EPA/540/2-89/045
SUPERFUNDTREATABILITY
CLEARINGHOUSE
Document Reference:
McDevitt, N., J. Noland, and P. Marks. "Contract DAAK 11-85-C-0007 (Task Order 4)
Bench Scale Investigation of Volatile Organic Compounds (VOC's) from Soil."
Technical Report AMXTH-TE-CR-86092 prepared by Roy F. Weston, Inc.,
for USATHAMA (U.S. Army). 120pp. January 1987.
EPA LIBRARY NUMBER:
Superfund Treatability Clearinghouse -FCMK
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SUPERFUND TREATABILITY CLEARINGHOUSE ABSTRACT
Treatment Process: Physical/Chemical - Low Temperature Stripping
Media: Soil/Generic
Document Reference: McDevitt, N., J. Noland, and P. Marks. "Contract
DAAK 11-85-C-0007 (Task Order 4) Bench Scale
Investigation of Volatile Organic Compounds (VOC's)
from Soil." Technical Report AMXTH-TE-CR-86092
prepared by Roy F. Weston, Inc., for USATHAMA (U.S.
Army). 120 pp. January 1987.
Document Type: Contractor/Vendor Treatability Study
Contact: Eric Kaufman
U.S. DOD/USATHAMA
Aberdeen Proving Ground, MD 21009
301-671-2270
Site Name: Letterkenny Army Depot (NPL - Federal facility)
Location of Test: Chambersburg, PA
BACKGROUND; The U.S. Army is investigating technologies to effectively
treat soil contaminated by organic compounds. Low temperature thermal
stripping is one alternative which couples two mechanisms: a) removal by
volatilization and b) removal by aeration. Two individual studies were
conducted to separate the effects of each mechanism. This treatability
study evaluates the effects of aeration on VOC removal efficiency.
OPERATIONAL INFORMATION; Soils at the site are gravelly sand fill, and
native material consisting of sandy clay and sandy silt. Soils contaminated
with VOCs were taken from Area K of Letterkenney Army Depot and is a mixture
of these soils. Average concentration of 1,2 trans dichloroethylene,
trichloroethylene (TCE), and tetrachloroethylene were 115, 222 and 95 ppm,
respectively. Samples of 4.5 liters each were used in the bench-scale
tests. Soils were analyzed for their VOC content and then aerated in a
bench-scale aeration unit. The target residence time was 260 minutes.
Total VOC were analyzed at the aeration unit outlet. In this manner, the
input/output VOC concentration could be determined.
Sampling and analytical techniques are explained for soils, moisture
content, temperatures and other variables in the experiments. QC measures
in the report include explanations of equipment calibration procedures,
analyses of blanks and duplicate samples.
PERFORMANCE: The effect of total VOC concentrations in the soils, air tem-
perature, and soil temperature on the VOC removal efficiency were investi-
gated. Results indicated that VOC removal efficiency is directly
proportional to the total concentration of contaminants in the soil. Table
I shows the results of increasing contaminant concentration on the removal
efficiency of VOCs. The same table shows no correlation between soil bed
temperature and removal efficiency. As the inlet air temperature decreased,
there was an increase in removal efficiency. However, this increase may be
3/89-19 Document Number: FCMK
NOTE: Quality assurance of data may not be appropriate for all uses.
-------
due to the corresponding increase in total VOC contaminant levels. There
appears to be a correlation between the moisture content of the air streams
and the removal efficiency, but the authors suggest additional testing prior
to drawing conclusion from the currently available data.
A conclusion in the report is a comparison of VOC removal efficiencies
associated with aeration element to the thermal element VOC removal effi-
ciencies. The authors claim that the role of aeration in thermal stripping
is minimal (a separate June 86 report is referenced). No data is presented
from the companion report concerning the thermal element VOC removal
efficiencies. The authors also qualify their statement indicating that
their conclusions apply to the conditions evaluated in this study (i.e.,
inlet air temperature, etc.).
CONTAMINANTS:
Analytical data is provided in the treatability study report. The breakdown
of the contaminants by treatability group is:
Treatability Group
W04-Halogenated Aliphatic
Solvents
W07-Heterocyclics and Simple
Aromatics
W13-0ther Organics
CAS Number
127-18-4
156-60-5
79-01-6
1330-20-7
TOT-VAC
Contaminants
Tetrachloroethene
Trans-1,2-dichlorethene
Trichloroethene
Total Xylenes
Total Volatile Organics
TABLE 1
SUMMARY OF OPERATING DATA
Total VOC
Test Concentration
Run I ug/kg
1 647
2 1,538
3 291,940
4 2,256,100
Average
Soil Bed
Temp (F)
105
90
115
102
Average
Inlet
Temp (F)
163
144
148
137
Average Inlet
Air Moisture
Content
(% by vol.)
1.90
2.20
0.80
1.00
VOC
Removal
Efficiency
55
70
81
93
Note: This is a partial listing of data. Refer to the document for more
information.
3/89-19 Document Number: FCMK
NOTE: Quality assurance of data may not be appropriate for all uses.
-------
Installation Restoration General
Environmental Technology
Report No. AMXTH-TE-CR-86092
Contract DAAK 11-85-C-0007 0"ask Order 4)
Bench-Scale Investigation of Air Stripping
of Volatile Organic Compounds (VOC's)
From Soil
Technical Report
January 1987
Prepared for
U.S. ARMY TOXIC AND HAZARDOUS MATERIALS AGENCY
Aberdeen Proving Ground (Edgewood Area), Maryland 21010
Roy F. Weston, Inc.
West Chester
Pennsylvania
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SECURITY CLASSIFICATION of THIS PAGE fir>i«n Dm»»
REPORT DOCUMENTATION PAGE
READ INSTRUCTIONS
BEFORE COMPLETING FORM
1. REPORT NUMBER
AMXTH-TE-CR-86092
2. COVT ACCESSION NO
3. RECIPIENT'S CATALOG NUMBER
4. TITLE r*itf SuMI>'«>
Installation Restoration General Environmental
Technology Development
Task Order 4. Bench Scale Investigation of Air
Stripping of Volatile Organic Compounds (VOC's
from soil _______
S. TYPE OF REPORT * PERIOD COVERED
Final Report
May 1985 to January 198
)«. PERFORMING ORC. REPORT NUMBER
7. AUTHORO)
Nancy P. McDevitt
John W. Noland, P.E.
Peter J. Marks
«. CONTRACT OR GRANT NUMBERO*
B. PERFORMING OMOANIZATION NAME AND ADDRESS
Roy F. Weston, Inc.
Weston Way
West Chester, PA 19380
10. PROGRAM ELEMENT. PROJECT. T
AREA * WORK UNIT NUMBERS
II. CONTROLLING OFFICE NAME AND ADDRESS
U.S. Army Toxic & Hazardous Materials Agency
Aberdeen Proving Ground
Edgewood Area, MD 21010
I*. REPORT DAT!
January 1987
19. NUMBER OF PAGES
I A. MONITORING AGENCY NAME * AOORESSf" tfffemt Inm ControfUntf Office.)
IS. SECURITY CLASS. (»f Otlf neortj
Unclassified i
TUT OECLASSIFICATION/DOWNORAOING
SCHEDULE
U. DISTRIBUTION STATEMENT (»t *!• Jti
Distribution unlimited; approved for public release
17. DISTRIBUTION STATEMENT (of (ft* •••tracr oatonrf te Block SO, II dttturmit tnm
IB. SUPPLEMENTARY NOTES
Contract Project Officer - Ms. Donna L. Koltuniak
(AMXTH-TE-D)
1*. KEY WORDS fContfaMM an ranrM *Uu II a«CMMrr «rf Idmatltr *T Mode o»6orj
Volatile Organic Compounds (VOC's) Porous Plate
Thermal Volatization Low temperature thermal stripping
Aeration Unit
Diffuser Plate
20. ABSTRACT <
t Mtmtltr *T Woe* i
This report presents the results of a benchscale investigation which
evaluated the role of aeration in thermal stripping of volatile organic
compounds (VOC's) from soil.
The project included: Process equipment design, development of a test
plan, bench scale investigation and evaluation of results.
EDITION OF 1 MOV «S IS OBSOLETE
SECURITY CLASSIFICATION OF THtS PACE fWlMn Dmtm gntmnd)
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CONTENTS
Page
Paragraph 1 EXECUTIVE SUMMARY 1
2 INTRODUCTION 4
2 . 1 Background 4
2.2 Purpose of the report 4
2.3 Objectives of the benchscale study.. 4
2.4 Report organization 5
3 TEST SITE 6
3.1 Test site location and
description 6
3.2 Waste characteristics 6
3.3 Site/soil characteristics 9
3.3.1 Site characteristics 9
3.3.2 Soil characteristics 9
4 DESCRIPTION OF THE PROCESS EQUIPMENT.. 13
4 . 1 Aeration unit 13
5 EXPERIMENTAL VARIABLES 15
5.1 Independent variables 15
5.1.1 Feed soil composition/conditions ... 15
5.1.2 Inlet air composition/conditions ... 15
5.2 Control variables 17
5.2.1 Control variables held constant
at all levels 17
5.2.2 Control variables held constant
at various levels 17
5.3 Response variables measured 17
5.3.1 Soil composition/conditions 17
5.3.2 Air composition/conditions 19
6 SAMPLING TECHNIQUES AND ANALYTICAL
METHODS 20
6.1 Field sampling techniques 20
6.1.1 Soil sampling techniques 20
6.1.1.1 VOC's 20
6.1.1.2 Moisture content 23
6.1.1.3 Temperature 23
6.1.1.4 Mass 23
6.1.2 Air sampling techniques 23
6.1.2.1 VOC's 23
6.1.2.2 Moisture content 23
6.1.2.3 Temperature 25
6.1.2.4 Flow rate 25
6.1.2.5 Pressure 25
6.2 Analytical techniques 26
6.2.1 VOC's in soil 28
6.2.1.1 Calibration 28
6.2.1.2 Quality Control 29
6.2.2 Moisture content in soil 29
11
0440B
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CONTENTS
Paragraph 7 PRESENTATION OF DATA 30
7.1 Soil 30
7.2 Air 30
8 ANALYSIS OF RESULTS 43
9 CONCLUSIONS AND RECOMMENDATIONS 47
9.1 Conclusions 47
9.2 Recommendations 47
APPENDICES
A - ORGANIC WASTE CHARACTERISTICS
OF SITE SOILS AT LEAD
(Determined During Preliminary
Investigation) A-l
B - GRAIN SIZE GRADATION CURVES
CORRESPONDING TO FILL SOIL AND
NATIVE SOILS B-l
C - ANALYTICAL METHODS C-l
D - SUPPLEMENTAL DATA D-l
ill
0440B
-------
LIST OF TABLES
TABLE 3-1
3-2
5-1
5-2
6-1
6-2
6-3
7-1
7-2
7-3
7-4
7-5
8-1
8-2
Concentration range of VOC's
determined to be present in Area
K-l (Based on testing performance
10, 11, 12 June 1985) 10
VOC concentrations in excavated soils
from Phase I of the pilot
investigation 11
Summary of test variables for the
aeration unit 16
Schedule of test runs for the
aeration unit 18
Parameters monitored and/or sampled
for in soils 22
Parameters monitored and/or sampled
for in air stream 24
Analytical parameters and
methodologies 27
Summary of major test variables in
soil Test Run 1 32
Summary of major test variables in
soil Test Run 2 33
Summary of major test variables in
soil Test Run 3 34
Summary of major test variables in
soil Test Run 4 35
Summary of major test variables in
air 38
Summary of operating data 44
Summary of moisture content and
removal efficiency as a function
of time (Test Runs 3 and 4) 46
0440B
IV
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LIST OF FIGURES
FIGURE 3-1 General location map of the study area
on the Letterkenny Army Depot,
Franklin County, Pennsylvania 7
3-2 Locations of potential contaminant
sources East Patrol Road Disposal
Area, Letterkenny Army Depot 8
4-1 Schematic of air stripping process
equipment 14
6-1 Aeration unit instrumentation
sampling/analysis 21
7-1 Total VOC removal: Test Run 3 36
7-2 Total VOC removal: Test Run 4 37
7-3 VOC removal rate in the discharge
air stream - Test Run 1 39
7-4 VOC removal rate in the discharge
air stream - Test Run 2 40
7-5 VOC removal rate in the discharge
air stream - Test Run 3 41
7-6 VOC removal rate in the discharge
air stream - Test Run 4 42
0440B
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1. EXECUTIVE SUMMARY
Soils at several U.S. Army Materiel Command (AMC)
installations have been contaminated with a variety of organic
compounds as a result of past solvent handling practices. In
many cases the contaminated soil has resulted in the
degradation of underlying groundwater supplies.
In order to limit contaminant migration, the U.S. Army
Toxic and Hazardous Materials Agency (USATHAMA) is investi-
gating technologies to effectively treat the contaminated soil.
One treatment alternative is low temperature thermal stripping
of volatile organic compounds (VOC's) from soil. The concept of
low temperature thermal stripping essentially couples two
removal mechanisms:
(a) Removal by thermal volatization.
(b) Removal by aeration.
To determine the singular effect of these removal mech-
anisms, two separate studies were conducted at the Letterkenny
Army Depot (LEAD), located in Chambersburg, Pennsylvania. A
pilot study was conducted to evaluate removal by thermal
volatization. During the pilot study, a thermal processor was
used to heat and consequently dry the contaminated soil. The
net effect of heating the soil was to evaporate volatile
contaminants in the soil. In addition to the pilot study, a
separate benchscale study was conducted to evaluate removal by
aeration. The benchscale investigation was conducted simul-
taneously with the pilot investigation. A portion of the soils
excavated for use in the pilot study were used in the bench-
scale investigation. This report presents the results of the
benchscale study conducted during the period from 28 August
1985 to 13 September 1985.
The primary objective of the benchscale investigation was
to determine the role of aeration in thermal stripping.
Secondary objectives included the following:
(a) Determination of the impact of varying design param-
eters (i.e., inlet air pressure, operating tempera-
ture) on system performance (i.e., VOC removal
efficiency).
(b) Evaluation of the feasibility for a pilot-scale
demonstration of the air stripping concept.
0440B
-------
Soils from the site of the two lagoons that were apparently
used for the disposal of organic liquids were chosen for
treatment. This selection was based on the type, variety,
concentration, and volatile nature of the compounds found in
this area. Two types of soil existed at this site: fill soil
and native soil. A grain size analysis indicated that the fill
material consisted of gravelly sands, and the native soil
consisted of sandy clay/sandy silt.
For the benchscale application, an aeration unit was
specially designed and fabricated. A shallow bed of contam-
inated soil was placed on top of the aeration surface. The unit
allowed intimate contact between the air stream and
contaminated soil. The net effect was to aerate the soil,
thereby stripping the VOC's from the contaminated soil.
Four test runs were completed during the benchscale
investigation. Two levels of inlet air pressure and, thus, two
levels of inlet air temperature were evaluated to determine the
effect on VOC removal efficiency: 3 pounds per square inch
(psi) and 5 psi. The resulting inlet air temperatures were
144°F and 137°F for 3 psi and 148°F and 163°F for 5 psi. The
discharge temperatures for each pressure are not the same
because inlet air conditions (i.e., ambient temperature and
moisture content) affect the outlet temperature and were
different on each day of testing.
i
Based on review of the data associated with all test runs,
the following conclusions are presented:
1. VOC removal efficiency is related to total VOC
concentration in feed soils.
2. There is no apparent correlation between the soil bed
temperature and VOC removal efficiency.
3. Inlet air temperature appears to be inversely related
to VOC removal efficiency.
4. There is no apparent correlation between the moisture
content in the inlet air and the VOC removal effi-
ciency .
5. The greatest VOC removal occurs during evaporation of
moisture from the soil.
6. Processed soil moisture content provides an indication
of VOC removal efficiency and possibly processed soil
VOC residuals.
0440B
-------
Comparison of the VOC removal efficiencies associated
with the aeration element and the thermal element
(discussed in a separate report1) indicates that the
role of aeration in thermal stripping is minimal. This
conclusion applies to those conditions evaluated in
this study (i.e., inlet air pressure, inlet air
temperature, inlet air moisture content, ambient air
temperature, and test duration).
'Task 11. Pilot Investigation of Low Temperature Thermal
Stripping of Volatile Organic Compounds (VOC's) From Soil
Report No. AMXTH-TE-CR-86074, June 1986.
0440B
-------
2. INTRODUCTION
2.1 Background. Soils at -several U.S. Army Materiel
Command (AMC) installations have been contaminated with a
variety of organic compounds as a result of past solvent
handling practices. In many cases the contaminated soil has
resulted in the degradation of underlying groundwater supplies.
In order to limit contaminant migration, the U.S. Army
Toxic and Hazardous Materials Agency (USATHAMA) is investi-
gating technologies to effectively treat the contaminated soil.
One treatment alternative is low temperature thermal stripping
of volatile organic compounds (VOC's) from soil. The concept of
low temperature thermal stripping essentially couples two
removal mechanisms:
(a) Removal by thermal volatization.
(b) Removal by aeration.
