range of 600 to 650°F, residual concentrations of all eight OCL
pesticides were < 0.33 mg/kg per compound.
Woolfolk Chemical Works
Canonie performed a bench-scale treatability test on OCL pesti-
cide contaminated soils from the Woolfolk Chemical Works facil-
ity.11 The bench-scale test equipment consisted of an RTA, a six-
micron pot filter, two stainless-steel condensers, and a granular
activated carbon adsorption system. The rotary tube was electrically
heated and had a variable speed drive. Tests were conducted with
1,500 gram batches of soil treated at temperatures of 650 and 750°F.
The RTA was preheated to a temperature approximately 50°F higher
than the target soil test temperature for each run. This higher initial
temperature was used to accommodate the drop in dryer temperature
when soil, at ambient temperature, was poured into the preheated
dryer. Each test was run at a soil total treatment time of 12 minutes
and drum rotation speed of 4 revolutions per minute (rpm).
Pesticide removal efficiencies for individual compounds ranged
from > 87.1 to > 99.5 percent for the test performed at a soil
temperatures of 650°F. For the 750°F soil temperature test, pesticide
removal efficiencies ranged from > 98.7 to > 99.9 percent. At 750°F,
the concentrations of all pesticides except endosulfan I were below
detection limits in the treated soil. Analysis of the liquid condensate
determined that many of the pesticides were present, indicating that
some function of the desorbed pesticides were captured in the
scrubber water.
T H Agriculture and Nutrition
Williams Environmental Services, Inc. performed a static tray
treatability test on OCL pesticide-contaminated soil from the T H
Agriculture & Nutrition Company, Inc. (THAN) property in Albany,
Georgia.12 The test equipment included a muffle furnace with
firebrick-lined interior, temperature controller, and 1,750 watt elec-
trical heating system. A series of 100 gram samples of contaminated
soil were heated for periods of 36 or 51 minutes to achieve soil
treatment temperatures of 500, 700, and 900°F. The soil time at
temperature was 6 minutes for all tests.
The site target cleanup level for this project was 90 percent total
removal efficiency from soil for fifteen specific OCL pesticides.
Measured total pesticide removal efficiencies from soil for the fifteen
OCL pesticides are presented in the following:
Test
Soil Treatment Time
Temperature 36 51
Minutes (percent) Minutes (percent)
500 >86.85 >90.28
700 >99.89 >99.90
900 >99.91 >99.91
 These data indicate that the optimum soil treatment conditions
were 700°F and 36 minutes total treatment time. This set of treatment
conditions resulted in significantly higher pesticide removal efficien- Total Soil Treatment
cies than the two tests conducted at 500°F. In contrast, the two tests Time s 3(8 Minutes
conducted at a soil treatment temperature of 900°F exhibited only too
slightly higher removal efficiencies than the tests conducted at 700
120
°F. A summary of treatment data for the DDT family of compounds
(DDT/DDD/DDE) from the 500°F/36 minute test is presented in 100
Figure 6. 80
Residual
Data for the 500°F/36 minute test indicated that all pesticides, Pesticide
(mg/kg) 80
except for DDE, were removed from soil at greater than 90 percent Z.
efficiency. The concentration of DDE in the treated soil was approxi- \Y. Y. .,..' /DDPT
mately 4 times higher than the concentration in the untreated soil. DDD
DDT has been reported to undergo dehydrochlorination at tempera-
tures above the melting point to form DDE.19 Since DDT is the major UNTREATED 800 700 900
contaminant at the site, this reaction would explain the increase in 8oN Treatment Tamperature (°F)
DDE concentration after treatment at the 500°F temperature. How-
ever, results from the 700°F/36 minute test show that DDE is readily
removed from soil at > 99 percent efficiency for this set of conditions. Figure 6. DDT compound family tray test data.

