EPA/540/2-89/023
SUPERFUNDTREATABILITY
CLEARINGHOUSE
Document Reference:
Koppers Co., Inc. "Evaluation of an Engineered Biodegradation System at the Nashua,
N.H. Site." Technical report prepared for Keystone Environmental Resources, Inc.
Approximately 106 pages. April 1987.
EPA LIBRARY NUMBER:
Superfund Treatability Clearinghouse -EWGC
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SUPERFUND TREATABILITY CLEARINGHOUSE ABSTRACT
Treatment Process:
Media:
Document Reference:
Document Type:
Contact:
Site Name:
Location of Test:
Biological - Aerobic
Soil/generic
Koppers Co., Inc. "Evaluation of an Engineered
Biodegradation System at the Nashua, N.H. Site."
Technical report prepared for Keystone Environ-
mental Resources, Inc. Approximately 106 pages.
April 1987.
Contractor/Vendor Treatability Study
Ann Hegnauer
Keystone Environmental Resources, Inc.
1050 Connecticut Avenue, NW, Suite 300
Washington, DC 20036
202-429-6552
Nashua Site NH (NPL)
Nashua, NH
BACKGROUND; The treatability study report presents the results of both
laboratory and field studies conducted by Koppers on soils from the Nashua,
N.H., NPL site. The purpose of these studies was to provide the necessary
data to evaluate a full-scale design for the Engineered Biodegradation
System (EBDS) to treat wood preservative residues found in the soils at
this site.
OPERATIONAL INFORMATION; The laboratory bench-scale studies consisted of a
soil pan study and a soil column study. The soil pan study evaluated the
influence of soil moisture, nutrients, and level of waste application on
biodegradation. The soil column study evaluated the mobility of waste
constituents in soil, air, and water.
In the pilot-scale field study, which was performed onsite, the
treatment unit with an area of 10,000 sq ft was loaded with 1 foot of
contaminated soil. The soil from the Nashua site was not characterized.
Cow manure, lime, water, and fertilizer were added, and the mixture was
rototilled to maintain aerobic conditions. The test was run for
approximately 6 months.
PERFORMANCE; Highest initial contaminant concentrations were 7707 ppm for
oil and grease, 2143 ppm for PAH, and 133 ppm for PCP. In the field
investigation, over 80X of PCP and napthalene, and 90% of the PAHs were
chemically/biologically degraded by the pilot-scale EBDS. The pilot-scale
aerobic design was applied to the soils utilizing operating parameters
(i.e., moisture content, additive agents like fertilizer and lime)
established from the bench scale study. The EBDS unit promotes the growth
of unspecified indigenous microorganisms to biodegrade contaminants.
Both the potential problems of fugitive emissions and leachate run-off
were addressed in the pilot study design. Tests results for both of the
potential problems showed that negligible amounts of runoff and fugitive
3/89-8 Document Number: EWGC
NOTE: Quality assurance of data may not be appropriate for all uses.
-------
emissions were generated. Bench-scale data and pilot-scale data is
available in the document.
The study does not report the analysis for potential toxic inter-
mediates (transformation products) that may be produced from the microbial
degradation. Further, no QA/QC protocols are reported in the document.
The document reports total waste analysis and toxicity characteristic
leaching procedure (TCLP) extract analysis data. There were no influent
TCLP analyses to match the effluent TCLP concentrations remaining in the
soil.
CONTAMINANTS;
Analytical data is provided in the treatability study report. The
breakdown of the contaminants by treatability group is:
Treatability Group CAS Number Contaminants
W03-Halogenated Phenols, 87-86-5 Pentachlorophenols
Cresols, Thiols
W08-Polynuclear Aromatics TOT-PAH Total Polycyclic
Aromatic Hydrocarbons
tfl3-0ther Organics TOT-OIL Oil and Grease
3/89-8 Document Number: EWGC
NOTE: Quality assurance of data may not be appropriate for all uses.
-------
j€ \ ;- \\
_SZ_,
\KEYSTONE
\ ENVIRONMENTAL RESOl Rf ES. INC
\—j 1-r --T-
1050 Connecticut Avenue. NW Suite 300. Washington. D.C. 20036
June 12, 1987
Mr. James Antizzo
US EPA WH 548E
401 M Street,S.W.
Washington, D.C. 20006
Dear Mr. Antizzo:
As per our phone conversation of yesterday, I am
forwarding directly to you, detailed information on our
land treatment system — the Engineered Biodegredation
System (EBDS).
I mentioned to you during our conversation, that some
of our information would be confidential in nature, and that
we would appreciate your taking every effort to ensure that
it remained so. As it turns out, the information contained
in the enclosed package, has been submitted to the State of
New Hampshire and so, is now in the public domain.
Therefore, you need not be concerned about the release of
the information.
Additional information is available on the EBDS system.
We did not f rward it to you at this time because it is
quite bulky. It includes information on QA/QC procedures
and more details on how the system was run.
We thought it best for you and your staff to review the
enclosed first, and then give me a call if you have
additional questions or the need for more information.
Thank you for your consideration in this matter.