To determine the singular effect of these removal mech-
anisms, two separate studies were conducted at the Letterkenny
Army Depot (LEAD), located in Chambersburg, Pennsylvania. A
pilot study was conducted to evaluate removal by thermal
volatization. During the pilot study, a thermal processor was
used to heat and consequently dry the
net effect of heating the soil was
contaminants in the soil. In addition
was conducted
investigation
investigation.
separate benchscale study
aeration. The benchscale
taneously with the pilot
excavated for use in the
contaminated soil. The
to evaporate volatile
to the pilot study, a
to evaluate removal by
was conducted simul-
A portion of the soils
pilot study were
used in the
scale investigation. This report presents the results
benchscale study conducted during the period from 28
1985 to 13 September 1985.
bench-
of the
August
2.2 Purpose of the report. The purpose of this report is
to present the results and conclusions of a benchscale
investigation that evaluated the concept of air stripping of
VOC's from soil. A description of test conditions and process
equipment is contained herein.
Objectives of the benchscale study.
2.3
objective of the benchscale investigation
role of aeration in thermal stripping.
included the following:
The primary
was to determine the
Secondary objectives
'Task 11. Pilot Investigation of Low Temperature Thermal
Stripping of Volatile Organic Compounds (VOC's) From Soil,
Report No. AMXTH-TE-CR-86074, June 1986.
0440B
-------
(a) Determination of the impact of varying design param-
eters (i.e., inlet air pressure, operating tempera-
ture) on system performance (i.e., VOC removal
efficiency).
(b) Evaluation of the feasibility for a pilot-scale
demonstration of the air stripping concept.
2.4 Report organization. The information contained in this
report has been organized into 9 sections:
Section Title
1 Executive Summary
2 Introduction
3 Test Site
4 Description of the Process Equipment
5 Experimental Variables
6 Sampling Techniques and Analytical
Methods
7 Presentation of Data
8 Analysis of Results
9 Conclusions and Recommendations
The Appendices provide additional data and analyses:
Appendix Title
A Organic Waste Characteristics of Site
Soils at LEAD (Determined During
Preliminary Investigations)
B Grain Size Gradation Curves Correspond-
ing to Fill Soil and Native Soil
C Analytical Methods
D Supplemental Data
0440B
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3. TEST SITE
3.1 Test site location and description.
investigation was conducted at
(LEAD). LEAD, formerly known as
consists of 7,899 hectares (nearly 20,000
situated in the south-central section of
Franklin County, near the city o£ Chambersburg.
map for the installation is presented in Figure
The benchscale
the Letterkenny Army Depot
Letterkenny Ordnance Depot,
acres) of land
Pennsylvania in
A site location
3-1.
LEAD was established on 7 January 1942 with the mission of
ammunition storage. The present expanded mission of LEAD
includes the receipt, storage, inventory, maintenance, and
demilitarization of ammunition; the overhaul, rebuilding, and
testing of wheeled and tracked vehicles; and the issue and
shipment of Class III chemicals and petroleum.2 Some facility
operations have included cleaning and stripping, plating,
lubrication, demolition, chemical and petroleum transfer and
storage, and washout/deactivation of ammunition.3
Soils excavated from Area K-l were used in the benchscale
investigation (as well as the pilot investigation discussed in
Subsection 2.1). Area K-l is one of seven potential hazardous
waste disposal sites located in the East Patrol Road Disposal
Area (EPRDA). EPRDA is located east of California Avenue, south
and west of East Patrol Road, and north of Building 370. The
location of Area K-l is shown in Figure 3-2.
3.2 Waste characteristics
and quantified
LEAD.4 In addition
zinc, lead, copper,
However, since the benchscale
contaminants were not evaluated
Previous efforts have identified
the contaminants present in the site soils at
to VOC's, concentrations of asbestos,
and cadmium have been found in Area K-l.
study addressed VOC's only, other
and will not be discussed.
2USATHAMA Installation Assessment of Letterkenny Army Depot,
January 1980.
3Battelle, Interim Report, Environmental Contamination Survey
of Letterkenny Army Depot (LEAD), Part 1: Exploratory Phase,
Draft, May 1982.
"Letterkenny Army Depot Remedial Investigation and Feasibility
Study, Report No. DRXTH-AS-CR-83247, February 1984.
0440B
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PENNSYLVANIA
PITTSBURGH
HARHISBUHG \ NJ
* PHILADELPHIA
• ' ' ^(
TO PITTS8U«OH(!^\.
*. M«^SL/ /
SHIPPENSBtjRG
X S S /
LETTERKENNY
xrv. ,--
CHAMB|RS8LIRG
LETTERKENNY
ARMY DEPOT
TOW noun 11.
CNAMMMSMMG
FIGURE 3-1 GENERAL LOCATION MAP OF THE STUDY AREA ON THE
LETTERKENNY ARMY DEPOT, FRANKLIN COUNTY, PENNSYLVANIA
-------
CD
Suspected contamination sources at LEAD
A. Waste disposal trenches
B. Clay-lined oil burning pit
C. Landfill
D. IWTP lagoons
E. Oil burning pit
F. IWTP ditch sludge burial spread
G. Landfill
H. LandfHI
I. Landfill
J. Landfill
K-1. Lagoon
K-2. Partial revetments
K-3. Revetments
K-4. Linear magnetic anomaly
Source Ballelle. December. 1982 (Geophysical Report)
\Y
FIGURE 3-2 LOCATIONS OF POTENTIAL CONTAMINANT SOURCES
EAST PATROL ROAD DISPOSAL AREA, LETTERKENNY ARMY DEPOT
-------
Prior to the pilot study and benchscale investigation, a
field sampling program was conducted on 10, 11, and 12 June
1985. During this program, soil sampling was conducted in Area
K-l. Eleven boreholes were drilled to a depth of 10 feet. Five
composite soil samples per borehole were collected at various
depths. All soil samples were analyzed for those VOC's listed
on the Hazardous Substance List (HSL). A list of the VOC' s
contained on the HSL, as well as their detection limits, is
provided in Appendix A. A list of VOC's determined to have been
present in Area K-l, along with their corresponding concen-
tration range, is also contained in Appendix A. For conven-
ience, the major compounds that were found to be present in
Area K-l are shown, along with maximum and average concen-
trations, in Table 3-1.
The pilot study was conducted simultaneously with the
benchscale investigation and was completed in two phases:
Phase 1-18 test runs; Phase 2-10 test runs. A summary of
the VOC concentrations in the excavated soils used in Phase 1
and Phase 2 is included in Table 3-2. A detailed list of VOC
concentrations for each test run is included in Appendix A.
3.3 Site/soil characteristics.
3.3.1 Site characteristics. Area K-l is the site of two
lagoons that were allegedly used for the disposal of organic
liquids, as evidenced by the high concentrations of organic
contaminants found in the soil. However, excavation operations
indicated that a wide variety of miscellaneous debris was also
deposited at this site. Typically, at a depth of approximately
3 to 5 feet an assortment of miscellaneous objects were
unearthed (i.e., brake drums, wire, bolts, metal washers,
bottles, shell casings, rubble, and trash).
3.3.2 Soil characteristics. The soil series for Area K-l
are classified as Urban Land. According to the Soil Conservation
Service (SCS) of Franklin County, Pennsylvania, urban land is
land that is so altered that identification of soils is not
feasible. This series generally consists of nearly level to
sloping land that has been affected by urban development.
Included in this unit are soils that have been cut and filled
with earth and trash material.
0440B
-------
TABLE 3-1.
CONCENTRATION RANGE OF VOC'S DETERMINED TO BE
PRESENT IN AREA K-l (BASED ON TESTING PERFORMED
ON 10, 11, 12 JUNE 1985)
Volatile
organic
compound
1,2-Trans Dichloroethylene
Trichloroethylene
Tetrachloroethylene
Xylene
Other VOC's
Average
concentration
(ppm)
115
222
95
7
7
Maximum
concent ration
(ppm)
>1,300
>3,500
>3,800
47
600
(i.e., Chlorobenzene,
EthyIbenzene, Methylene
chloride, Toluene, Vinyl
chloride, Cio-allyl Benzene,
Dichlorobenzene, methyl ethyl
benzene, n-propylbenzene,
Trimethyl benzene)
ppm = parts per million
10
0440B
-------
TABLE 3-2. VOC CONCENTRATIONS IN EXCAVATED SOILS FROM
PHASE 1 AND PHASE 2 OF THE PILOT INVESTIGATION
Volatile
organic
compound
Phase 1
1,2-Trans Dichloroethylene
Trlchloroethylene
Tetrachloroethylene
Xylene
Other VOC's
Phase 2
1,2-Trans Dichloroethylene
Trlchloroethylene
Tetrachloroethylene
Xylene
Other VOC's
Average
concentration
(ppm)
252
2,729
745
86
38
18
>146
>94
>62
11
Maximum
concentration
(ppm)
1,200
20,000
4,800
460
270 ,
74
>390
>260
>7, 190
35
0440B
11
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Excavations in Area K-l indicated that a gravelly sandy
silt fill covered the surface to an approximate depth of 2
feet. From 2 to 5 feet below ground surface, miscellaneous fill
material consisting of gray silty clay with sand, gravel, black
ash, and metallic debris was encountered. Native soils varying
from orange brown, sandy, gravelly plastic clays to slightly
plastic clayey silts were generally observed between 5 to 7
feet. In addition, a perched water table was occasionally
observed at the interface of the native soil and fill.
12
0440B
-------
4. DESCRIPTION OF THE PROCESS EQUIPMENT.
4.1 Aeration unit. The aeration unit, evaluated in the
benchscale study is used industrially to aid in the withdrawal
of dry, relatively free flowing material from storage bins and
silos. The unit supplies a low-pressure diffused air surface
which fluidizes a thin layer of material, thereby promoting
flow by gravity.
For the benchscale application, a shallow bed of contami-
nated soil was placed on top of the aeration surface. A
constant flow rate of air was diffused by the surface. The unit
allowed intimate contact between the air stream and contam-
inated soil. The net effect was to aerate the soil, thereby
stripping the VOC's from the contaminated soil.
An illustration of the aeration unit is presented in Figure
4-1. The heart of the aeration unit is an aluminum oxide porous
plate housed in a cast iron casing. The porous plate and
housing measures 15-1/2 inches long by 15-1/2 inches wide by 3
inches thick and results in approximately 150 square inches of
surface area. The casing is flange mounted on the underside of
an open-bottom container. The container walls are approximately
2 feet high and constructed of stainless steel on three sides
and safety glass on the fourth side (to view the soil during
treatment). The container wall constructed of safety glass is
removable for access to the unit (loading, sampling, etc). The
"door" is attached with a series of C-clamps. Originally the
door was to be bolted on; however, the process of removing the
bolts was too time-consuming during soil sampling. The top of
the container has a pitched stainless steel cover with a 2-inch
diameter air discharge pipe.
The diffuser plate casing was fitted with a standard pipe
connection (3/4-inch diameter) to admit process air. The unit
was designed to accommodate 15 dry standard cubic feet per
minute (dscfm) of air at a pressure of up to 5 pounds per
square inch (psi). A low pressure rotary lobe blower supplied
the process air. The air stream was diffused by the porous
plate, passed through a stationary bed of soil (approximately
1-1/2 inches high), exited the unit through the air discharge
line, and, finally, was directed to an afterburner for
conversion of the VOC's to hydrochloric acid, carbon dioxide,
and water vapor.
The afterburner (designed and fabricated primarily for use
in the pilot study that was being conducted simultaneously)
operated at a minimum temperature of 1,000°C (1,832°F) and had
a residence time of greater than two seconds. The afterburner
was propane-fired, using a North American burner rated at 1.5
million British thermal units (Btu) per hour. The afterburner
operated in conjunction with a refractory-lined stack that was
18 inches in diameter and 20 feet high.
13
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To
Afterburner
C-Clamps
Door
(Safety Glass)
Blower
Safety
Valve
FIGURE 4-1 SCHEMATIC OF AIR STRIPPING PROCESS EQUIPMENT
14
-------
5. EXPERIMENTAL VARIABLES
The variables of the benchscale study were classified as
follows:
(a) Independent variables - Those variables impractical to
control and allowed to vary randomly throughout the
tests. No attempts were made to modify or control
independent variables.
(b) Control variables - Those variables with values
selected and maintained during test operations.
(c) Response variables - Those variables with values that
were a function of the selected operating conditions.
Table 5-1 provides a summary of test variables associated
with the aeration unit. A brief discussion of the variables is
included in the following subsections.
5.1 Independent variables. As shown in Table 5-1, there
were two independent variables associated with the benchscale
study. These independent variables were the feed soil
composition/conditions (i.e., VOC concentrations, moisture
content, and temperature) and the inlet air composition/
conditions (i.e., VOC concentrations, moisture content, and
ambient temperature).
5.1.1 Feed soil composition/conditions. One goal of the
benchscale study was to determine the capability of the air
stripping equipment to treat actual contaminated soils.
Therefore, the composition/conditions of the soils in Area K-l
were not altered prior to being introduced to the unit. The VOC
concentration and moisture content of feed soils were a
function of the location and depth of soils excavated for
treatment. The temperature of the feed soils depended on
ambient conditions at the time of the test (soils were stored
in sealed metal containers on the processing pad) .
5.1.2 Inlet air composition/conditions. Various activities
involving the contaminated soils (i.e., sampling, excavation)
took place during the benchscale study. Therefore, the
potential existed for trace concentrations of fugitive VOC's to
be present in the influent air stream. No attempts were made to
modify the inlet VOC concentration, although it was monitored
(as discussed in subsection 6.1.2.4). The moisture content and
temperature of the air stream were a function of ambient
conditions.
15
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TABLE 5-1. SUMMARY OF TEST VARIABLES FOR THE AERATION UNIT
A. INDEPENDENT VARIABLES
Feed Soil Composition/Conditions
• VOC Concentrations
• Moisture Content
• Temperature
Air Inlet Composition/Conditions
• VOC Concentrations
• Moisture Content
• Ambient Temperature
B. CONTROL VARIABLES
Held Constant Throughout Testing Program «
• Feed Soil Volume
• Air Flow Rate
• Soil Residence Time
Held Constant At Various Levels
• Air Pressure at Inlet
C. RESPONSE VARIABLES MEASURED
Soil Composition/Conditions
• VOC Concentrations (during and after batch test)
• Moisture Content (during and after batch test)
• Temperature (during batch test)
• Mass (before and after batch test)
Air Composition/Conditions
• VOC Concentrations (discharge air)
• Moisture Content (discharge air)
• Temperature (inlet and discharge air)'
• Pressure (discharge)
16
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5.2 Control variables. As shown on Table 5-1, there were
three variables held constant at all levels (i.e., feed soil
volume, air flow rate, and soil residence time) and one
variable held constant at various levels (i.e., inlet air
pressure). A schedule of test runs, as well as control
variables, is shown in Table 5-2.
5.2.1 Control variables held constant at all levels. A
constant volume of soil (approximately 4.5 liters) was treated
during each batch test run. Soil was manually delumped and
rocks and oversized items were removed. The constant volume
resulted in approximately 10 pounds of contaminated soil. The
approximate bed height was 1.5 inches.
A constant volume, low pressure rotary lobe blower
maintained an air flow rate of approximately 15 dry standard
cubic feet per minute (dscfm) during each test run.
The soil residence time was approximately 260 minutes for
each test run, but varied slightly.
5.2.2 Control variables held constant at various levels.
The pressure of the inlet air stream was evaluated at two
levels: 3 psi and 5 psi. The major reason for varying pressure
was to evaluate two levels of inlet air temperature (as
temperature is directly related to blower discharge pressure
due to the associated heat of compression).
5.3 Response variables measured.
5.3.1 Soil composition/conditions. Treated soils were
sampled at the end of Test Runs 1 and 2 to determine the
overall VOC removal efficiency. In addition, to determine the
VOC removal trend (over time), the aeration unit was opened and
soils were sampled at discrete intervals during Test Runs 3 and
4 .
The temperature of the soil bed, dependent on the
temperature of the inlet air stream, was monitored at discrete
intervals over the duration of each test run.
The mass of the soil changed over the duration of the test
run as moisture in the soil evaporated. To determine the
approximate amount of moisture that exited the unit as water
vapor, the mass of the feed and processed soils were measured
for each test run.
17
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TABLE 5-2. SCHEDULE OF TEST RUNS FOR THE AERATION UNIT
Test
run
1
2
3
4
Test
run
date
8/29/85
9/6/85
9/12/85
9/13/85
Volume
of soi 1
treated
( liters)
4 . 5
4.5
4. 5
4. 5
Target
air
flow
rate
(dscf m)
15
15
15
15
Target
soi 1
residence
time
(minutes)
260
260
260
260
Target
inlet
air
pressure
(psi)
5
3
5
3
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18
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5.3.2 Air composition/conditions. The VOC concentration in
the discharge air was monitored over the duration of each test
run to determine the VOC removal trend.
The moisture contents of the inlet air stream and discharge
air stream were monitored at the beginning and end of each test
run.
The temperature of the inlet air stream was a function of
the blower discharge pressure (due to the heat of compression).
To determine the air temperatures corresponding to selected
discharge pressures, the temperature of the inlet air stream
was monitored at discrete intervals during each test run.
The pressure of the air stream discharging the aeration
unit was monitored at discrete intervals during each test run
to determine the pressure drop over the unit.
19
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6. SAMPLING TECHNIQUES AND ANALYTICAL METHODS
A brief discussion of the techniques used to sample the
soil and air streams, as well as the laboratory methods used to
analyze the samples, is contained in the following subsections.