Rocky Mountain Arsenal/Shell percent organic carbon, 22 percent sand, 57 percent silt, 21 percent
Shell Development Company conducted a series of laboratory- clay), and "Houston soil" (1.4 percent organic carbon, 9 percent sand,
scale treatability studies in 1989 to evaluate the potential use of 38 percent silt, 52 percent clay). Soil samples were spiked with
thermal desorption for treating pesticide-contaminated soils from the lindane to a concentration of 5 percent by weight.
Rocky Mountain Arsenal (RMA) site near Denver, Colorado.13 Test equipment consisted of a thermogravimetric analyzer (Cahn
Testing was conducted at Shell's Westhollow Research Center in balance) which gives a time resolved weight loss as a contaminated
Houston, Texas. soil sample is heated and the organic compounds are stripped by a hot
Three different "model" uncontaminated soil samples were col- gas. Soil samples with a mass of 1.5 grams per sample were
lected from the Houston area which exhibited a range of properties, suspended in a vial in an enclosed heating system. Rapid heating of
including variations in organic carbon content, clay content, and silt the sample to the target temperature level was achieved by closing a
content. The model soils consisted of sand, "Norwood soil" (0.9 moveable cylindrical furnace around the glass sample enclosure. Gas
temperature was monitored above and be-
Table III. Laboratory and bench-scale thermal desorption studies. low the sample. Hot air was used as the
stripping medium at a flow rate of 2 liters
Test per minute. Experiments were carried out at
desorption temperatures of 212,392,572,
and 752"f.
Canonie Environmental Rotary tube 10 The results of the 392°F desorption test
Litchfield Park, AZ are presented in Figure 7. Test results indi-
cated that approximately 95 percent of the
Canonie Environmental Woolfolk Chemical Works/ 11 lindane was removed from the sand sample
Services, Inc/Hazen Research Fort Valley, GA
at a total treatment time of approximately
33 minutes. Lindane desorption kinetics
Williams Environmental 7 H Agriculture and Nutrition/ Static tray 12
were much slower for the other two soil
Services, Inu. Albany, 6A
samples, with lindane desorption rate de-
Shell Development Company Rocky Mountain Arsenal 13 creasing as a function of the clay content of
Denver, CO furnace the soil. Clay type soils have much lower
permeabilities than sand, which would tend
MKE-Shell/ 14 to decrease the rate of diffusion of organics
IT Corporation Denver, CO out of the soil matrix. Clay soils also have a
higher surface area per unit mass than sand.
Roy K Weston/ 15 '1 tie high surface area to mass ratio appar-
IT Corporation Denver, CO Rotary tube ently enhances the degree of adsorption of
the pesticides to the soil particles, thereby
decreasing desorption rates.
16
Rocky Mountain Arsenal/MKE
Arlington, TN A series of RTA test runs were per-
formed by IT Corporation for MK-Envi-
Delft University Quartz tube 17 ronmental Services and Shell Development
furnace Company in 1990 on soil samples from the
RMA.14 The tests were performed at soil
Delft University 18 largettemperaturesof572,842,andl,202°F
and soil time at temperatures of 15,30, and

AIR & WASTE • Vol. 43 • December 1993 • 1615

 CONTROL TECHNOLOGY

6
Mixed Basin Soils

g
y Norwood ( 2 1 % clay)
z
Simple 4 160
/ ^ ^ ^ Houston (52% clay)
Weight
140
Loss ,
(%) 3 120
Residual 100
Aldrin
2 (mg/kg) 80
60
7
0.47
1 40
I/y Desorption Temperature - 392 ° F
20 L ^../L..m... (a)
0 Time at
Temperature
0 (a) / (a) /
(minutes)
C> 10 20 30 40 BO 60 70 340 422 642 622
Total Treatment Time (minutes) 8oH Treatment Temperature (*F)
(a) Condition not tasted

Figure 7. Lindane desorption rate versus soil type.