Ann Hegnauer
Senior Program Manager
202/429-6552
encl:
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\KEYSTONE
\ ENVIRONMENTAL RESOURCES. INC.
\_y
1050 Connecticut Avenue, NW Suite 300, Washington, D.C. 20036
June 4, 1987
Mr. James Antizzo
US EPA WH-548E
401 M Street, S.W.
Washington, D.C. 20006
Dear Mr. Antizzo:
In response to your request to Mr. Richard Fortuna of
the Hazardous Waste Treatment Council, please find enclosed
an abstract which describes the land treatment system
developed by Keystone Environmental Resources.
This system, called an Engineered Biodegredation System
(EBDS), was developed to handle wastes containing
pentachlorophenol (PCP) and coal tar-related materials,
e.g., polynuclear aromatic hydrocarbons (PAHs). It has
been successfully tested both at the bench level and in
various field tests. One such field test was performed on a
1/4 acre plot at a former wood treating site. The EBDS
system was operated at this 1/4 acre site from May -
September of 1986. Monitoring of the soil, air and
groundwater was performed all during the 6 months of
operation. The results of this monitoring are discussed in
the attached paper.
A second year of operation at this site was begun in
early May of this year.
We would be happy to provide you with more specific
data on the EBDS system at any time. Should you wish to
obtain additional information or a briefing on our EBDS
system, please feel free to call me in Washington, D.C.
at 429-6552.
Ann Hegnauer'
Senior Program Manager
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ENGINEERED BIODEGREDATION SYSTEM
PROCESS DESCRIPTION
KEYSTONE ENVIRONMENTAL RESOURCES, INC
GENERAL DESCRIPTION
The Engineered Biodegredation System (EBDS) is a unit
process that treats contaminated soil utilizing the capacity
of the soil matrix to biodegrade and immobilize the
contaminants of concern.
EBDS is an aerobic soil mixture approximately 0.5 to
1.5 feet deep that is managed to promote the growth of
indigenous microorganisms to biodegrade contaminants and to
promote immobilization of contaminants (see attached table).
Depending on site characteristics, containment
characteristics and regulations, EBDS can be placed upon a
variety of foundations, e.g. a prepared ground surface, low
permeability liners, or a concrete pad.
The final design application of this system is
dependent upon the soil type and characteristics,
hydrogeologic conditions, meteorological conditions, the
proximity of the site to receptors, potential emissions,
potential exposure pathways and/or acceptable exposure
levels.
RESULTS
Based on a series of bench, pilot and full-scale
operations, results of the EBDS process on wastes from
wood treating facilities indicate:
on soils:
over 80% of PCP removal
over 90% of PAH removal
decomposition products were not toxic by either
microtox or daphnia acute toxicity assays
air emissions:
0.1% to 15% of naphthalene and
some non-carcinogenic PAH's and
less than 0.1% of PCP and carcinogenic PAHs.
\KEYSTONE
\ ENVIRONMENTAL HtSOl UflS. INC
\___l
-------
leachate emissions:
PCP and PAHs were not detected in soil
below zone of incorporation
TCLP tests at end of pilot EBDS had non-
detectable levels of PCP and PAHs
groundwater monitoring results showed
nondetectable levels of PAHs and PCPs
\KEYSTONE
\ ENVIRONMENTAL RCSOlltrES. INf
\ /
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KEYSTONE'S EBDS UNIT PROCESS
ZONE OF
INCORPORATION
0.5 - 1.5 FT.
• PERIODIC
TILLING
CONTAMINANTS UNIFORMLY INCORPORATED
INTO SOIL MATRIX WHERE BIODEGHAUATION
AND IMMOBLIZATION OF CONTAMINANTS OCCURS
RUN-ON
AND
PUN-OFF
PERCOLATION
OF
SOIL WATER
-------
EVALUATION OF AN ENGINEERED BIODEGRADATION SYSTEM
AT THE NASHUA, N.H. SITE
PREPARED BY:
(COPPERS COMPANY, INC.
440 COLLEGE PARK DRIVE
MONROEVILLE, PA 15146
APRIL, 1987
KEYSTONE ENVIRONMENTAL RESOURCES, INC.
DOCUMENT NUMBER: 157098-00
Copyright Keystone Environmental Resources, Inc. 1987
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Statement of Proprietary Interest
This document describes a proprietary process of Keystone Environmental
Resources, Inc., the Engineered Biodegradation System, EBDS1", which was
developed by Keystone at a former plant site of Koppers Company, Inc.,
at Nashua, N.H. Certain sensitive portions have been removed but will
be made available in confidence to clients.