An instrumentation diagram showing the location of measuring
devices is included in Figure 6-1.
6.1 Field sampling techniques.
6.1.1 Soil sampling techniques. A list of the soil
parameters that were monitored and/or sampled for analysis is
contained in Table 6-1. As shown, four parameters were
monitored and/or sampled for in the field: those VOC's listed
on the HSL (Appendix A), moisture content, temperature, and
mass .
6.1.1.1 VOC's. A 40-milliliter volatile organic analysis
(VOA) vial was filled with feed soil, soil at intermediate
stages of treatment (only during Test Runs 3 and 4), and
treated soils for analysis of those VOC's on the HSL. The feed
soil was sampled after it was manually delumped and placed in
the aeration unit. The soil bed was sampled at various
locations and depths to obtain a sample that was thought to be
representative. No attempt was made to minimize VOC losses
during delumping activities or placement into the aeration
unit. Since the feed soil sample was not collected until after
these activities were completed, the VOC concentrations in the
samples should be representative of actual conditions at the
beginning of the test.
When soils were sampled during the test run (Test Runs 3
and 4), the following sequence of events occurred:
1. The blower was shut off.
2. The C-clamps on the front door were removed.
3. The front door was removed.
4. VOA bottles were filled with soil.
5. The front door and C-clamps were replaced.
6. The blower was turned on and the test run resumed.
The entire sampling operation took about five to 10
minutes. No attempt was made to minimize VOC losses during
intermediate sampling activities. It was thought that the
amount of VOC's lost during sampling would be minimal when
compared to those VOC's driven off during operation of the unit
(i.e., 15 dry standard cubic feet per minute at a minimum
temperature of 137°F). The soil samples were stored on ice
until delivery to the WESTON laboratory.
20
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Feed
Soil
Ambient
Air
.VOC Concentrations
% Moisture
Blower
To
Atmosphere
I
}
.VOC Concentrations
% Moisture
Total Mass
Discharge
Air
Aeration
Unit
VOC Concentrations
% Moisture
i VOC Concentrations
% Moisture
Total Mass
Treated
Soil
A
F
T
E
R
B
U
R
N
E
R
Key
^^^^
Tl
Fl
PI
Sampling/Analysis Conducted
Temperature Instrument
Flow Instrument
Pressure Instrument
FIGURE 6-1 AERATION UNIT INSTRUMENTATION AND SAMPLING/ANALYSIS
-------
TABLE 6-1. PARAMETERS MONITORED AND/OR SAMPLED FOR IN SOILS
1. VOC's
2. Moisture Content
3. Temperature
4.
Mass
Feed Soil
Soil during treatment
(Test Runs 3- and 4 only)
Treated Soil
Feed Soil
Soil during treatment
(Test Runs 3 and 4 only)
Treated Soil
Feed Soil
Soil during treatment
(All test runs)
Feed Soil
Treated Soil
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6.1.1.2 Moisture content. A 40-mi11iliter VOA vial was
filled with feed soil, soil being treated (during Test Runs 3
and 4) and treated soils. The soil samples were stored on ice
until delivery to the WESTON laboratory for analysis.
6.1.1.3 Temperature. The temperature of the soil was
monitored using a chromel-alumel thermocouple. A hole was
drilled in the aeration unit wall and the thermocouple was
inserted into the soil bed. The thermocouple was fully embedded
in the soil and was not exposed to the air or porous plate. The
thermocouple was wired to a multipoint calibrated digital
pyrometer for accurate reading of temperature. The soil bed
temperature was monitored and recorded at 5-minute intervals
over the entire duration of the test.
6.1.1.4 Mass. As discussed in Subsection 5.2.1, a constant
volume of soil (approximately 4.5 liters) was treated during
each batch test run. An aluminum cake pan was used to measure
the soil volume. A scale (accurate to ±1 pound) was used to
weigh the soil and cake pan. The weight of the empty cake pan
was then subtracted to determine the soil mass. Soils were
weighed before and after each batch test run.
6.1.2 Air sampling techniques. A list of the parameters
that were monitored and/or sampled for in the air stream is
contained in Table 6-2. As shown, five parameters were
monitored and/or sampled for in the field: VOC's, moisture
content, temperature, flow rate, and pressure. A brief
discussion of the air sampling techniques is contained in the
following subsections.
6.1.2.1 VOC's. Total VOC's in the aeration unit outlet
were monitored by a continuous emissions monitoring (GEM)
system during each test run. Gross VOC concentrations were
monitored using an AID Model 590 volatile organics monitor/GC
(photoionization detector with 10.0 electron-volt lamp). Tygon
tubing connected the sample test port in the discharge line to
the inlet port on the portable field instrument.
The CEM system measured gross VOC concentrations in the
linear range from 1 to 600 ppm (by volume, dry basis) relative
to the calibration gas (benzene). The total VOC concentrations
were recorded at 5-minute intervals during each test run.
6.1.2.2 Moisture content. ' The moisture content of the
inlet and outlet air streams was monitored at the beginning and
end of each test run. The moisture content of the aeration unit
inlet (blower discharge), assumed to be the same as ambient
air, was measured using a sling psychrometer and associated
psychrometric chart.
23
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TABLE 6-2. PARAMETERS MONITORED AND/OR SAMPLED FOR IN
THE AIR STREAM
1. VOC'S
2. Moisture Content
3. Temperature
4. Flow Rate
5. Pressure
Ambient Air
Discharge Air
Ambient Air
Discharge Air
Ambient Air
Inlet Air
Discharge Air
Discharge Air
Inlet Air
Discharge Air
0440B
24
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The moisture content of the aeration unit outlet air was
determined using the wet bulb temperature (measured by
inserting a chromel-alumel thermocouple with wet sock into the
outlet line), the dry bulb temperature (measured by inserting a
chromel-alumel thermocouple into the outlet line), and a
psychrometric chart.
Moisture contents were monitored and recorded at the begin-
ning and end of each test run.
6.1.2.3 Temperature. The temperature of the air stream was
monitored at three locations: ambient air, aeration unit inlet
(blower discharge), and aeration unit outlet.
The temperature of the ambient air was monitored using a
mercury thermometer. Ambient air was monitored and recorded
every 30 minutes.
The temperature of the inlet air stream increased with the
blower discharge pressure (due to heat of compression). The
corresponding temperature of the aeration unit inlet was
monitored using a bimetal thermometer inserted into the blower
discharge line. The temperature of the inlet stream was
monitored and recorded every five minutes.
A bimetal thermometer was also inserted into the aeration
unit outlet stream to monitor temperature. The temperature was
monitored and recorded every five minutes during each test run.
6.1.2.4 Flow rate. The flow rate of air into the aeration
unit was assumed to be the same as the flow rate of air out of
the unit. Standard pitot tubes were used in conjunction with
inclined manometers to measure the flow in the outlet stream.
The flow rate was monitored and recorded at the beginning and
end of each test run.
6.1.2.5 Pressure. The pressure on the blower was
controlled by adjusting the weight of washers on a 1-inch
diameter safety relief valve. As metal washers were removed
from the valve, the corresponding blower discharge pressure
decreased.
The pressure was originally to be monitored using a bourdon
C-tube pressure gauge. However, two gauges purchased in the
field both malfunctioned; therefore, the blower discharge
pressure was estimated, as discussed below.
25
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The washers were weighed using a balance scale (accurate to
±1 gram). The resulting mass was 1,795 grams. This weight was
converted to pressure using the following equation:
pounds
Pressure ( ) =
Weight of washers (pounds)
inch'5 Area of safety relief valve (inch2)
(1,795 grams) x (1 pound/454 grams)
(jc/4) x (1 inch)
= 5.0 psi
Two levels of discharge pressure were evaluated: 5 psi and
3 psi. To determine the weight of washers that must be removed
from the relief valve to maintain 3 psi, the following equation
was used:
pounds weight of washers (grams) x (1 pound/454 grams)
3 = •-
inch2 U/4) x (1 inch)2
Weight of washers = 1,070 grams
This weight corresponded to 8 washers (actual weight of
washers was 1,090 grams, resulting in an actual discharge
pressure of 3.06 psi).
The pressure in the aeration unit outlet stream was
measured using a water column pressure gauge. The differential
pressure between the discharge air and atmospheric air was
monitored and recorded every five minutes during each test run.
6.2 Analytical techniques. All soil samples were stored on
ice until delivery to the WESTON laboratory. Upon arrival at
the laboratory, all chain-of-custody forms were signed and
samples were recorded in a bound logbook. All sample containers
were maintained at 4°C until analyzed. No sample was retained
longer than allowable holding times (i.e., 14 days). Analytical
parameters and methods are listed in Table 6-3. Detailed
descriptions of the analytical methods are contained in
Appendix C. A brief discussion is contained in the following
subsections.
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26
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TABLE 6-3. ANALYTICAL PARAMETERS AND METHODOLOGIES
Parameter Method1
A. VOC's in soil. EPA Contract Laboratory Protocol
(CLP) for GC/MS Analysis of
Purgeable Organics in Soils and
Sediments.
B. Moisture Content of Soil. Standard Method 209G.
'Descriptions of the methods are provided in Appendix C.
27
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6.2.1 VOC's in soil. Volatile organics in soil samples
were analyzed using the EPA Contract Laboratory Protocol (CLP)
method for "GC/MS Analysis of Purgeable Organics in Soils and
Sediments." Low level samples (i.e., those containing 5 to 2000
parts per billion (ppb)) were by the "low level protocol" in
which an inert gas was bubbled through a mixture of a 0.005 to
5 gram sample and reagent water contained in a purging chamber
at elevated temperatures. The purgeables were efficiently
transferred from the aqueous phase to the vapor phase. The
vapor was swept through a sorbent column where the purgeables
were trapped. After purging was completed, the sorbent column
was heated and backflushed with the inert gas to desorb the
purgeables onto a gas chromatographic column. The gas
chromatograph was temperature programmed to separate the
purgeables which were then detected with a mass spectrometer.
Samples containing higher levels (i.e., greater than 2000
parts per billion (ppb)) of purgeable organics were analyzed
using the "medium level protocol." In this procedure a measured
amount of soil was extracted with methanol. A portion (5 to 100
milliliters) of the methanol extract was diluted to 5
milliliters with reagent water. An inert gas was bubbled
through this solution at ambient temperature in a specifically
designed purging chamber. The purgeables were effectively
transferred from the aqueous phase to the vapor phase. The
vapor was swept through a sorbent column where the purgeables
were trapped. After purging was completed, the sorbent column
was heated and backflushed with the inert gas to desorb the
purgeables onto a gas chromatographic column. The gas
chromatograph was temperature programmed to separate the
purgeables which were then detected with a mass spectrometer as
described in the CLP methods for "GC/MS Analysis of Purgeable
Organics in Soils and Sediments," provided in Appendix C.
The calibration and quality control measures taken by the
analytical laboratory are discussed in the following subsec-
tions .
6.2.1.1 Calibration. Mass spectrometers are tuned on a daily
basis to manufacturer's specifications with FC-43. In addition,
once per shift, these instruments are tuned with decafluorotri-
phenylphosphine (DFTPP) or 4-bromo-fluorobenzene (BFB) for
semivolatiles or volatiles, respectively. Ion abundances will
be within the windows dictated by the specific program require-
ments. Once an instrument has been tuned, initial calibration
curves for analytes (appropriate to the analyses to be per-
formed) are generated for at least three solutions containing
known concentrations of authentic standards of compounds of
concern. The calibration curve will bracket the anticipated
working range of analyses.
28
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Calibration data, to include the correlation coefficient, will
be entered into laboratory notebooks to maintain a permanent
record of instrument calibrations.-
6.2.1.2 Quality Control. During each operating shift, a
midpoint calibration standard is analyzed to verify that the
instrument responses are still within the initial calibration
determinations. The calibration check compounds will be those
analytes used in the EPA Contract Laboratory Program's
multicomponent analyses (e.g., priority pollutants and
hazardous substances list) with the exception that benzene is
used in place of vinyl chloride (volatiles) and di-n-octyl
phthalate is deleted from the semivolatile list.
The response factor drift (percent RSD) will be calculated
and recorded. If significant (>30 percent) response factor
drift is observed, appropriate corrective actions will be taken
to restore confidence in the instrumental measurements.
All GC/MS analyses will include analyses of a method blank
in each lot of samples. In addition, appropriate surrogate
compounds specified in EPA methods will be spiked into each
sample. Recoveries from method spikes and surrogate compounds
are calculated and recorded. All extractable analyses are
accompanied by method spike/method spike duplicate data.
Duplicate samples will be analyzed for analytical lots of
20 or more.
Audit samples will be analyzed periodically to compare and
verify laboratory performance against standards prepared by
outside sources.
6.2.2 Moisture content in soil. The moisture content of
soil was determined using Standard Method 209G. A copy of the
method is provided in Appendix C. As a quality control measure,
one laboratory blank and one replicate per batch (i.e., maximum
of 20 samples)were also analyzed.
29
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7. PRESENTATION OF DATA
7.1 Soil. Summaries of pertinent data corresponding to
the soil medium for Test Runs 1, 2, 3, and 4 are included in
Tables 7-1, 7-2, 7-3, and 7-4, respectively. Note that the
detection limits for the feed soil and processed soil are
different. This is because the detection limit depended on
three factors:
1. the dilution factor,
2. the exact mass of soil weighed for analysis, and
3. the percent of moisture in the soil.
These three factors were different for each soil sample.
The factor that had the greatest impact on detection limit was
the dilution factor. The procedure for dilution is as follows:
1. Weigh mass of soil (target mass is recommended by
analytical method).
2. Conduct analysis on soil, ensuring that the concen-
trations of target compounds are within the calibra-
tion range.
3. If the target compounds are not within the calibration
range, use a lesser amount of soil than that used
initially (i.e., a higher dilution factor and thus
higher detection limit) .
Also, note that some contaminant levels are estimated
levels. In these cases, the mass spectral data indicated that
the compound of concern was present, but the result was less
than the specified detection limit but greater than zero.
Estimations were made using the peak height and response factor.
To illustrate the trend of VOC removal, the total. VOC
concentrations in soils sampled during Test Runs 3 and 4 are
shown as a function of time in Figures 7-1 and 7-2, respec-
tively.
A detailed list of soil bed temperatures is shown as a
function of time in Table D-l in Appendix D.
7.2 Air. A summary of pertinent data corresponding to the
air stream is shown in Table 7-5.
To evaluate the trend of VOC removal a detailed list of the
total VOC concentration (as ppm by volume) in the discharge air
stream is shown for each test run in Table D-2 in Appendix D.
For illustration, the VOC removal trend (converted to pounds
per hour) is shown graphically for each test run in Figures 7-3
through 7-6. Note that the removal trend is similar for each
30
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test run; however, the ordinate on each figure is different.
Therefore, the figures are not directly comparable (i.e.,
initial concentration for Test Run 4 is approximately 0.045
Ib/hr, whereas initial concentration for Test Run 2 is
approximately 0.002 Ib/hr).
A detailed summary of inlet and outlet
included in Table D-3 in Appendix D.
air temperatures is
31
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TABLE 7-1. SUMMARY OF MAJOR TEST VARIABLES IN SOIL
TEST RUN 1
Conditions: Inlet Pressure - 5 psi
Residence Time - 230 minutes
Average Inlet Air Temperature - 163°F
A. VOC Concentrations (ug/kg)
1,2-Trans Dichloroethylene
Trichloroethylene
Tetrachloroethylene
Xylene
Other VOC's
Total VOC's
Feed
soi 1
33*
19*
19*
490
86*
647
Remova 1
Treated efficiency
soil ( percent )
11**
43**
6**
23**
206
289
67
-126
68
95
-140
55
B. Moisture Content
(Percent by weight)
17.8
0.6
97
C. Mass (pounds)
10
20
* Estimated value
** Estimated value
detection limit was 120 ug/kg
detection limit was 50 ug/kg.
32
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TABLE 7-2. SUMMARY OF MAJOR TEST VARIABLES IN SOIL
TEST RUN 2
Conditions:
Inlet Pressure - 3 ps'i
Residence Time - 245 minutes
Average Inlet Air Temperature - 144°F
Remova1
Feed Treated efficiency
soil soil (percent)
A. VOC Concentrations (ug/kg)
1,2-Trans Dichloroethylene
Trichloroethylene
Tetrachloroethylene
Xylene
Other VOC's
Total VOC's
ND
ND
ND
1,500
3_8
1,538
ND
9*
ND
340
109
458
77
-187
70
B. Moisture Content
(Percent by weight)
11.9
8.7
27
C. Mass (pounds)
11
18
ND - Not Detected
* Estimated value - detection limit was 50 ug/kg.