Figure 9. Aldrin tray test data.
Mlx8el B8>ln So
S^r-—&. "» overall pesticide removal efficiency. Various combinations of these
^V Tray Test Data
two factors can produce the same residual concentrations of the target
pesticides.
A total of 22 RTA tests were conducted on four soil matrices. The
Pesticide
Removal
RTA runs were performed using soil temperatures of 392,482,572,
Efficiency 39 662,and 752°F, with soil treatment times at temperature of 5,10,15,
(%) \ 20, and 30 minutes. The treatability data indicated that soil treatment
temperatures of 482 to 572°F were sufficient to achieve the target
• Aldrin + Isodrin \
cleanup levels for the site. The data also indicated that soil treatment
temperatures of 662 to 752°F resulted in removal of pesticides to non-
* Dieldrin D Endrin Soil Treatment Time at
Temperature - 10 Minutes
detectable levels in the treated soil. DDE was concluded to be the
i i
most difficult compound to remove from the soil, presumably
200 300 4t)0 S00
because it is a thermal decomposition product of DDT.
Soil Treatment Temperature (' F)

Arlington Blending and Packaging/Ebasco

Figure 8. Pesticide removal efficiency versus soil temperature.
60 minutes. Soil with initial aldrin, dieldrin, and endrin concentra-
tions of 395,160, and 225 mg/kg respectively were treated to non-
detectable levels at each set of treatment conditions. Analytical
detection levels varied from 0.008 to 0.032 mg/kg.
Rocky Mountain Arsenal/Weston
A series of static tray and RTA treatability tests were performed
by IT Corporation for Roy F. Weston on soil samples from the
RMA.15 Tests were conducted on four different soil matrices. Twenty
static tray tests were conducted on two soil matrices to establish
optimum soil treatment time and time at temperature conditions for
a series of RTA tests. Static tray tests were conducted at soil treatment
temperatures of 340,422,542, and 622°F and soil times at tempera-
ture of 0, 5,10, and 20 minutes. The static tray test samples were
analyzed for aldrin, endrin, isodrin, and dieldrin.
Desorption data for dieldrin, aldrin, endrin, and isodrin at the soil
treatment test temperatures are shown in Figure 8. Data are presented
for tests conducted with mixed basin soils at a soil treatment time at
temperature of 10 minutes. The data for these four compounds
indicate there is a lower temperature limit of approximately 340°F
below which very little desorption takes place. At temperatures in the
range of 340 to 542°F, desorption occurs relatively rapidly.
An example set of tray test data for aldrin is presented in Figure
9. Similar pesticide removal efficiency patterns were noted for the
other three pesticides. The data in Figure 9 indicate that both
treatment time and time at temperature have significant effects on the
A series of RTA tests were performed by Chemical Waste
Management for Ebasco Services on soils from the Arlington Blend-
ing and Packaging site, a former pesticide formulation operation.16
The RTA unit consisted of an indirectly heated rotary dryer with a 48
inch long heated cylinder with an inside diameter of 4 inches. The
RTA was purged with nitrogen gas during the test. Two tests were
conducted at a soil treatment temperature of 900°F and one test was
conducted at a soil treatment temperature of 800°F. A soil total
treatment time of 85 minutes was used during all tests. The concen-
tration of chlordane was reduced from 4,520 mg/kg in the untreated
soil to 3.4 mg/kg in the treated soil (99.9 percent removal efficiency).
The concentration of pentachlorophenol was reduced from 19 mg/kg
in the untreated soil to < 0.63 mg/kg in the treated soil (> 96.7 percent
removal efficiency).
Delft University
Researchers at Delft University in the Netherlands conducted
fundamental thermal desorption research on the removal of aldrin,
dieldrin, and lindane from three types of contaminated soils.17 Tests
were conducted in a quartz tube furnace at a soil total treatment time
of 30 minutes. Tests were conducted with a dune sand, humic sand,
and peat-clay mixture. Each soil was spiked with 1,800 mg/kg of the
test compound. The objective of the test was to determine the soil
temperature required to meet the Netherlands cleanup standard of 0.1
mg/kg for each of the three pesticides. The study concluded that the
minimum soil treatment temperature required depended on the soil
type, with higher temperatures required as the humic content of the
soil increased. The researchers concluded that adsorption of pesti

1616 • December 1993 • Vol. 43 • AIR & WASTE

 of treatment temperature on the removal efficiency of lindane from
Sandy Soil sandy soil is shown in Figure 10. The percentage of lindane removed
Quart* Tube
Furnace Data from the soil after 30 minutes exposure at the target test temperature
is plotted versus various soil treatment temperatures.
Tests indicated that the soil type had a major effect on the residual
Lindane
lindane concentration. At a treatment temperature of 752°F, the
Removal concentration of lindane in the sandy soil was reduced to 0.1 mg/kg.
Efficiently
(%) 99.9
At similar treatment conditions, the concentration of lindane in the
clay-peat soil was only reduced to 2.9 mg/kg.