Not Applicable
0440B
33
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TABLE 7-3. SUMMARY OF MAJOR TEST VARIABLES IN SOIL
TEST RUN 3
U)
Conditions: Inlet Pressure - 5 psi
Residence Time - 285 minutes
Average Inlet Air Temperature - 148°F
Inter-
mittent
Soil
Feed Sample 1
Soil (68 minutes) (
A. VOC Concentrations (ug/kg)
1.2-Trans Dichloroethylene 98,000 26,000
Trichloroethylene 125,000 >260,000
Tetrachloroethylene 57,000 65,000
Xylene 8,200 4,800
Other VOC's 3,740 2.092
Total VOC's 291,940 >357,892
B. Moisture Content
(Percent by weight) 17.6 11.5
C. Mass (pounds) 10 NM
Inter- Inter-
mittent mittent Overall
Soil Soil Removal
Sample 2 Sample 3 Treated Efficiency
136 minutes) (204 minutes) Soil (percent)
15,000 17,000 18,000 82
39,000 35,000 35,000 72
5,900 3,000 2,500 96
230' 300*" 330"*' 96
232" 65"* 1,108 70
60,362 55.365 56,938 81
<0.10 <0.10 0.5 97
NM NM 8 20
NM - Not Measured
" Estimated value - detection limit was 350 ug/kg.
** Estimated value - detection limit was 400 ug/kg.
*** Estimated value - detection limit was 850 ug/kg.
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TABLE 7-4. SUMMARY OF MAJOR TEST VARIABLES IN SOIL
TEST RUN 4
u>
tn
Conditions: Inlet Pressure - 3 psi
Residence Time - 285 minutes
Average Inlet Air Temperature - 137°F
Inter- Inter-
mittent mittent
Soil Soil
Feed Sample 1 Sample 2
Soil (68.5 minutes) (136 minutes)
A. VOC Concentrations (ug/kg)
1,2-Trans Dichloroethylene 265.000 105,000 23,000
Trichloroethylene 1,420,000 1,350,000 131,000
Tetrachloroethylene 495.000 450,000 57,000
Xylene 56,500 24,000 6,100
Other VOC's 19,600 7,750" 3,540
Total VOC's 2,256,100 1.936.750 220,640
B. Moisture Content
(Percent by weight) 18.8 12.6 3.2
C. Mass (pounds) 10 NM NM
Inter-
mittent Overall
Soil Removal
Sample 3 Treated Efficiency
(204 minutes) Soil (percent)
15.000 22,000 92
62,000 104,000 93
14,000 28,500 94
1.300 1.300 98
1,310"* 2,236""" 89
93,610 158.036 93
4.4 0.7 96
NM 9 10
NM - Not Measured
* Estimated value - detection limit was 3,000 ug/kg.
"* Estimated value - detection limit was 1,200 ug/kg.
*** Estimated value - detection limit was 570 ug/kg.
0440B
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O
>
5
o
1900 •
1800 •
1700 •
1600 •
1500 •
1400 •
1300 •
1200 •
1100 •
1000 •
900 •
800 •
700 •
600 •
500 •
400 •
300 •
200
100 •
c
^^^^^_
— x
\
X
3 20 40 60 80 100 120 140 160 180 200 220 240 260 280 300
Time
(Minutes)
FIGURE 7-1 TOTAL VOC REMOVAL: TEST RUN 3
36
-------
Total VOC Concentration
(PPM)
88888
o>
o
o
8 8
ro u
8 8
00 (O O
O O O
000
o
o
ru
o
o
c
3D
m
O)
o
ro
o
o
UJ
O
O
3D
m
O
c §
« «
00
o
8
3D
C
IO
o
to
o
8?
o
00
o
-------
TABLE 7-5. SUMMARY OF MAJOR TEST VARIABLES IN AIR
Test Run Test Run Test Run Test run
1 2 3 4
Inlet Outlet Inlet Outlet Inlet Outlet Inlet Outlet
A. Pressure 5 0.005 3 0.005 5 0.005 3 0.005
B. Total VOC's <1 * <1 ** <1 *** <1 ***•
(ppm/volume
as benzene)
C. Moisture Content 1.90 2.40 2.20 2.30 0.80 2.30 1.00 2.30
(Percent by weight)
0. Flow Rate NM 11.10 NM 11.11 MM 10.86 NM 11.45
(dscfm)
NM - Not Measured
* See Figure 7-3
** See Figure 7-4
*""* See Figure 7-5
38
-------
VOC REMOVAL RATE (Ib/hr)
p p p p p
b o
o o
8888888
3
-» NJ O4
i i 1
^ t/l O)
1 [ 1
vj
1
09 5O
I I
J
/"
p p p p p p
P b b b b b
o -»-».*-._»
•N _
o
o
c
3)
m
-•j
CO
0°
I 3D
> m
m<
09 _
o ^
d -
^ rr
> Z (6 .
en ->
o
m
to
3D
c
tv)
O -(
o
2 J
0 !
j
NJ
oo H
o
m
CO
c
-------
TEST RUN 2
^
xl
p
£
VOC REMOVAL
u.uuo —
0.0028 -
0.0026 -
0.0024 -
0.0022 -
0.002 -
0.0018 -
0.0016 -
0.0014 -
0.0012 -
0.001 -
0.0008 -
0.0006 -
0.0004 -
0.0002 -
0 -
(
\
\A
^-v^
I I 1 1 I
) 40 80
\
T"
120 160
TIME (minutes)
200
240
280
FIGURE 7-4 VOC REMOVAL RATE IN THE
DISCHARGE AIR STREAM - TEST RUN 2
-------
TEST RUN 3
l_
X
^f
jlJ
2
J
o
u
on
o
o
u.uuo —
0.0028 -
0.0026 -
0.0024 -
0.0022 -
0.002 -
0.0018 -
0.0016 -
0.0014 -
0.0012 -
0.001 -
0.0008 -
0.0006 -
0.0004 -
0.0002 -
— |
(
I
i
;
1
1 i
~\
\ A/ \
\A
1
\ r — i 1 ~T~ — r r - ~r --•-]•• i j i i i T 1
3 40 80 120 160 200 240 280
TIME (minutes)
FIGURE 7-5 VOC REMOVAL RATE IN THE
DISCHARGE AIR STREAM - TEST RUN 3
-------
0.05
0.04
FUST KUN 4
to
i.
r.
.0
Ui 0.03 -
o:
_j
b
3 °-02 -
K.
U
§
0.01 -
c
\
^^^
^\^_^- -— -^_ ^' \ ,^x^ . ^^^^
^x
i ' i i i i ii T r "i r~ "i "" i i "
1 40 80 120 160 200 240 280
~1
TIME (minutes)
FIGURE 7-6 MOC REMOVAL RATE IN THE
DISCHARGE AIR STREAM - TEST RUN 4
-------
8. ANALYSIS OF RESULTS
Analytical results were reviewed to determine the experi-
mental variables that significantly affected VOC removal
efficiency. Summaries of pertinent data are contained in Tables
8-1 and 8-2.
Analytical results indicated that VOC removal efficiency is
directly related to the total VOC concentration in the feed
soils, as shown in Table 8-1. As the feed concentration in each
consecutive test run increased, there was a corresponding
increase in total VOC removal efficiency. This result is
predictable since the driving force for mass transfer is the
difference between the VOC concentration in the air stream and
the VOC concentration in the soil. Therefore, an increase in
the driving force results in an increase in mass transfer and a
corresponding increase in VOC removal efficiency. It appears
that, for the duration of test periods evaluated (i.e., 230 to
285 minutes), aeration is not sufficient for volatization when
the driving force is low (i.e., low VOC concentrations). No
conclusion can be made regarding the affect of aeration during
much longer test runs (i.e., multiple hours), since extended
length runs were not evaluated.
Two operating temperatures were reviewed to determine the
effect on VOC removal: 1) the average soil bed temperature and
2) the average inlet air temperature. As shown in Table 8-1
there is no apparent correlation between the soil bed tempera-
ture and the VOC removal efficiency. However, there does appear
to be a relationship between the inlet air temperature and the
VOC removal efficiency. As the inlet air temperature decreased
there was a resulting increase in removal efficiency. This
correlation suggests that, in this application and with this
type of equipment, a lower inlet air temperature improved
stripping. However, it may be that the increase in removal
efficiency is merely due to the corresponding increase in feed
concentration, as discussed above.
The moisture content of the inlet air stream was also
evaluated. As shown in Table 8-1, a decrease in the moisture
content of the inlet air resulted in an apparent increase in
removal efficiency. The explanation for this may be twofold: 1)
the drier air had a greater capacity to absorb moisture from
the soil; and 2) as the moisture evaporated from the soil the
VOC' s also evaporated (the VOC' s may be in solution in the
moisture). This seems to suggest that air with a lower moisture
content is more efficient at removing VOC's. However, the
correlation is not strong. It may be adviseable to test a
broader range of moisture content to further evaluate this
effect.
43
0440B
-------
TABLE 8-1 SUMMARY OF OPERATING DATA
Average
Inlet Air
Total Average Average Moisture
VOC Feed Soil Bed Inlet Air Content VOC
Test Run Concentration Temperature Temperature (percent by Removal
Number (ug/kg) (°F) (°F) volume) Efficiency
1
2
3
4
547
1,538
291,940
2,256,100
105
90
115
102
163
144
148
137
1.90
2.20
0.30
1.00
55
70
81
93
0440B
44
-------
Table 8-2 contains the VOC concentrations and soil moisture
contents corresponding to Test Runs 3 and 4. VOC removal
efficiencies are also included. Analysis of this data indicates
that moisture content in the soil is a major indication of VOC
removal efficiency. Note that for each test run, the greatest
VOC removal occurs when the moisture evaporates from the soil.
For Test Run 3, 97.5 percent of the total removal occurred
between the time the test started (when the moisture content
was 17.6 percent) and at 136 minutes into the test run (when
the moisture content was <0.10 percent). A similar trend was
followed during test run 4; 96.8 percent of total VOC removal
occurred in the first 136 minutes of the run (moisture dropped
from 18.8 percent to 3.2 percent). This relationship between
moisture content and removal efficiency supports the theory
that the majority of VOC's are removed when the moisture
evaporates.
45
0440B
-------
TABLE 8-2. SUMMARY OF MOISTURE CONTENT AND REMOVAL EFFICIENCY AS A FUNCTION OF TIME
(TEST RUNS 3 AND 4)
Intermittent Intermittent Intermittent Treated
Feed Soil Soil Sample Soil Sample Soil Sample Soil Sample
Sample (t = (t= (t = (t=
(t = 0) 68 minutes) 136 minutes) 204 minutes) 285 minutes)
Total VOC Concentration (ug/kg)
Test Run 3;
Cumulative Removal
Efficiency
(percent)
Moisture Content
(percent by
weight)
291,940 >357,892
-23
17.6
11.5
60,362
79
<0.10
55,365
81
<0.10
56,938
81
0.5
Total VOC Concentration (ug/kg)
Test Run 4: 2,256,100 1,936,750 220,640
Cumulative Removal
Efficiency
(percent)
Moisture Content
(percent by
weight)
18.8
14
12.6
90
3.2
93,610
96
4.4
158,036
93
0.7
Not Applicable
0440B
4S
-------
9. CONCLUSIONS AND RECOMMENDATIONS
9.1 Conclusions. Based on review of the data associated
with all test runs, the following conclusions are presented:
1. Total VOC concentration is directly related to VOC
removal efficiency.
2. There is no apparent correlation between the soil bed
temperature and VOC removal efficiency.
3. Inlet air temperature appears to be inversely related
to VOC removal efficiency.
4. There is no apparent correlation between the moisture
content in the inlet air and the VOC removal effi-
ciency.
5. The greatest VOC removal occurs during evaporation of
moisture from the soil.
6. Processed soil moisture content provides an indication
of VOC removal efficiency and possibly processed soil
VOC residuals.
7. Comparison of the VOC removal efficiencies associated
with the aeration element and the thermal element
(discussed in a separate report1) indicates that the
role of aeration in thermal stripping is minimal. This
conclusion applies to those conditions evaluated in
this study (i.e., inlet air pressure, inlet air
temperature, inlet air moisture content, ambient air
temperature and test duration).
9.2 Recommendations. Based on the results of this field
demonstration program, the following recommendations are
presented:
1. Apply the conclusions of this report to the evaluation
and/or optimization of the thermal stripping process,
specifically:
(a) Utilize a minimal air flow rate since the role of
aeration in thermal stripping appears to be
minimal.
'Task 11. Pilot Investigation of Low Temperature Thermal
Stripping of Volatile Organic Compounds (VOC's) From Soil,
Report No. AMXTH-TE-CR-86074, June 1986.
47
0440B
-------
(b) Further evaluate the effects of moisture content
in the inlet air stream. Although this study
indicated that ther-e is no apparent correlation
between the moisture content in the inlet air and
the VOC removal efficiency, a very narrow range
was evaluated (i.e., 0.8 to 2.2 percent by
volume). In future studies, evaluate a broad
range of moisture contents (i.e., dehumidified
air to saturated air).
(c) Evaluate addition of moisture to soil (i.e.,
before and during tests to determine the effect
on VOC removal efficiency.
(d) Evaluate use of an inert carrier gas (i.e.,
nitrogen or combustion gases from oil heating
unit) instead of air. Although the use of an
inert carrier gas is not expected to improve VOC
removal efficiency, it will improve the safety of
the system (i.e., by avoiding the explosive
limits associated with volatile hydrocarbons in
air).
Evaluate results from Task Order 4, an ongoing
benchscale study to investigate in situ volatilization
of VOC' s from soil, to confirm the findings of this
study.
Conduct bench/pilot studies to further evaluate the
effect of operating parameters on VOC removal
efficiency (i.e., a greater range of temperatures,
different soil bed heights, a variety of moisture
contents in air, etc.).
Further investigate the correlation between processed
soil moisture content and VOC concentration to
determine if soil moisture content could be used to
monitor, predict, and/or control soil VOC decontam-
ination effectiveness. During investigations, the soil
moisture content and VOC concentration should be
monitored before, during, and after aeration to
determine if a correlation exists.
48
0440B
-------
APPENDICES
APPENDIX A - ORGANIC WASTE CHARACTERISTICS OF SITE SOILS AT LEAD
(DETERMINED DURING PRELIMINARY INVESTIGATIONS)
APPENDIX B - GRAIN SIZE GRADATION CURVES CORRESPONDING TO FILL
SOIL AND NATIVE SOIL
APPENDIX C - ANALYTICAL METHODS
APPENDIX D - SUPPLEMENTAL DATA
0440B
-------
APPENDIX A
ORGANIC WASTE CHARACTERISTICS OF SITE SOILS AT LEAD
(DETERMINED DURING PRELIMINARY INVESTIGATIONS)
0440B
-------
TABLE A-l.
VOLATILE ORGANIC COMPOUNDS (VOC'S)
THE HAZARDOUS SUBSTANCE LIST (HSL)
INCLUDED ON
Detection limits*
Volatile
organic
compounds
1.
2.
3 .
4 .
5.
6.
7.
8.
9 .
10.
11.
12.
13.
14.
15.
16.
17.
18.
19.
20.
21.
22.
23 .
24 .
25.
Chloromethane
Bromomethane
Vinyl Chloride
Chloroethane
Methylene Chloride
Acetone
Carbon Disulfide
1, 1-Dichloroethene
1, 1-Dichloroethane
Trans-l,2-Dichloroethene
Chloroform
1, 2 -D ichloroethane
2-Butanone
1,1, 1-Tr ichloroethane
Carbon Tetrachlor ide
Vinyl Acetate
Bromodichloromethane
1,1,2, 2-Tetrachloroethane
1,2-Dichloropropane
Trans-1 , 3-Dichloropropene
Trichloroethene
Dibromochloromethane
1,1, 2-Tr ichloroethane
Benzene
Cis-1, 3-Dichloropropene
Low
water3
ug/L
10
10
10
10
5
10
5
5
5
5
5
5
10
5
5
10
5
5
5
5
5
5
5
5
5
Low soil/
sediment b
ug/Kg
10
10
10
10
5
10
5
5
5
5
5
5
10
5
5
10
5
5
5
5
5
5
5
5
5
aMedium Water Contract Required Detection Limits (CRDL) for
Volatile HSL Compounds are 100 times the individual Low Water
CRDL.
"Medium Soil/Sediment Contract Required Detection Limits
(CRDL) for Volatile HSL Compounds are 100 times the individual
Low Soil/Sediment CRDL.
•Detection limits listed for soil/sediment are based on wet
weight.
A-l
0440B
-------
TABLE A-l. (CONTINUED)
Detection limits*
Volatile
organic
compounds
26.
27.
28.
29.
30.
31.
32.
33.
34 .
35.
2-Chloroethyl Vinyl Ether
Bromof orm
2-Hexanone
4-Methy 1-2-pentanone
Tetrachloroethene
Toluene
Chlorobenzene
Ethyl Benzene
Styrene
Total Xylenes
'LOW
water3
ug/L
10
5
10
10
5
5
5
5
5
5
Low soil/
sediment b
ug/Kg
10
5
10
10
5
5
5
5
5
5
aMedium Water Contract Required Detection Limits (CRDL) for
Volatile HSL Compounds are 100 times the individual Low Water
CRDL.
"Medium Soil/Sediment Contract Required Detection Limits
(CRDL) for Volatile HSL Compounds are 100 times the individual
Low Soil/Sediment CRDL.
*Detection limits listed for soil/sediment are based on wet
weight.
A-2
0440B
-------
TABLE A-2. CONCENTRATION RANGE OF VOLATILE ORGANIC COMPOUNDS (VOC'S) DETERMINED
TO BE PRESENT IN AREA K-l (BASED ON TESTING PERFORMED ON 10-12 JUNE 1985)*
Concentration (ug/g)**
Borehole Borehole Borehole Borehole
Compound 1234
1. Volatiles on Hazardous Substance List (HSL)
Acetone
Benzene
Bromomethane
Bromof orrn
2-Butanone
Carbon Disulfide
Carbon Tetrachloride
Chlorobenzene 0.33-240
Chlorodibromomethane
Chloroethane
2-Chloroethylvinyl Ether
Chloroform
Chloromethane
Dichlorobromomethane
1,1-Dichloroethane
1,2-Dichloroethane
1,1-Dichloroethylene
1,2-Dichloropropane
1,3-Trans Dichloropropene
1,3-Cis Dichloropropene
Ethylbenzene 3.5-4.3 0-3.7 0.73-5.9 0-0.C02
2-Hexanone
Methylene Chloride 0-4.3
4-Methyl-2-Pentanone
Styrene
1,1,2,2-Tetrachloroethane
Tetrachloroethylene
Toluene
1, 2-cis/trans
Dichloroethylene
0.39-28
0-16
5.8->1300
0.012-0.6
0.03-76
0.008-29
13-390
0-0.047
0-0.002
0.07-4.8
*For reference, the locations of soil borings' drilled in Area K-l during the waste
characterization phase of the pilot study are shown in Figure A-l.
**Concentration ranges correspond to the minimum and maximum concentrations observed for
all discrete samples (i.e., 1.5--3.51, 3.5--5.01, 5.0'-6.5', 6.5'-8.0', 8.0'-10.0'}.
A-3
0440B
-------
TABLE A-2. (CONTINUED)
Concentration (uq/g)**
Compound
1. Volatiles on Hazardous
1,1, 2-Trichloroethane
1,1, 1-Trichloroethane
Trichloroethylene
Vinyl Acetate
Vinyl Chloride
Xylene
Total Volatiles
2. Others
Cio-Allyl Benzene
Dichlorobenzene
Methyl Ethyl Benzene
n-Propylbenzene
Trimethyl Benzene
Total Others
TOTAL
Borehole
1
Substance List (HSL)
0.84-16
0-2.1
25-32
35.86-
1643.2
20-30
3-600
0.07-30
4-7
30-110
57.07-777
92.93-
2420.2
Borehole
2
( continued)
0.03-27
0.006-25
0.078-
132. 3
0.03-10
0-10
0-3
0.13-60
0.16-83
0.238-215.3
Borehole
3
0-14
0.078-300
0-2.6
4-31
17.816
772.5
0.009-100
2.3-9
0-2.9
8.4-37
10.709-148.9
28.525-921.4
Borehole
4
0.02-1.1
0-0.006
0.09-5.957
0-0.07
0-0.07
0.09-6.027
*For reference, the locations of soil borings drilled in Area K-l during the waste
characterization phase of the pilot study are shown in Figure A-l.
**Concentration ranges correspond to the minimum and maximum concentrations observed for
all discrete samples (i.e., 1.5'-3.5', 3.5'-5.0', 5.0--6.51, 6.5'-8.0', B.O'-IO.O1).
A-4
0440B
-------
TABLE A-2. (CONTINUED)
Concentration (uq/g)'
Compound
Borehole
5
Borehole
6
Borehole
7
Borehole
8
1. Volatiles on Hazardous Substance List (HSL)
Acetone
Benzene
Bromomethane
Bromoform
2-Butanone
Carbon Bisulfide
Carbon Tetrachloride
Chlorobenzene
Chlorodlbromomethane
Chloroethane
2-Chloroethylvinyl Ether
Chloroform
Chloromethane
Dichlorobromomethane
1,1-Dichloroethane
1,2-Dichloroethane
1,1-Dichloroethylene
1,2-Dichloropropane
1,3-Trans Dichloropropene
1,3-Cis Dichloropropene
Ethylbenzene
2-Hexanone
Methylene Chloride
4-Methyl-2 -Pentanone
Styrene
1,1,2,2-Tetrachloroethane
Tetrachloroethylene
Toluene
1,2-cis/trans
Dichloroethylene
0-0.28
0-1.7
0.012-0.064
0.46-5.2
0-0.44
0-0.26
0.3-2.7
0.97-4.3
0-0.6
0.07-0.76
0.009-4.2
4.9-8.2
0.098-990
0-4.9
210->3800
10-130
0-1.8
0.15-11
0.058-17
0.9-920
*For reference, the locations of soil borings drilled in Area K-l during the waste
characterization phase of the pilot study are shown in Figure A-l.
**Concentration ranges correspond to the minimum and maximum concentrations observed for
all discrete samples (i.e., 1.5'-3.5', 3.5'-5.0', 5.0'-6.5', 6.5'-8.0', 8.0'-10.0').
A-5
0440B
-------
TABLE A-2. (CONTINUED)
Compound
1. Volatiles on Hazardous
1,1, 2-Trichloroethane
1,1, 1-Trichloroethane
Trichloroethylene
Vinyl Acetate
Vinyl Chloride
Xylene
Total Volatiles
2. Others
Cio-Allyl Benzene
Dichlorobenzene
Methyl Ethyl Benzene
n-Propylbenzene
Trimethyl Benzene
Total Others
TOTAL
Concentration (ug/q)**
Borehole Borehole Borehole
557
Substance List (HSL) (continued)
34-48
0.047-1.2 0.056-330 25->3500
0-4.3
0.049-25 5.1-24
0.519-8.164 6.452 284.1-
1371.04 7506.9
2-20
0-0.4 7-200 0.9-2.4
0.5-24 0-10
0.72-5.6
3.7-66 0-43
0-0.4 13.92- 0.9-55.4
315.6
0.519-8.564 20.372 285-
1686.64 7562.3
Borehole
8
1.2-3000
4.4-4.8
0.32-47
7.528
4001. 6
0-5
0.5-20
0.4-11
0-4
2.5-50
3.4-90
10.928
4091.6
*For reference, the locations of soil borings drilled in Area K-l during the waste
characterization phase of the pilot study are shown in Figure A-l.
**Concentration ranges correspond to the minimum and maximum concentrations observed for
all discrete samples (i.e., 1.5'-3.5', 3.5'-5.0', 5.0'-6.5', 6.5'-8.0', 8.0'-10.0').
A-6
0440B
-------
:*srj««i,a»eui:»i»is
TABLE A-2. (CONTINUED)
Concentration (uq/qr)**
Borehole Borehole Borehole
Compound 9 10 11
1. Volatiles on Hazardous Substance List (HSL)
Acetone
Benzene
Bromomethane
Bromoform
2-Butanone
Carbon Disulfide
Carbon Tetrachloride
Chlorobenzene
Chiorodibromethane
Chloroethane
2-Chloroethylvinyl Ether
Chloroform
Chloromethane 0-0.1
Dichlorobromomethane
1,1-Dichloroethane
1, 2-Dichloroethane
1,1-Dichloroethylene 0-0.01
1,2-Dichloropropane
1,3-Trans Dichloropropene
1,3-Cis Dichloropropene
Ethylbenzene
2-Hexanone
Methylene Chloride
4-Methyl-2-Pentanone
Styrene
1,1,2,2-Tetrachloroethane
Tetrachloroethylene 0.006-170 0.016-0.83 0-0.007
Toluene 0-0.006
1, 2-cis/trans
Dichloroethylene 4.5-74 0.05-0.08 0.007-0.023
*For reference, the locations of soil borings drilled in Area K-l during
the waste characterization phase of the pilot study are shown in
Figure A-l.
**Concentration ranges correspond to the minimum and maximum concentra-
tions observed for all discrete samples (i.e./ 1.5'-3.5', 3.5'-5.0',
5.0--6.51, 6.5--8.01, S.O'-IO.O1).
A-7
0440B
-------
TABLE A-2. (CONTINUED)
Compound
Concentration (ug/g)**
Borehole
9
Borehole
10
Borehole
11
Volatiles on Hazardous Substance List (HSL) (continued)
1,1,2-Trichloroethane
1,1,1-Trichloroethane
Trichloroethylene
Vinyl Acetate
Vinyl Chloride
Xylene
Total Volatiles
0-30
0.14-1700
8-11
12.646
1985.01
0.01-2.5
0.05-0.24
0.012-0.06
0.138-3.81
0.012-0.037
0.019-0.073
Others
Cio-Allyl Benzene
Dichlorobenzene
Methyl Ethyl Benzene
n-Propylbenzene
Trimethyl Benzene
Total Others
TOTAL
2-11
0-4
0-20
2-35
14.646
2020.01
0-0.08
0.02-0.1
0.02-0.13
0-0.02
0.13-0.44
0.17-0.77
0.308-4.58 0.019-0.073
*For reference, the locations of soil borings drilled in Area K-l during
the waste characterization phase of the pilot study are shown in
Figure A-l.
**Concentration ranges correspond to the minimum and maximum concentra-
tions observed for all discrete samples (i.e., 1.5'-3.5', 3.5'-5.0',
5.0--6.51, 6.5'-8.0', S.O'-IO.O').
A-8
0440B
-------
o
01
o
Processing Area
40' x 40' Concrete Pad
Existing Dike
V
1
/
/
I
ID
Well E-7
Excavation Area
]p
Existing Dike
I
Well E-5
//
//
40 0 40 80 Ft.
Scale in Feet
FIGURE A-1 LOCATION OF SOIL BORINGS DRILLED IN AREA K-1 DURING
THE WASTE CHARACTERIZATION PHASE OF THE PILOT STUDY
-------
TABLE A-3. VOC CONCENTRATIONS IN EXCAVATED SOILS FROM PHASE 1 OF THE PILOT INVESTIGATION (PPM BY WEIGHT)
I
M
O
Test
Run
No. Oichloroethvlene
I. Phase
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
Average
I Test Runs
0.48
110.00
3.10
0.21
830.00
770.00
1.20
110.00
1,200.00
270.00
100.00
62.00
130.00
310.00
140.00
BOL
252.30
Trichloroethylene
0.64
3.600.00
1.50
0.29
20,000.00
8,400.00
1.50
1,200.00
2,640.00
2,200.00
830.00
39.00"
1,600.00
2,200.00
950.00
BDL
2,728.90
Tetrachl oroethylene
0.13*
4.800.00
4.70
0.81
580.00
39.00"
0.84"
190.00
BDL
1,300.00
530.00
30.00"
230.00
2.300.00
1.900.00
8.00"
744.60
Xylene
0.12"
35.00"
0.26
BDL
460.00
240.00
BDL
97.00"
47.00*
110.00
60.00
NO EX
29.00"
150.00
140.00
13.00*
NO EX
86.30
Other VOC's
0.03"
10.40*
0.06"
0.04"
117.00"
56.00"
0.62"
12.05"
269.60
26.60"
17.30*
C A V A T I 0 N
BDL
28.30*
35.00*
40.80
C A V A T I 0 N
BDL
38.40'
Total VOC's
1.40
8,555.40
9.62
1.35
21,987.00
9,505.00
4.16
1,609.05
4,156.60
3,906.60
1,537.30
160.00
2,138.30
4,985.00
3,043.80
8.00
3,850.60
"Estimated value
BDL = Below Detection Limit
0440B
-------
TABLE A-3. (CONTINUED)
Test
Run
No. Dichloroethylene Trichloroethylene Tetrachloroethylene
II. Phase II Test Runs
19 1.80* BDL
20
21 0.02* 0.08*
22 0.45* BDL
23
24 74.00 >390.00
25
26
27 13.00* 340.00
2fi
Average 17.85 > 146. 02
BDL
NO EXCAVATION
0.03*
BDL
NO EXCAVATION
>260.00
NO EXCAVATION
NO EXCAVATION
210.00
>94.01
Xylene Other VOC's Total VOC's
6.30 1.50* 9.60
0.10 BOL 0.22
79.00 34.76 114.21
>7,190.00 16.80 >930.80
35.00* BOL 598.00
>62.08 10.61 >330.57
•Estimated Value
BDL - Below Detection Limit
0440B
-------
APPENDIX B
GRAIN SIZE GRADATION CURVES CORRESPONDING TO FILL
SOIL AND NATIVE SOIL
6060A
-------
100
90
80
70
E
o>
|60
Q
c50
i.
0)
^40
0.
30
20
10
o
Hydrometer Analysis —
_<».. = ::
„.«;•:::
I.'*"
US Standard Sieves #200 #100*70 #50 #40 #30 #16 #10 #8 #4 naysis
Tyler Standard Sieves #200 #100 #65 #48 #35 #28 #14 # 9 #8 #4 *•" ^ r w- 2Vj" 3'
2
i
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t « • '
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f
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-001 .002 .005 .01 .02 .05 .1 .2 .5 1.0 2.0 5 10 20
Gram Size in Millimeters
Un.ledSo.ls C| 0, Sl|(
Classification
Sand
Fine | Medium Coarse
Symbol
0
Sample
D60
Specific Gravity
Gravel
Fine 1
Description of Sample
Fu.u-€
'"*""•" S"WD
~ +•
~*
1
I
—4
—
—
j
^ f
n ~^
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1 r
!
+.. J
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1 (
i ^
- - iuu
~
- - 90
- - 80
- - /u
- - 60
--50
4U
- 30
on
^(J
— 1U
-
n
50 100
Coarse
Cobbles
«isiit\2/£
0!
KS
hA'ANTt
Gradation Curves
-------
Hydrometer Analysis -
^
100
US Standard Sieves #200
Tyler Standard Sieves #200
#100*70 #50 #40 #30
#100 #65 #48 #35 #28
#16 #10 #8 #4
#14 # 9 #8 #4
- Sieve Analysis
1 V n,"
2'/2" 3"
100
90
.002
.005
.01
.02
.05
.1 .2 .5 1.0
Grain Size in Millimeters
2.0
10
20
50
United Soils
Classification
C| o, S|N
Sand
Medium
Coarse
Fine
Gravel
~T-
Coarse
100
Cobbles
Symbol
td
NJ
Sample
D60
Specific Gravity
Description of Sample
So.'
Gradation Curves
-------
APPENDIX C
ANALYTICAL METHODS
EPA CONTRACT LABORATORY
PROTOCOL FOR GC/MS
ANALYSIS, PURGEABLE
ORGANICS IN WATER, SOILS
AND SEDIMENTS
STANDARD METHOD 209G
0440B
-------
EPA CONTRACT LABORATORY PROTOCOL FOR GC/MS ANALYSIS
PURGEABLE ORGANICS IN WATER, SOILS, AND SEDIMENTS
6060A
-------
IV.
1. CC/MS Analysis of Purgeable Organic*
1.1 Summary of Methods
1.1.1 Water samples
An inert gas is bubbled through a 5 mL sample contained in a
specifically designed purging chamber at ambient temperature.
The purgeables are efficiently transferred from the aqueous
phase to the vapor phase. The vapor is swept through a sorbent
column where the purgeables are trapped. After purging is com-
pleted, the sorbent column is heated and backflushed with the
inert gas to desorb the purgeables onto a gas chromatographic
column. The gas chromatograph is temperature programmed to
separate the purgeables which are then detected with a mass
spectrometer.
An aliquot of the sample is diluted with reagent water when
dilution is necessary. A 5 «L aliquot of the dilution is
taken for purging.
1.1.2 Sediment/Soil Samples
1.1.2.1 Low Level. An inert gas is bubbled through a mixture
of a 5 gm sample and reagent water contained in a sug-
gested specially designed purging chamber (illustrated
on page D-95) at elevated temperatures. The purgeables
are efficiently transferred from the aqueous phase to
the vapor phase. The vapor is swept through a sorbent
column where the purgeables are trapped. After purging
is completed, the sorbent column is heated and back-
flushed with the inert gas to desorb the purgeables
onto a gas chromatographic column. The gas chromato-
graph is temperature programmed to separate the purge-
ables which are then detected with a mass spectrometer.
01
Rev: 9/84
-------
IV.
1.1.2.2 Medium Level. A Matured amount of soil is extracted
with me thancl. A portion of the methanol extract is
diluted to 5 mi. vich reagent water. An inert gas
is bubbled through this solution in a specifically
designed purging chamber at ambient temperature.
The purgeables are effectively transferred from the
aqueous phase to the vapor phase. The vapor is swept
through a aorbent column where the purbeables are
trapped* After purging ia completed, the sorbent
column is heated and backflushed vlth the inert gas
to desorb the purgeables onto a gas cbromatographic
column. The gas chromatograph is temperature pro*
grammed to separate the purgeables which are then
detected with a mass spectrometer.
1.2 Interferences
1.2.1 Impurities in the purge gas, organic compounds out-gassing
from the plumbing ahead of the trap, and solvent vapors in the
laboratory account for the majority of contamination problems.
The analytical system must be demonstrated to be free from
contamination under the conditions of the analysis by running
laboratory reagent blanks as described in Exhibit E. The use
of non-TFE tubing, non-TFE thread sealants, or flow controllers
with rubber components in the purging device should be avoided.
1.2.2 Samples can be contaminated by diffusion of volatile organics
(particularly fluorocarbons and methylene chloride) through
the septum seal into the sample during storage and handling.
A holding blank prepared from reagent water and carried through
the holding period and the analysis protocol serves as a check
on such contamination. One holding blank per case must be
analyzed.