Soil Treatment Time - 30 minutes

Scale-Up of Laboratory, Bench, and Pilot Scale Test Data
A key issue in any laboratory, bench, or pilot-scale study is how
200 300 400 S00 600 700 well the treatment results predict the performance that can be
Soil Treatment Temperature (*F) achieved in a full-scale system. Toxaphene data were used to
compare scale-up results because it is one of the most common
Figure 10. Lindane removal efficiency versus soil temperature. contaminants at several of the sites discussed earlier. Thermal
desorption data for toxaphene from several full-scale studies are
summarized in Table IV. Toxaphene thermal desorption data from
cides onto organic material plays a role in the increased temperature
several bench-scale studies are summarized in Table V.
requirements to remove pesticides from soils with high humic
Full-scale data in Table IV was available from systems operating
contents. A summary of the soil temperatures required to meet the 0.1
at soil treatment temperatures in the range of 600 to 750°F and with
mg/kg cleanup objectives for each soil matrix is presented in the
initial concentrations of toxaphene in soil of 18 to 760 mg/kg. Bench-
following:
scale data from Table V were selected for comparison that was
Dune Humic Peat/
collected from tests conducted over the same soil treatment tempera-
Sand Sand Clay
ture range. The bench-scale data were also limited to tests conducted
Pesticides (°F) (°F) (°F)
with soils which had initial toxaphene concentrations of less than 800
Lindane 752 842 >842 mg/kg.
Mdrin662 752 _ Figure 11 compares toxaphene removal efficiencies from soil that
Dieldrin 662 752 were obtained in the bench-scale and full-scale studies, Figure 12
presents a comparison of the residual toxaphene concentrations (mg/
A second study was conducted to evaluate the use of thermal kg) that were obtained in the bench-scale and full-scale studies. Both
desorption for treating lindane contaminated soils.18 Experiments figures indicate that there is a reasonably good agreement between
were carried out with three types of soils: sand, humic sand, and clay- bench-scale and full-scale results. However, bench-scale tests appear
peat. Each soil was contaminated with lindane at concentrations of up to achieve slightly lower residual concentrations and slightly higher
to 2,000 mg/kg. Samples were heated for 5 to 60 minutes in a quartz removal efficiencies than are achieved in full-scale systems. It should
tube furnace at temperatures ranging from 302 to 932°F. The effect be noted that the data in Figure 11 and Figure 12 were collected from

Table IV. Full-scale thermal desorption data for toxaphene.

Feed

N/A
90.17
Old Marsh Aviation 713 35-40 0.3
Old Marsh Aviation 700 3§.4O 1.1
Old Marsh Aviation 700 30-35 270 1.3
Old Marsh Aviation 013 40-45 42

OKI iwafsn Av»uon

OW Marsh Aviation 110 0*31
T H Agr, & Nutrition 1,053 <1,7
THAor,& Nutrition 1,002 <0.17
Williams T H Agr & Nutrition 833
THA0J.& Nutrition 1,034 > 99.32
US Flying 700 10
Malone 700 nth N/A

AIR & WASTE • Vol. 43 • December 1993 • 1617

 CONTROL TECHNOLOGY

several different studies. Differences in other parameters, such as
initial contaminant concentrations, soil total treatment time, soil time
at temperature, initial soil moisture content, soil particle size, and soil
humic content could account for some of the variation between
bench-scale and full-scale results.
Conclusions
(1) The key process parameters affecting the removal efficiency of
pesticides from contaminated soil by thermal desorption are the
soil treatment temperature, the total treatment time, and the
treatment time at temperature. Various combinations of these
parameters can be used to achieve the same residual pesticide
concentration levels.
(2) Data from full-scale applications and treatability tests indicate
thermal desorption can treat the specific OCL pesticides studied
to achieve residual concentrations of 0.1 to 1.0 mg/kg at soil
treatment temperatures in the range of 500 to l,000°F and soil
total treatment times in the range of 8 to 40 minutes.
(3) Pesticide removal efficiencies of greater than 99 percent for
OCL pesticides are achievable at typical thermal desorption
system operating temperature and treatment time conditions.