C-2
5/B4
-------
1.2.3 Contamination by carry over can occur whenever high level and
low level samples are sequentially analyzed. To reduce carry
over, the purging device and sampling syringe must be rinsed
with reagent vater between saaple analyses. Whenever an
unusually concentrated sample is encountered, it should be
followed by an analysis of reagent water to check for cross
contamination. For samples containing large amounts of 'water-
soluble materials, suspended solids, high boiling compounds
or high purgeable levels, it may be necessary to wash out /
the purging device with a detergent solution, rinse it with /
distilled vater, and then dry it in a 105*C oven between
analyses. The trap and other parts of the system are also
subject to contamination; therefore, frequent bakeout and
purging of the entire system may be required.
1.3 Apparatus and Materials
1.3.1 Micro syringes - 25 uL and larger, 0.006 inch ID needle.
1.3.2 Syringe valve - two-way, with Luer ends (three each), if
applicable to the purging device.
1.3.3 Syringe - 5 mL, gas tight with shut-off valve.
1.3.4 Balance-Analytical, capable of accurately weighing 0.0001 g.
and a top-loading balance capable of weighing O.lg.
1.3.5 Glassware
1.3.5.1 o Bottle - 15 mL, screw cap, with Teflon cap liner.
o Volumetric flacks - class A with ground-glass stoppers.
o Vials - 2 mL for CC autosampler.
C-3
5/84
-------
IV.
1.3.6 Purge and Crap device - The purge and crap device consists of
Chree separate pieces of equipment; che sample purger, crap
and Che desorber. Several complete devices are now commercially
available.
1.3.6.1 The sample purger BUBC be designed Co accept 5 ml
samples with a water column at least 3 cm deep. The
gaseous head space between Che water column and Che
trap must have a total volume of less Chan 15 mL. The
purge gas must pass through Che water column as finely
divided bubbles vlch a diameter of less Chan 3 mo at
Che origin. The purge gas Bust be introduced no more
than 5 mm from che base of che water column. The
sample purger, illustrated in Figure 1, meets these
design criteria. Alternate sample purge devices may
be utilized provided equivalent performance is
demonstrated.
1.3.6.2 The trap must be at least 25 cm long and have an inside
diameter of at lease 0.105 inch. The Crap must be
packed Co contain che following minimum lengths of
absorbents: 1.0 cm of aethyl silicone coated packing
(3Z OV-1 on Chromosorb W or equivalent), 15 cm of 2,6-
diphenylene oxide polymer (Tenax-GC 60/80 mesh) and 8
cm of silica gel (Davison Chemical, 35/60 mesh, grade
15, or equivalent). .The minimum specifications for the
crap are illustrated in Figure 2.
1.3.6.3 The desorber should be capable of rapidly heating
che trap Co 180*C. The polymer seccion of che
crap should noC be heated higher Chan 180'C and
che remaining sections should not exceed 220"C.
The desorber design, illustrated in Figure 2, meets
Chese criteria.
C-4
5/84
-------
1.3.6.4 The purge and trap device may be assembled as a
aeparate unit or be coupled to a gas chromatograph
•s Illustrated in Figures 3 and A.
1.3.6.5 A heater or heated bath capable of maintaining the
purge device at 40CC + 1'C.
1.3.7 GC/MS system
1.3.7.1 Gas chromatograph - An analytical system complete with
• temperature programmable gas chromatograph suitable
for on-column Injection and all required accessories
including syringes, analytical columns, and gases.
1.3.7.2 Column - 6 ft long x 0.1 in ID glass, packed with IX
SP-1000 on Carbopack B (60/80 mesh) or equivalent.
<
1.3.7.3 Mass spectrometer - Capable of scanning from 35
to 260 amu every seven seconds or less, utilizing
70 volts (nominal) electron energy in the electron
impact ionization mode and producing a mass spectrum
which meets all the criteria in table 2 when 50 ng
of 4-bromofluorpbenzene (BFB) is injected through
the gas chromatograph inlet*
1.3.7.4 GC/MS interface - Any gas chromatograph to mass
spectrometer interface that gives acceptable cali-
bration points at 50 ng or less per injection for
each of the parameters of interest and achieves all
acceptable performance criteria (Exhibit E) may
be used. Gas chromatograph to mass spectrometer
Interfaces constructed of all-glass or glass-lined
materials are recommended. Glass can be deactivated
by silanizing with dichlorodimethylsilane.
05
5/84
-------
IV.
1.3.7.5 Data system - A computer system must be interfaced
to the BASE spectrometer that allows the continuous
acquisition and storage on machine readable media
of all mass spectra obtained throughout the duration
of the chromatographic program. The computer must
have software that allows searching any CC/MS data
file for ions of a specified mass and plotting such
ion abundances versus time or scan number. This
type of plot is defined as an Extracted Ion Current
Profile (E1CP). Software must also be available that
allows Integrating the abundance in any ECIP between
specified time or scan number limits.
1.4 Reagents
1.4.1 Reagent water - Regent water is defined as water in which an
interferent is not observed at the HDL of the parameters of
interest.
1.4.1.1 Reagent water may be generated by passing tap water
through a carbon filter bed containing about 453 g of
activated carbon (Calgon Corp., Filtrasorb-300 or
equivalent ).
1.4.1.2 A water purification system (Millipore Super-Q or
equivalent) may be used to generate reagent water.
1.4.1.3 Reagent water may also be prepared by boiling water
for 15 minutes. Subsequently, while maintaining the
temperature at 90*C, bubble a contaminant -free inert
gas through the water for one hour. While still hot,
transfer the water to a narrow-mouth screw-cap bottle
and seal with a Teflon-lined septum and cap.
1.4.2 Sodium thlosulfate - (ACS) Granular.
C-6
5/84
-------
IV.
1.4.3 Methano1 - Pesticide quality or eqvuivalent.
1.4.4 Stock standard solutions - Stock standard aolutlonc Bay be
prepared from pure standard materials or purchased and must
be traceable to EMLS/LV supplied standards. Prepare stock
standard solutions in aethanol using assayed liquids or gases
as appropriate.
1.4.4.1 Place about 9.8 mL of methanol into a 10.0 nL tared
ground glass stoppered volumetric flask. Allow the
flask to stand, unstoppered, for about 10 minutes or
until all alcohol wetted surfaces have dried. Weigh
the flask to the nearest 0.1 ng.
1.4.4.2 Add the assayed reference material as described below.
1.4.4.2.1 Liquids - Using a 100 uL syringe,
immediately add two or more drops of
assayed reference material to the flask
then reweigh. The liquid must fall
directly into the alcohol without
contacting the neck of the flask.
1.4.4.2.2 Gases - To prepare standards for any of
the four halocarbons that boil below 30°C
(bromomethane, chloroethane, chloromethane,
and vinyl chloride), fill a 5 mL valved
gas-tight syringe with the reference
standard to the 5.0 mL nark. Lower the
needle to 5 mm above the netHanoi meniscus.
Slowly Introduce the reference standard
above the surface of the liquid. The
heavy gas rapidly dissolves in the
methanol.
C-7
5/84
-------
1.4.4.3 Reweigh, dilute to volu*e, •topper, then nix by
Inverting the flask several tines. Calculate the
concentration in mlcrograac per microliter from the
net gain in weight. When compound purity it assayed
to be 961 or greater, the weight Bay be used without
correction to calculate the concentration of the stock
standards may be used at any concentration if they are
certified by the manufacturer. Commercial standards
oust be traceable to EMSL/LV supplied standards.
1.4.4.4 Transfer the stock standard solution into a Teflon-
sealed screw-cap bottle. Store, with minimal head-
space at -10°C to -20*C and protect from light.
1.4.4.5 Prepare fresh standards weekly for the four gases and
2-chloroethyl-vinyl ether. All other standards must
be replaced after one month, or sooner if comparison
with check standards indicate a problem.
1.4.5 Secondary dilution standards - Using stock standard solutions,
prepare secondary dilution standards in methanol chat contain
the compounds of Interest, either singly or mixed together.
(See GC/MS Calibration in Exhibit E). Secondary dilution
standards should be stored with minimal headspace and should
be checked frequently for signs of degradation or evaporation,
especially just prior to preparing calibration standards from
them.
1.4.6 Surrogate standard spiking solution. Prepare stock standard
solutions for toluene-d8, p-bromofluorobenzene, and 1,2-
dichloroethane-d4 in methanol as described In Paragraph 1.4.4.
Prepare a surrogate standard spiking solution from these stock
standards at a concentration of 250 ug/10 mL In methanol.
C-8
Rev: 9/84
-------
1.4.7 Purgeable Organic Matrix Standard Spiking Solution
1.4.7.1 Prepare a spiking volution in Bethanol that contains
the following compounds at a concentration of 250
ug/10.0 ml:
Purgeable Organlcs
1,1-dichloroethene
trichloroethene
chlorobenzene
toluene
benzene
1.4.7.2 Matrix spikes, also serve as duplicates; therfore, add
an aliquot of this solution to each of two portions
from one sample chosen for spiking.
1.4.8 BFB Standard - Prepare a 25 ng/uL solution of BFB in Bethanol.
1.4.9 Great care must be taken to maintain the integrity of all stan-
dard solutions. It is recommended that all standard solutions
be stored at -10*C to -20*C in screw cap amber bottles with
teflon liners.
1.5 Calibration
1.5.1 Assemble a purge and trap device that meets the specification
in paragraph 1.3.6. Condition the trap overnight at 180°C in
the purge mode with an inert gas flow of at least 20 mL/min.
Prior to use, daily condition traps 10 minutes while back-
flushing at 180°C with the column at 220eC.
1.5.2 Connect the purge and trap device to a gas chromatograph.
The gas chromatograph must be operated using temperature and
flow rate parameters equivalent to those in paragraph 1.7.1.2
Calibrate Che purge and trap-GC/MS system using Che internal
standard technique (paragraph 1.5.3).
C-9
y 5/84
-------
IV.
1.5.3 Internal standarc calibration procedure. The three internal
standards are bromochloromethane , 1 ,4-dlf luorobenzene , and
chlorobenzene-dj.
1.5.3.1 Prepare calibration standards at a minimum of five
concentration levels for each HSL paraaeter. The
concentration levels are specified in Exhibit E.
Aqueous standards nay be stored up to 24 hours, if
held in sealed vials with zero headspace as described
in paragraph 1.7. If not so stored, they mist be
discarded after an hour.
1.5.3.2 Prepare a spiking solution containing each of Che
Internal standards using the procedures described In
paragraphs 1.4.4 and 1.4.5. It is recommended that
the secondary dilution standard be prepared at a
concentration of 25 ug/mL of each internal standard
compound. The addition of 10 uL of this standard
to 5.0 mL of sample or calibration standard would
be equivalent of 50 ug/L.
1.5.3.3 Analyze each calibration standard, according to
paragraph 1.7 adding 10 uL of internal standard
spiking solution directly to the syringe. Tabulate
the area response of the characteristic ions against
concentration for each compound and internal standard
and calculate response factors (RF) for each compound
using equation 1.
EQ. 1 RF
A,
• — 2
C-10
5/84
-------
IV.
Where:
Ax • Area of the characteristic ion for the compound
to be measured.
Alg • Area of the characteristic ion for the
specific internal standard from Exhibit E.
C^g • Concentration of the internal standard.
GX • Concentration of the compound to be measured.
1.5.3.4 The average response factor (RF) must be calculated
for all compounds. A system performance check must
be Bade before this calibration curve is used. Five
compounds (the system performance check compounds)
are checked for a minimum average response factor.
These compounds (the SPCC) are chloromethane, 1,1-
dichloroethane, bromoform, 1,1,2,2-tetrachloroethane,
and chlorobenzene. Five compounds (the calibration
check compounds, CCC) are used to evaluate the curve.
Calculate the Z Relative Standard Deviation (ZRSD)
of RF values over the working range of the curve.
A minimum ZRSD for each CCC must be met before the
curve Is valid.
ZRSD • Standard deviation z 100
mean
See instructions for Form VI, Initial Calibration
Data for more details.
1.5.3.5 Check of the calibration curve should be performed
once every 12 hours. These criteria are described in
detail in the instructions for Form VII, Continuing
Calibration Check. The minimum response factor for
the system performance check compounds must be checked
If this criteria is met, the response factor of all
C-ll
5/8-
-------
compounds a.e calculated and reported. A percent
difference of the daily response factor (12 hour)
compared to the average response factor from the
initial curve is calculated. The maximum percent
difference allowed for each compound flagged as
'CCC' in Form Vll is checked. Only after both
these criteria are met can sample analysis begin.
1.5.3.6 Internal standard responses and retention times in
all samples must be evaluated Immediately after or
during data acquisition. If the retention time for
any internal standard changes by more than 30 seconds
from the latest daily (12 hour) calibration standard,
the chromatographic system must be inspected for mal-
functions and corrections made as required. If the
extracted ion current profile (E1CP) area for any
internal standard changes by more than a factor of
two (-5OX to -Hi002), the mass spectrometric system
must be inspected for malfunction and corrections
made as appropriate. When corrections are made,
re-analysis of samples analyzed while the system
was malfunctioning is necessary. Retention time and
E1CP area records shall be maintained in appropriate
form by the laboratory as a part of its internal
quality control (Exhibit E).
1.6 CC/MS Operating Conditions
1.6.1 These performance tests require the following instrumental
parameters:
Electron Energy: 70 Volts (nominal)
Mass Range: 35 - 260
Scan Time: to give at least 5 scans per peak
but not to exceed 7 seconds per scan.
be
Scne
-------
1.7 Sample Analysis
1.7.1 Water Samples
1.7.1.1 All samples and standard solutions Must be allowed to
warm to ambient temperature before analysis.
1.7.1.2 Recommended operating conditions for the gas chromato-
graph - Column conditions: Carbopak B (60/80 nesh with
1Z SP-1000 pakced in a 6 foot by 2 sn ID glass column
with helium carrier gas at • flow rate of 30 »L/min.
Column temperature is isothermal at 45*C for 3 minutes,
then programmed at 8*C per minute to 220*C and held
for 15 minutes.
1.7.1.3 After achieving the key ion abundance criteria, cali-
brate the system daily as described in Exhibit E.
1.7.1.4 Adjust the purge gas (helium) flow rate to 40 + 3 mL/
min. Variations from this flow rate may be necessary to
achieve better purging and collection efficiencies for
some compounds, particularly chloromethane and bromoform.
1.7.1.5 Remove the plunger from a 5 mL syringe and attach a
closed syringe valve. Open the sample or standard
bottle which has been allowed to come to ambient temper-
ature, and carefully pour the sample into the syringe
barrel to just short of overflowing. Beplace the
•yringe plunger and compress the sample. Open the
syringe valve and vent any residual air while adjusting
the sample volume to 5.0 mL. This process of taking an
aliquot destroys the validity of the sample for future
analysis so if there is only one TOA rial, the analyst
should fill a second syringe at this time to protect
against possible loss of sample integrity* This second
sample is maintained only until such a time when the
C-13
-------
IV.
analyst has determined chat the first sample has been
analyzed properly. Filling one 20 mL syringe would
allow the use of only one syringe. If a second
analysis is needed from Che 20 mL syringe, it must be
analyzed within 24 hours. Care must also be taken to
prevent air from leaking inco Che syringe.
1.7.1.6 The purgeable organics screening procedure (SecCion
III, paragraph 1.0), If used, will have shown the
approximate concentrations of major sample components.
If a dilution of the sample vas indicated, this
dilution shall be made just prior to GC/HS analysis
of the sample.
1.7.1.6.1 The following procedure vill allow for
dilutions near the calculated dilution
factor from the screening procedure:
o All dilutions are made in volumetric
flasks (10 mL to 100 mL).
o Select the volumetric flask that will
allow for the necessary dilution. Inter-
mediate dilutions may be necessary for
extremely large dilutions.
o Calculate the approximate volume of
reagent water which will be added to
the volumetric flask selected and add
slightly leas than this quantity of
reagent water to the flask.
o Inject the proper aliquot from the
syringe prepared in paragraph 1.7.1.5
into the volumetric flask. Aliquots
of less than 1 mL increments are pro-
hibited. Dilute the flask to the mark
with reagent water. Cap the flask,
invert, and shake three times.
o Pill a 5 mL syringe with the diluted
•ample as in paragraph 1.7.1.5.
C-14
5/84
-------
o If this is an intermediate dilution,
use it and repeat above procedure to
achieve larger dilutions.
1.7.1.7 Add 10.0 uL of the surrogate aplking solution (1.4.6)
and 10.0 uL of the internal standard spiking solution
(1.5.3.2) through the valve bore of the syringe, then
close the valve. The surrogate and internal standards
nay be mixed and added as a single spiking solution.
The addition of 10 uL of the surrogate spiking solution
to 5nL of sample is equivalent to a concentration of
50 ug/L of each surrogate standard*
1.7.1.8 Attach the syringe-syringe valve assembly to the
syringe valve on the purging device* Open the syringe
valves and inject the sample into the purging chamber.
1.7.1.9 Close both valves and purge the sample for 12.0+ 0.1
<
minutes at ambient temperature.
1.7.1.10 At the conclusion of the purge time, attach the trap
to the chromatograph, adjust the device to the desorb
mode, and begin the gas chromatographic temperature
rogram. Concurrently, introduce the trapped materials
to the gas chrommatographic column by rapidly heating
the trap to 180'C while backf lushing the trap with an
inert gas between 20 and 60 mL/min for four minutes.
If this rapid heating requirement cannot be met, the
gas chromatographic column must be used as a secondary
trap by cooling it to 30*C (or subambient^ if problems
persist) Instead of the recommended initial temperature
of 45°C.
1.7.1.11 While the trap is being desorbed into the gas chroma -
tograph, empty the purging chamber* Wash the chamber
with a minimum of two 5 mL flushes of reagent water
to avoid carry-over of pollutant compounds.
C-15
5/84
-------
IV.
1.7.1.12 After detorbing the Maple for four minutes, recondi-
tion the trap by returning the purge and trap device
to the purge »ode. Wait 15 seconds then close the
syringe valve on the purging device to begin gas flow
through the trap.. The trap temperature should be
maintained at 180*C. Trap temperatures up to 230*C
nay be employed, however the higher temperature will
shorten the useful life of the trap. After approxi-
mately seven minutes turn off the trap heater and
open the syringe valve to stop the gas flow through
the trap. When cool, the trap is ready for the next
sample.
1.7.1.13 If the initial analysis of a sample or a dilution of
a sample indicates saturated ions of HSL compounds,
the sample must be reanalyzed at a higher dilution.
When a sample is analyzed that has saturated ions
from a compound, this analysis must be followed by a
blank reagent water analysis. If the blank analysis
is not free of interferences, the system must be
decontaminated. Sample analysis may not resume until
a blank can be analyzed that is free of Interferences.
1.7.1.14 For low and medium level water samples, add 10 uL
of the matrix spike solution (1.4.7) to the 5mL of
sample purged. Disregarding any dilutions, this is
equivalent to a concentration of 50 ug/L of each
matrix spike standard.
1.7.1.15 All dilutions must keep the response of the major
constituents (previously saturated peaks) in the
upper half of the linear range of the curve.
C-16
5/84
-------
IV.
1.7.2 Sediment/Soil Samples
Two approaches may be taken to determine whether the low level
or medium level method may be followed.
o Assume the sample is low level and analyze a 5 gram sample
o Use the X factor calculated from the optional Hexadecane
screen (Section 111), paragraph 1.7.2.1.3
If/freaks are saturated from the analysis of a 5 gran sample,
a smaller sample size oust be analyzed to prevent saturation.
However, the smallest sample size permitted is 1 gm. If smaller
than 1 gram sample size is needed to prevent saturation, the
medium level method must be used.
1.7.2.1 Low Level Method
The low level method is based on purging a heated
sediment/soil sample mixed with reagent water
containing the surrogate and internal standards.
Use 5 grams of sample or use the X Factor to determine
the sample size for purging.
o If the X Factor is 0 (no peaks noted on the
hexadecane screen), analyze a 5 gm sample.
o If the X Factor is between 0 and 1.0, analyze
a 1 gm sample.
1.7.2.1.1 The GC/MS system should be set up as in
1.7.1.2 - 1.7.1. A. This should be done
prior to the preparation of the sample
to avoid loss of volatiles from standards
and sample.
C-17
Rev: 9/84
-------
1.7.2.1.2 Leaove the plunger Iran a 5 ml "Luerlock"
type syringe equipped with a syringe valve
and fill until overflowing with reagent
water. Leplace the plunger and compress
the water to vent trapped air. Adjust the
volume to 5.0 mL. Add 10 uL each of the
•urrogate spiking solution (1.4.6) and the
Internal standard solution to the syringe
through the valve. (Surrogate spiking
solution and internal standard solution may
be mixed together). The addition of 10 uL
of the surrogate spiking solution to 5 grs
of sediment/ soil is equivalent to 50 ug/kg
of each surrogate standard.
1.7.2.1.3 The sample (for volatile organic*) consists
of Che entire contents of Che sample con-
tainer. Do not discard any supernatant
liquids. Hiz the contents of Che sample
container with a narrow metal spatula.
Weigh the amount determined in 1.7.2.1 Into
a tared purge device. Use a top loading
» balance. Note and record the actual weight
to the nearest 0.1 g*c.
1.7.2.1.3.1 Immediately after weighing the
sample weigh 5-10 g of the
sediment into a tared crucible.
Determine the percent moisture
by drying overnight at 105*C.
Allow to cool in a desiccator
before weighing. Concentrations
of Individual analytes will be
reported relative to che dry
weight of sediment.
C-18
lev: 9/84
-------
IV.
Percent aoifture
gm of saaple-gTB of dry cample
go of sample * 1^)U " * moisture
1.7.2.1.4 Add the .spiked reagent water to the purge
device and connect the device to the purge
and trap system. NOTL: Steps 1.7.2.1.2 -
1.7.2.1.3, prior to the attachment of the
purge device, must be performed rapidly to
avoid loss of volatile organics. These
steps Dust be performed in a laboratory free
of solvent fumes.
1.7.2.1.5 Heat the sample to AO°C ± 1'C and purge the
sample for 12 ±0.1 minutes.
1.7.2.1.6 Proceed with the analysis as outlined in
1.7.1.10 - 1.7.1.13. Use 5 ml of the
same reagent water as the reagent blank.
1.7.2.1.7 For low level sediment/soils add 10 uL of
the matrix spike solution (1.4.7) to the 5
mL of water (I."/.2.1.2). The concentration
for a 5 gram sample would be equivalent to
50 ug/kg of each matrix spike standard.
1.7.2.2 Medium Level Method
The medium level method is based on extracting the sedi-
ment/soil sample with methanol. An aliquot of the meth-
anol extract is added to reagent water containing the
surrogate and internal standards. This is purged at
ambient temperature. All samples with an X Factor >1.0
should be analyzed by the medium level method. If sat-
urated peaks occurred or would occur when a 1 gram sam-
ple was analyzed, the medium level method must be used.
C-19
Rev: 9/84
-------
IV.
1.7.2.2.1 The sample (for volatile organics)
consists of the entire contents of the
sample container. Do not discard any
supernatent liquids. Hix the contents
of the sample container with a narrow
metal spatula. Weigh A go (wet weight)
into a tared 15 ml vial. Use a top
loading balance. Note a nd record the
actual weight to the nearest 0.1 gin.
Determine the percent moisture as In
1.7.2.1.3.1.
1.7.2.2.2 Quickly add 9.0 ml of methanol, then
1.0 mL of Che surrogate spiking solution
i
to the vial. Cap and shake for 2 minutes.
NOTE: Steps 1.7.2.2.1 and 1.7.2.2.2 must
be performed rapidly to avoid loss of
volatile organics. These steps must be
performed in a laboratory free of solvent
fumes.
1.7.2.2.3 Pipette for storage approximately 1 mL of
extract to a GC vial using a disposable
pipet. The remainder may be disposed of.
Transfer approximately 1 mL of the
reagent methanol to a GC vial for use
as the method blank for each case or
set of 20 samples, whichever is greater.
These extracts may be stored in the dark
at 4°C prior to analysis.
C-20
Rev: 9/84
-------
IV.
The addition of a 100 uL aliquot of each
of these extracts In paragraph 1.7.2.2.6
will give a concentration equivalent to
6,200 ug/kg of each surrogate standard.
1.7.2.2.4 The GC/MS system should be set up as In
1.7.1.2 - 1.7.1.A. This should be done
prior to the addition of the nethanol
extract to reagent water.
1.7.2.2.5 The following table can be used to deter-
mine the volume of methanol extract to
add to the 5 mL of reagent water for
analysis. If the Hexadecane screen
procedure was followed use the X factor
(Option B) or the estimated concentration
(Option A) to determine the appropriate
volume. Otherwise, estimate the concen-
tration range of the sample from the low
level analysis to determine the appropriate
volume. If the sample was submitted as a
medium level sample, start with 100 uL.
All dilutions must keep the response of
the major constituents (previously saturated
peaks) in the upper half of linear range
of the curve.
C-21
Rev: 9/84
-------
IV.
X Factor
Estimated
Concentration Range*/
Take this Volume of
Methanol Extract2/
ug/kg
uL
0.25 - 5.0
0.5 - 10.0
2.5 - 50.0
12.5 - 250
500 - 10,000
1000 - 20,000
5000 - 100,000
25,000 - 500,000
100
50
10
100 of 1/50 dilution3/
Calculate appropriate dilution factor for concentrations exceeding the table.
I/ Actual concentration ranges could be 10 to 20 times higher than this if
the compounds are halogenated and the estimates are from GC/FID.
21 The volume of methanol added to the 5 mL of water being purged should be
kept constant. Therefore, add to the 5 mL syringe whatever volume of
methanol is necessary to maintain a volume of 100 uL added to the syringe.
3/ Dilute an aliquot of the methanol extract and then take 100 uL for
analysis.
C-22
Rev: 9/8A
-------
i v
1.7.2.2.6 Remove the plunger froo a 5 mL "Luerlock"
type syringe equipped with a syringe valve
and fill until overflowing with reagent
water. Replace the plunger and compress
the water to vent trapped air. Adjust the
volume to 4.9 mL. Pull the plunger back
to 5 mL to allow volume for the addition
of sample and standards. Add 10 uL of the
internal standard solution. Also add the
volume of methanol extract determined in
1.7.2.2.5 and a volume of aethanol solvent
to total 100 uL (excluding methanol in
standards).
1.7.2.2.7 Attach the syringe-syringe valve assembly
to the syringe valve or the purging device.
Open the syringe valve and inject the water/
methanol sample into the purging chamber.
1.7.2.2.8 Proceed with the analysis as outlined in
1.7.1.9 - 1.7.1.13. Analyze all reagent
blanks on the same instrument as the sam-
ples. The standards should also contain
100 uL of methanol to simulate the sample
conditions.
1.7.2.2.9 For a aatrix spike in the medium level sed-
iment/soil samples, add 8.0 mL of methanol,
1.0 mL^of surrogate spike solution (1.A.6),
and 1.0 mL of matrix spike solution (1.4.7)
in paragraph 1.7.2.2.2. This results in a
6,200 ug/kg concentration of each matrix
spike standard when added to a 4 gm sample.
Add a 100 uL aliquot of this extract to 5 mL
of water for purging (as per paragraph
1.7.2.2.6).
Rev: 9/84
C-23
-------
IV.
Qualitative Analysis
1.8.1 The target compounds listed in the Hazardous Substances List
(USL), Exhibit C, shall be identified by an analyst competent in
the interpretation of mass spectra (see Bidder Pre-Award Labora-
tory Evaluation Criteria) by comparison of the sample mass spec-
trum to the mass spectrum of a standard of the suspected compound.
Two criteria must be satisfied to verify the identifications: (1)
elution of the sample component at the same GC relative retention
time as the standard component, and (2) correspondence of the
sample component and standard component mass spectra.
1.8.1.1 For establishing correspondence of the GC relative
retention time (RRT), the sample component RRT must com-
pare within + 0.06 RRT units of the RRT of the standard
component. For reference, the standard must be run on
the sane shift as the sample. If coelution of interfer-
ing components prohibits accurate assignment of the sam-
ple component RRT from the total ion chromatogram, the
RRT should be assigned by using extracted ion current
profiles for ions unique to the component of interest.
1.8.1.2 For comparison of standard and sample component mass
spectra, mass spectra obtained on the contractor's GC/
MS are required. Once obtained, these standard spectra
may be used for identification purposes, only if the
contractor's GC/MS meets the daily turning requirements
for BFB or DFTPP. These standard spectra may be
obtained from the run used to obtain reference RRTs.
1.8.1.3 The requirements for qualitative verification by
comparison of mass spectra are as follows:
(1) All ions present in the standard mass spectra at
a relative intensity greater than 10 Z (most abundant
ion in the spectrum equals 100Z) must be present in
the sample spectrum.
C-24
Rev: 9/84
-------
IV.
(2) The relative intensities of ions specified in (1)
•use agree within plus or minus 20Z between the stan-
dard and sample spectra. (Example: For an ion with
an abundance of 50Z in the standard spectra, the
corresponding sample abundance Bust be between 30
and 70 percent).
(3) lone greater than 10Z in the sample spectrum but
not present in the standard spectrum must be consid-
ered and accounted for by the analyst making the
comparison. In Task III, the verification process
should favor false negatives.
1.6.2 A library search shall be executed for Non-HSL sample components
for the purpose of tentative identification. For this purpose,
the most recent available version of the EPA/NIH Mass Spectral
Library shall be used. Computer generated library search rou-
tines should not use normalization routines that would misrepre-
sent the library or unknown spectra when compared to each other.
1.8.2.1 Up to 10 substances of greatest apparent concentra-
tion not listed in Exhibit C for the purgeable organic
fraction shall be tentatively identified via a forward
search of the EPA/NIH mass spectral library. (Sub-
stances with responses less than 102 of the internal
standard are not required to be searched in this
fashion). Only after visual comparison of sample
spectra with the nearest library searches will the mass
spectral interpretation specialist assign a tentative
identification.
1.8.2.2 Guidelines for making tentative identification: (1)
Relative intensities of major ions In the reference
spectrum (ions greater than 10Z of Che most abundant
ion) should be present in the sample spectrum.
c_25 9/84
-------
IV.
(2) The relative intensities of the major ions should
•gree within + 20Z. (Example: For an ion with an
abundance of 50 percent of the standard spectra, the
corresponding sample Ion abundance Bust be between 30
and 70 percent.)
(3) Molecular ions present in reference spectrum
should be present in sample spectrum.
(4) Ions present in the saaple spectrun but Dot in
the reference spectrum should be reviewed for possible
background contamination or presence of co-eluting
compounds.
(5) lone present in the reference spectrum but not in
the sample spectrum should be reviewed for possible
subtraction from the sample spectrum because of back-
ground contamination or co-eluting compounds. Data
system library reduction programs can sometimes
create these discrepancies.
•%
1.8.2.3 If in the opinion of the mass spectral specialist,
no valid tentative identification can be made, the
compound should be reported as unknown. The mass
spectral specialist should give additional classif-
ication of the unknown compound, if possible (i.e.
unknown aromatic, unknown hydrocarbon, unknown acid
type, unknown chlorinated compound). If probable
molecular weights can be distinguished, include them.
1.9 Quantitative Analysis
1.9.1 HSL components identified shall be quantified by the internal
standard method. The Internal standard used shall be the one
nearest the retention time to that of a given analyte. The
C-26
5/84
-------
IV.
EICP area of the characteristic ions of analytes listed in
Tables 2 and 3 are used. The response factor (RF) from the
dally standard analysis is used to calculate the concentration
in the sample. Use the response factor as determined in para-
graph 1.5.3.3 and the following equations:
Water (low and medium level)
Concentration ug/L - (Ais)(RF)(Vo)
Where:
Ax • Area of the characteristic ion for the compound to be
measured
Ais • Area of the characteristic ion for the specific internal
standard from Exhibit E.
Ig - Amount of internal standard added in nanograms (ng)
V0 • Volume of water purged in mlllillters (ml) (take into
account any dilutions)
Sediment/Soil (medium level)
Concentration ug/kg - (A3C)(Ig)(Vt)
(Als)(RF)(V1)(W6)(D)
Sediment/Soil (low level)
Concentration ug/kg - ^^x'^s'
(Als)(RF)(Ws)(D)
(Dry weight basis)
Where:
A,, Ig, Als - same as for water, above
Vt - Volume of total extract (uL) (use 10,000 uL
or a factor of this when dilutions are made)
VA - Volume of extract added (uL) for purging
D • 100 - t moisture
100
Wg - Weight of sample extracted (gm) or purged
C-27 ' Rev; 9/86
-------
IV.
1.9.2 An estimated concentration for Non-HSL components tentatively
Identified shall be quantified by the Internal standard aethod.
For quantification, the nearest internal standard free of inter-
f ereces shall be used.
1.9.2.1 The formula for calculating concentrations is the
same as in paragraph 1.9.1. Total area counts ffoo
the total ion chroma tograms are to be used for both
the compound to be measured and the Internal standard.
A response factor (RF) of one (1) is to be assumed.
The value from this quantitatlon shall be qualified
as estimated. This estimated concentration should be
calculated for all tentatively identified compounds
as well as those identified as unknowns.
1.9.2.2 Xylenes (o,m, & p - isomers) are to be reported as
total Xylenes. Since o- and p-Xylene overlap, the
Xylenes must be quantltated versus m-Xylene. Tne
concentration of all Xylene Isomers must be added
together to give the total.
1.9.3 Calculate surrogate standard recovery on all samples, blanks
and spikes. Determine if recovery is within limits and report
on appropriate form.
1.9.3.1 Calculation for surrogate recovery.
Percent Surrogate Recovery • Qd_ X 100Z
where: Q^ • quantity determined by analysis
Qa • quantity added to sample
C-28
Rev: 9/84
-------
IV.
1.9.3.2 If recovery is-not within limits, the following is
required:
o Check to be sure there are no errors in calcula-
tions, surrogate solutions and Internal standards.
Also, check instrument performance.
o Recalculate the sample data if any of the above
checks reveal a problem.
o Reanalyze the sample if none of the above are a
problem.
o Report the data from both analyses along with
the surrogate data from both.
Table 2
Characteristic Ions for Surrogate and
Internal Standards for Volatile Organic Compounds
Compound Primary Ion Secondary Ion(s)
SURROGATE STANDARDS
4-Bromofluorobenzene 95 174, 176
1,2-Dichloroethane d-4 65 102
Toluene d-b 98 70, 100
INTERNAL STANDARDS
Bromochloromethane 128 49, 130, 51
1,4-Difluorobenzene 114 63, 88
Chlorobenzene d-5 117 82, 119
-29
Rev: 9/84
-------
IV.