Toxaphene Toxaphene
Q Bench-scale Data : +
+ Full-Seal* Data
90

+H-
Toxaphene Residual : •
Removal m Toxaphene El B + + +
Efficiency + D + Concentration +
D (mg/kg) D

99.9 1+ v ° D • Bench-saale Data

B
+ Full Scale Data

99.99 ,
600 700 ' 800 680 700 750
Soil Treatment Temperature CF) Soil Treatment Temperature (T)

Figure 11. Comparision of bench-scale versus full-scale data-toxaphene re- Figure 12. Comparision of bench-scale versus full-scale data-toxaphene re-
moval efficiency. moval residual concentration.

Table V. Bench-scale thermal desorption data for toxaphene.

Feed
Soil
perature

Canonie 500 8 1,505 0.333 99.98 12

Canonie 560 8 1,505 0.333 99.98 12
Canonie 600 8 1,505 0.333 99.98 12
Canonie 8 1,505 0,333 99.98 12
Canonie 12 <46 <0.40 -99.13 13
Canonie 12 119 <0.67 > 99.44 13
750 12 <46 <0.08 -99.83 13
750 12 119 < 0.067 > 99.94 13
THAgr. 500 111 0.33 9970 14
THAgr. & Nutrition 500 111 0.34 99.69 14
THAgr. & Nutrition 500 51 111 0.30 99.72 14
THAgr. 500 51 111 0.27 99.76 14
TH Apr. & Nutrition 700 85 <0.17 > 99.80 14
& Nutrition 700 85 <0.17 > 99.80 14
& Nutrition 700 51 85 <0.17 > 99.80 14
T H Agr. & Nutrition 700 51 85 <0.17 > 99.80 14
Williams & Nutrition 52 <0.17 > 99.67 14
THAgr. Nutrition
& 52 <0.17 > 99.67 14
THAgr. & Nutrition 51 52 <0.17 > 99.67 14
& Nutrition 900 51 <0.17 > 99.67 14