Table 3
Characteristic lone for Volatile HSL Compounds
Parameter
Primary Ion*
Secondary Ion(s)
Chloromethane
Bromomechane
Vinyl chloride
Cnloroethane
Methylene chloride
Acetone
Carbon disulfide
1 , 1-Dichloroethene
1 , 1 -Di chl or oe thane
trans-1 ,2-Dichloroethene
Chloroform
1 ,2-Di chl or oe thane
2-Butanone
1,1, 1-Trichloroethane
Carbon tetrachloride
Vinyl acetate
Bromodi chloromethane
1 , 1 ,2,2-Tetrachloroethane
1 ,2-Di chloropropane
trans-1 ,3-Dichloropropene
Tricolor oethene
Dibromochl or ome thane
1 , 1 ,2-Trichloroethane
Benzene
cis-1 ,3-Dichloropropene
2-Chloroethyl vinyl ether
Bromoform
2-Hexanone
4-Methyl-2-pentanone
Tetrachloroethene
Toluene
Chlorobenzene
Ethyl benzene
Styrene
Total xylenes
50
94
62
64
84
A3
76
96
63
96
83
62
72
97
117
43
83
83
63
75
130
129
97
78
75
63
173
43
43
164
92
112
106
104
106
52
96
64
66
««9, 51, 86
58
78
61, 98
65, 83, 85, 98, 100
61, 98
85
64, 100, 98
57
99, 117, 119
119, 121
86
85, 129
85, 131, 133, 166
65, 114
77
95, 97, 132
208, 206
83, 85, 99, 132, 134
-
77
65, 106
171, 175, 250, 252, 254, 256
58, 57, 100 '
58, 100
129, 131, 166
91
114
91
78, 103
91
* The primary ion should be used unless interferences are present, in which
case, a secondary ion may be used.
C-30
Rev: 9/84
-------
IV.
00
f S tmpl* In/ft
;•- /7cm 20 go vat irnngt noodlo
6mm 00 Aubbor Soptum
^ 10mm 00 */nin OD
Inloi -^/Stomlou Stool
'/tm OD1
10mm gloss frit
modium porosity
moloeulor
purgo
ooi lihot
Purgo fog
flow control
Pocti.
Gloss
wool
Grode 75
gol
Bmm
Bem
TonoM 16cm
3% ov-1 1ern\
Glott
wool
Cotnpfouion tilting
-nut ond forrulot
14ft 7+/foot fottttonco
wiro wroppod told
Thormocoupto/conrroHor
-tontot
Tubing 25 em
0.105 in I.D
0.128 in. O.D
ttomlost ttool
ur* 2.
Trop inlot
Trop poetingt ond construction to includo dotoro
C-31
5/84
-------
Corner got flow control
Prouuro rogulolor
Purge got
flow con If of
13X moloculor
tittor
option*! 4 -port column
vol
Int9t
control
Not,
All linot oot*
trop ond GC
thauM oo hootoo1
9 icn+motic of punjo ono" tnp dovteo — purge modo
Corrtof got ffow controf
*rot*uro roffulotor
Purgo got .
How control I ,
13X moloculor
' fiHor
L_L ^«- Confirmatory column
To
column
optionol 4-port column
tolocvon vorro
Moto
AH linot
trop ond GC
tnouH oo hooto*
to96'C
4. Schomottc of purgo on* trop oo*ico — oo*or» moo*
C-32
5/84
-------
PURGE INLET FITTING
F V3
SAMPLE OUTLET FITTING
3 > 6mm 0 0 GLASS TUBING
SEPTUM
CAP
40ml VIAL
Figure 5. Low Soils Implnger
C-33
5/84
-------
STANDAFID METHOD 209 G
6060A
-------
209 G. -Volatile and Fixed Matter in Nonfiltrable Residue and in
Solid and Semisolid Samples
1 General Discussion
This method is applicable to the deter-
mination of total residue on evaporation
and its fixed and volatile fractions in such
solid and semisolid samples as river and
lake sediments, sludges separated from
water and waste*ater treatment process-
es, and sludge cakes from vacuum filtra-
tion, centnfugation. or other sludge dewa-
tenng processes.
The determination of both total and vol-
atile residue in these materials is subject to
negative error due to loss of ammonium
carbonate [(NH4)..CO,] and volatile organ-
ic matter while drying. Although this is
true also for wastewater. the effect tends
to be more pronounced with sediments.
and especially with sludges and sludge
cakes.
The mass of organic matter recovered
from sludge and sediment requires a long-
er ignition time than that specified for resi-
due from wastewaters. effluents, or pol-
luted waters. Carefully observe specified
ignition time and temperature to control
losses of volatile inorganic salts.
Make all weighings quickly because wet
samples tend to lose weight by evapora-
tion. After drying or ignition, residues of-
ten are very hygroscopic and rapidly ab-
sorb moisture from the air.
2. Apparatus
See Sections 209A.2 and 209B.2.
3 Procedure
a. Solid uml u-muuliJ
1) Total residue and moisture —
ai Preparation of evaporating dish—Ig-
nite a clean evaporating dish at 550 = 50 C
for 1 hr in a muffle furnace Cool in a des-
iccator, weigh, and store in a desiccator
until ready for use.
bi Fluid samples—if the sample con-
tains enough moisture to flow more or less
readily, stir to homogenize, place 25 to
50 g in a prepared evaporating dish, and
weigh to the nearest 10 mg. Evaporate to
dry ness on a water bath, drv at 103 C for 1
hr. cool in an individual desiccator con-
taining fresh desiccant. and weigh.
c) Solid samples —If the sample con-
sists of discrete pieces of solid material
(dew-atered sludge, for example!, take
cores from each piece with a No. 7 cork
borer or pulverize the entire sample
coarsely on a clean surface b\ hand, using
rubber gloves. Place 25 to 50 g in a pre-
pared evaporating dish and weigh to the
nearest 10 mg. Place in an oven at 103 C
overnight. Cool in an individual desiccator
containing fresh desiccant and weigh Pro-
longed heating may result in a loss of vola-
tile organic matter and (NH<)..CO:. but
it usually is necessary to dry samples
thoroughly.
2> Volatile residue —Determine volatile
residue, including organic matter and vol-
atile inorganic salts, on (he total residue
C-34
-------
obtained in 1) above. Avoid loss of solids
by decrepitation bv placing dish in a cool
muffle furnace, heating furnace to 550 C.
and igniting for 60 mm. (First ignite sam-
ples containing large amounts of organic
matter over a gas burner and under an ex-
haust hood in the presence of adequate air
to lessen losses due to reducing conditions
and to avoid odors in the laboratory.) Cool
in a desiccator and reweigh Report results
as fixed residue (percent ash) and volatile
residue.
h. \onfillrahle residue /suspended
maiieri:
1) Preparation of glass-fiber filter-
Place a glass-fiber filter in a membrane fil-
ter holder. Hirsch funnel, or Buchner fun-
nel, with crinkled surface of filter facing
upward. Apply vacuum to the assembled
apparatus to seat filter. With vacuum ap-
plied, wash filter with three successive 20-
mL portions of distilled water. After the
water has filtered through, disconnect vac-
uum, remove filter, transfer to an alumi-
num or stainless steel planchet as a sup-
port, and dry in an oven at 103 C for 1 hr
(30 mm in a mechanical convection oven).
If volatile matter is not to be determined,
coo! filter in a desiccator to balance tem-
perature and weigh. If volatile matter is to
be determined, transfer filter to a muffle
furnace and ignite at 550 C for 15 min. Re-
move filter from furnace, place in a desic-
cator until cooled to balance temperature.
and weigh.
21 Treatment of sample—Except for
samples that contain high concentrations
of filtrable matter, or that filter very slow-
ly, select a sample volume 214 mL/cm2
filter area.
Place prepared filter in membrane filter
holder. Hirsch funnel, or Buchner funnel,
with wrinkled surface upward. With vacu-
um applied, wet filter with distilled water
to seat it against holder or funnel. Measure
well-mixed sample with a wide-tip pipet
or graduated cylinder. Filter sample
through filter using suction. Leaving suc-
tion on. wash apparatus three times
10-mL portions of distilled water, allowing
complete drainage between washings Dis-
continue suction, remove filter and dry t0
constant weight (see 209B.3r) at 103 C for
1 hr in an oven (30 min in a mechanical
convection oven). After drying, cool filter
in a desiccator to balance temperature and
weigh.
3) Filtration with Gooch crucibles—Al-
ternatively, use glass-fiber filters of 2.2 or
2.4 cm diam with Gooch crucibles and fo|.
low the procedure in Section 209D.3fc.
4i Ignition—Ignite filter with its non-
filtrable residue (total suspended matter)
for 15 min at 550 ± 50 C. transfer to a des-
iccator, cool to balance temperature, and
weigh.
4. Calculation
a. Solid and semisolid samples:
total residue =
volatile residue
fixed residue
A x lop
B
(A - O x 100
C x |00
b Sonfilirable residue (suspended mol-
ten:
mg nonfihrable volatile residue L
= (D ~ & * '-OP0
sample volume. mL
mg nonfiltrable fixed residue1!.
= C x i.OQO
sample volume. mL
where:
A = weight of dried solids, mg,
B = weight of wet sample, mg,
C = weight of ash, mg.
D = weight of residue before ignition, mg,
and
£ = weight of residue after ignition, mg.
5. Precision and Accuracy
See Section 209D.5.
C-35
-------
for Chemical Analysis of Water
Met"*
«nd Waste* 1974 L' S EPA. Technology
»nsfer. 6:?- '6- 74-003. pp 266-267
2~SoKOLOFF. V.p 1933 W.ter of crystalliza-
tion in tolaJ solids of water analysis I rut
EnK Chem.. Anal Ed 5 336
209 I. Bibliography
. EJ & H H WAGESHALS 1923
Studies of representative sewage plants.
Puh Health Bull No 132
HOWARD. CS 1933 Determination of total
dissolved solids in water analysis Ind
Eng Chem . Anal Ed 5 4
SIMONS. GE &B MORE> 1941. The effect of
drying time on the determination of solids
in sewage and sewage sludges Sewage
Works J 1^936
FISCHER. A.J AGE SIMONS 1944 The de-
termination of settleable sewage solids by
weight Hater Works Sex ape 91.37.
DICES.J iFE NUSSBERGER 1956 Noteson
the determination of suspended solids
Se«agf Ind. Wanes 28.237
CMANIN. G.. E H CHOW . R B ALEXANDER it.
j POWERS. 1958 Use of glass fiber filter
medium in the suspended solids determina-
tion Sewa/te Ind Wastes 30 1062
NISBALM. I 1958. New method for determina-
tion of suspended solids Sewage Ind.
Wastes 30 1066.
SMITH. A L & A.E GREENBERG 1963 Evalu-
ation of methods for determining sus-
pended solids in wastewater. J Water Pol-
iui Control Fed 35 940
GOODMAN. B L 1964 Processing thickened
sludge with chemical conditioners Pages
78 et seq in Sludge Concentration. Filtra-
tion and Incineration L'rm Michigan Con-
tinued Education Ser No. 113. Ann Arbor.
WYCKOFF. B M 1964 Rapid solids determina-
tion using glass fiber filters. Water Sex age
Works 111:277
C-36
-------
APPENDIX D
SUPPLEMENTAL DATA
0440B
-------
BSXOWUl. t*NTS
TABLE D-l. SOIL TEMPERATURE (°F)
Time
0 (1150)
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100
105
110
115
120
125
130
135
140
145
150
155
160
165
170
Test
Run 1
77
71
71
74
77
77
79
79
80
81
81
81
81
81
81
81
82
83
87
90
95
98
99
103
106
*
*
*
141
141
142
141
141
Test
Run 2
75
85
90
91
90
90
88
88
87
87
88
88
89
90
91
91
90
91
90
91
92
92
92
91
91
91
91
91
92
92
92
91
91
91
92
Test
Run 3
68
59
59
62
64
74
78
100
108
119
119
118
123
126
109
112
116
118
123
127
129
125
126
125
125
128
127
114
118
121
123
Test
Run 4
57
52
52
53
56
59
62
65
68
72
75
81
85
89
100
104
108
111
113
113
114
115
116
117
117
117
118
118
109
112
112
•Thermocouple popped out of soil, temperature measured
represented air temperature in the unit.
Not measured (sampling soil).
D-l
0440B
-------
TABLE D-l. (CONTINUED)
Time
175
180
185
190
195
200
205
210
215
220
225
230
235
240
245
250
255
260
265
270
275
280
285
Test
Run 1
143
144
143
143
143
143
144
143
140
Test
Run 2
92
91
91
92
92
92
92
93
92
91
91
91
92
93
93
Test
Run 3
123
124
123
121
120
121
121
123
124
123
128
123
128
128
128
128
130
130
128
129
128
128
Test
Run 4
115
116
118
117
118
120
122
121
121
"- — —
— — —
113
118 ,
118
115
116
116
120
121
120
121
121
122
Not measured (sampling soil)
0440B
D-2
-------
TABLE D-2.
TOTAL VOC CONCENTRATION IN OUTLET AIR STREAM
(PPM/VOLUME AS BENZENE)
Time
0
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100
105
110
115
120
125
130
135
140
145
150
Test
Run 1
___
21
20
19
18
18
18
18
18
18
18
17
18
18
18
17
18
17
18
17
16
15
15
14
14
12
9
Test
Run 2
12
11
11
10
10
10
10
9
9
9
9
9
8
8
8
8
8
7
7
7
6
6
5
5
4
4
3
Test
Run 3
7
6
6
6
5
5
4
4
4
4
4
3
3
3
3
3
3
2
2
3
2
3
3
3
3
Test
Run 4
94
93
90
88
87
85
83
81
80
76
73
67
66
70
68
66
65
62
62
68
72
72
72
_•_ — — —
Not measured (sampling soil)
0440B
D-3
-------
TABLE D-2. (CONTINUED)
Time
155
160
165
170
175
180
185
190
195
200
205
210
215
220
225
230
235
240
245
250
255
260
265
270
275
280
285
Test
Run 1
7
5
5
5
4
5
5
5
4
4
3
3
2
2
2
Test
Run 2
3
3
2
2
2
2
2
2
2
2
2
2
2
1
1
1
1
1
Test
Run 3
2
2
2
2
2
2
2
2
1
2
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
Test
Run 4
71
61
60
60
60
60
62
62
61
62
62
62
63
60
59
60
61
64
65
65
63
60
56
53
51
Not measured (sampling soil)
0440B
D-4
-------
TABLE D-3. AIR TEMPERATURES (°F)
Time
0
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100
105
110
115
120
125
130
135
140
145
150
Test
Inlet
90
109
134
145
152
156
160
162
165
164
166
166
167
168
169
169
168
168
169
167
168
167
166
166
167
167
167
168
168
169
run
1
Outlet
94
86
84
84
84
85
86
87
87
88
89
89
90
90
91
92
91
91
91
92
98
100
100
100
100
100
100
104
106
108
Test
2
Inlet
140
138
139
140
140
141
140
141
140
140
142
142
143
143
143
143
143
143
143
144
143
143
143
145
145
145
142
143
143
143
144
run
Outlet
83
84
89
90
91
91
90
90
90
91
92
92
94
96
98
98
100
102
103
104
108
108
110
111
111
113
113
114
115
116
116
Test
3
Inlet
89
113
137
139
144
148
151
152
152
151
152
154
152
151
130
144
147
148
152
155
156
153
152
153
155
152
153
154
135
run
Outlet
83
77
75
77
77
77
77
77
78
77
78
80
79
78
77
78
81
81
82
83
83
84
88
90
92
94
97
99
91
Test
4
Inlet
89
111
123
128
132
133
135
136
138
137
138
137
139
130
133
137
137
137
138
138
140
140
140
138
140
140
128
run
Outlet
64
63
64
64
67
79
68
69
72
73
73
73
76
73
73
74
74
75
77
77
79
80
82
80
81
82
80
Not measured (sampling soil)
0440B
D-5
-------
TABLE D-3. (CONTINUED)
Time
155
150
165
170
175
180
185
190
195
200
205
210
215
220
225
230
235
240
245
250
255
260
270
275
280
285
Test
1
Inlet
170
165
170
171
173
175
172
169
170
170
_ — _
167
168
166
run
Outlet
114
117
120
120
121
125
124
123
123
122
124
124
122
Test
2
Inlet
146
147
149
148
148
149
148
147
147
148
147
147
147
147
147
147
147
148
146
run
Outlet
118
118
119
119
120
120
120
120
120
120
120
120
120
120
120
120
120
120
121
Test
3
Inlet
146
150
148
149
149
149
149
150
150
150
152
152
151
147
152
154
154
155
155
155
156
156
157
156
154
run
Outlet
91
91
90
90
92
92
94
97
97
96
97
97
98
94
94
96
100
100
100
102
104
104
104
104
104
Test
4
Inlet
133
137
137
140
140
140
140
143
144
143
143
144
135
139
141
143
144
144
146
146
147
148
145
145
run
Outlet
83
83
83
84
88
SO
90
92
93
94
96
97
88
90
90
92
93
54
95
95
97
98
99
ICO
Not measured (sampling soil)
D-6
0440B
------- |