1618 • December 1993 • Vol. 43 • AIR & WASTE

 (4) Many of the references cited conclude that DDE is the most
difficult OCL pesticide to remove from soil. DDT decomposes
to DDE at elevated temperatures, resulting in "apparent" low
removal efficiencies for DDE at soil treatment temperatures
below 550°R
(5) Soil characteristics can have a significant effect on pesticide
removal efficiencies from soils at any given set of total treatment
time and temperature conditions. Key soil characteristics in-
clude initial soil moisture content, soil particle size distribution,
and the fraction of humic material.
(6) Evaporating moisture from the feed soil can be the largest
energy requirement in a thermal desorption application. There-
fore, the initial soil moisture content affects the residence time
required to heat the feed material to the target treatment tempera-
ture and has a significant effect on the soil throughput rate that
can be achieved.
(7) Soil particle size characteristics affect mass transfer rates and
adsorption of pesticides to the soil matrix, with soils containing
a large fraction of clay or silt being more difficult to treat than
soils containing a high sand fraction.
(8) Soil humic material content affects removal efficiency of pesti-
cides, most likely because of adsorption of pesticides to the
humic material.
References
1. U.S. EPA, "Thermal Desorption Treatment Engineering Bulletin," EPA/
540/2-91/008, May 1991.
2. J.J. Cudahy, W.L. Troxler, "1991 thermal remediation contractor survey,"
J. Air Waste Manage. Assoc. 42J844 (1992).
3. Canonie Environmental Services, Inc., "Demonstration Bulletin: Low
Temperature Thermal Aeration (LTTA) Process," U.S. EPA SITE Dem-
onstration program, EPA/540/MR-92/008.
4. SCS Engineers, "LTTA Proof-of-Process Oversight - Old Marsh Aviation
Site, Litchfield Park, Arizona," July 7,1992.
5. W.L. Troxler, S.K. Goh, "Performance Test Report for the T H Agriculture
and Nutrition Company Facility, Albany, Georgia," September 1993.
6. R.A. Games, T.F. McGowan, "Superfund Case Study: Test Result and
Project Summary of Pesticide-Contaminated Soil Incineration," paper
presented at HazMat 91 Conference, Atlanta, GA, October 1991.
7. T. Greers, EnviroTech Southeast, Inc., personal communication with
Steven K. Goh, Focus Environmental, Inc., February 12,1993.
8. Ecotechniek, Test Report from April 23-24,1991.
9. NBM, Test Report from September 1991.
10. Canonie Environmental Services, Inc., "Air Quality Permit Application
for Old Marsh Aviation Site Remediation, Litchfield Park, Arizona,"
January 1991.
11. CH2M Hill," Woolfolk Chemical Works Facility Remedial Investigation/
Feasibility Study Report," prepared for the U.S. EPA, July 1992.
12. Williams Environmental Services, "Treatability Study Report for Pesti-
cide Contaminated Soils from T H Agriculture & Nutrition Company, Inc.
property in Albany, GA," submitted to the U.S. EPA Region IV, August
1992.
13. W.F. Farmayan, L.W.R. Dicks, LA. Rhodes, "1989 Laboratory Thermal
Desorption Studies on RMA Basin Sediments and Contaminated Soils,"
West Hollow Research Center Technical Progress Report RMA 2-89,
August 1989.
14. IT Corporation, "Final Report for Morrison Knudsen Environmental
Services - Rocky Mountain Arsenal Basin F Thermal Desorption Studies,"
August 29,1990.
15. Roy F. Weston, "Final Treatability Test Report - Bench-Scale Studies for
Rocky Mountain Arsenal Soils," Contract No. DAAA 15-88-D-0023,
prepared for the U.S. Army Program Manager for Rocky Mountain
Arsenal Contamination Cleanup, November 1992.
16. Chemical Waste Management, Inc., "X*TRAX Laboratory Treatability
Study of Arlington Blending and Packaging Superfund Site, Arlington,
Tennessee" prepared for Ebasco Services Inc., May 23,1991.
17. E.W.B. De Leer, et. al. "The Thermal Cleaning of Soils Contaminated with
Organochlorine Compounds," paper presented at the 2nd International
Conference on Environmental Contamination, Amsterdam, The Nether-
lands, September 1986.
18. C. Borkent-Verhage, C. Cheng, L. de Galan, E.W.B. de Leer, "Thermal
Cleaning of Soil Contaminated with Hexachlorocyclohexane," in Con-
taminated Soil, J.W. Assink, WJ. van den Brink, Eds., Martinus Nijhoff
Publishers, Dordrecht, The Netherlands, 1986.
19. "The Agrochemicals Handbook," Third Edition, Royal Society of
Chemistry, Cambridge, England, 1991.
About the Authors
W.L. Troxler is a senior consultant with Focus Environmental,
Inc., 9050 Executive Park Drive, Suite A-202, Knoxville, TN 37923.
He is primarily responsible for projects that involve thermal
treatment of materials at Superfund sites, including treatability
studies, remedial designs, and project management. S.K. Goh is a
project engineer with Focus Environmental. LW.R. Dicks is a staff
research chemist at the Shell Development Company, Westhollow
Research Center, P.O. Box 1380, Houston, TX 77251-1380. He is
primarily responsible for evaluating applications of various types
of technologies to remedial action projects. This manuscript was
submitted for peer review on April 28,1993. The revised manu-
script was received on October 28,1993.

Air Pollution Engineering Manual

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For thirty years, environmental professionals have used this book as the definitive standard reference
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AIR & WASTE • Vol. 43 • December 1993 • 1619