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TABLE OF CONTENTS
LIST OF TABLES AND FIGURES
1.0 INTRODUCTION 1
2.0 EBDS": PRINCIPLES AND ISSUES 2
3.0 DESIGN OF EXPERIMENTAL STUDIES 5
3.1 Bench-Scale Laboratory Studies 5
3.2 Pilot-Scale Field Study 12
4.0 RESULTS AND DISCUSSION 17
4.1 Waste Constituent Degradation 17
4.2 Toxicity of Transformation Products 40
4.3 Emissions of Waste Constituents 45
5.0 SUMMARY AND CONCLUSIONS 64
References 67
APPENDICES
A. Toxicity Assessment of Selected Chemicals
B. Procedure for Computing Mass Balances
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LIST OF TABLES AMD FIGURES
TABLE 3-1 INITIAL CONDITIONS AND OPERATIONAL PROCEDURES FOR
SOIL PAN STUDY 6
TABLE 3-2 KEYSTONE PROPRIETARY EBDS"1 INFORMATION 8
TABLE 3-3 INITIAL CONDITIONS AND OPERATIONAL PROCEDURES FOR
SOIL COLUMN STUDY 10
TABLE 3-4 KEYSTONE PROPRIETARY EBDS1" INFORMATION 11
TABLE 3-5 KEYSTONE PROPRIETARY EBDS1" INFORMATION 15
TABLE 4-1 CONCENTRATIONS OF OIL AND GREASE (04G), PAH AND PCP
AS A FUNCTION OF DEPTH AND TIME IN SOIL COLUMNS... 22
TABLE 4-2 CONCENTRATIONS OF OIL AND GREASE (04G), PAHs AND PCP
AS A FUNCTION OF DEPTH AND TIME IN THE PILOT EBDS". 23
TABLE 4-3 CLASSIFICATION OF SELECTED PAHs BY THEIR
CARCINOGENICITY 26
TABLE 4-4 FINAL DIOXIN AND FURAN RESULTS FOR SOIL IN THE SOIL
PANS 33
TABLE 4-5 INITIAL AND FINAL DIOXIN AND FURAN RESULTS FOR SOIL
IN THE ZONE OF INCORPORATION IN THE SOIL COLUMNS.. 34
TABLE 4-6 TOXIC EQUIVALENCY FACTORS FOR DIOXIN AND FURAN
ISOMERS 36
TABLE 4-7 EQUIVALENT CONCENTRATIONS OF 2,3,7,8 TCDD IN THE
SOIL PANS 37
TABLE 4-8 EQUIVALENT CONCENTRATIONS OF 2,3,7,8 TCDD AS A
FUNCTION OF DEPTH AND TIME IN THE SOIL COLUMNS 38
TABLE 4-9 RESULTS OF DAPHNIA AND MICROTOX BIOASSAYS ON SOILS
FROM PILOT EBDS1" 41
TABLE 4-10 AMBIENT AIR CONCENTRATIONS UPWIND AND DOWNWIND OF
THE PILOT EBDS™ 46
TABLE 4-11 CONCENTRATION OF CONSTITUENTS IN SOIL AND LEACHATE
FROM SOIL COLUMN STORM SIMULATIONS 51
TABLE 4-12 COMPARISON OF MAXIMUM LEACHATE CONCENTRATIONS WITH
WATER QUALITY STANDARDS 52
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LIST OF TABLES AND FIGURES (Continued)
TABLE 4-13 TCLP RESULTS FOR PILOT EBDS" AFTER THREE MONTHS 55
TABLE 4-14 TCLP RESULTS FOR PILOT EBDS1" AFTER SIX MONTHS 57
TABLE 4-15 TCLP DIOXIN AND FURAN RESULTS FOR PILOT EBDS" AFTER
SIX MONTHS 58
TABLE 4-16 MONITORING WELL SAMPLING RESULTS (AUG., 1986) 61
TABLE 4-17 MONITORING WELL SAMPLING RESULTS (NOV., 1986) 62
FIGURE 2-1 SOIL TREATMENT ZONES IN A TYPICAL EBDS1" 3
FIGURE 3-1 KEYSTONE PROPRIETARY EBDS" INFORMATION 9
FIGURE 3-2 KEYSTONE PROPRIETARY EBDS" INFORMATION 13
FIGURE 4-1 REMOVAL PROCESSES ACTING ON A CHEMICAL 19
FIGURE 4-2 FATE OF CHEMICALS IN SOIL COLUMN Al 27
FIGURE 4-3 FATE OF CHEMICALS IN SOIL COLUMN 81 28
FIGURE 4-4 FATE OF CHEMICALS IN THE PILOT EBDS"1 31
FIGURE 4-5 ACUTE TOXICITY AND FREON EXTRACTABLES IN SOIL
COLUMNS 43
FIGURE 4-6 ACUTE TOXICITY AND FREON EXTRACTABLES IN PILOT
EBDS" 44
FIGURE 4-7 KEYSTONE PROPRIETARY EBDS" INFORMATION 47
FIGURE 4-8 EMISSIONS FROM THE PILOT EBDS" 49
FIGURE 4-9 KEYSTONE PROPRIETARY EBDS" INFORMATION 60
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1.0 INTRODUCTION
This report presents the results of laboratory and field studies
conducted on soils from the Nashua, N. H. site. These studies were
undertaken to provide the data base needed to evaluate the full scale
implementation of an Engineered Biodegradation System (EBDS1") to treat
the wood preservative residues found in the soils at the Nashua, N. H.
site.
The evaluation of any technology for treating industrial wastes
requires carefully identifying the criteria for judging the performance
of the technology. In evaluating the performance of the proposed
EBDS", criteria based on the public health and environmental risks that
could potentially arise in operating a full scale EBDS" are used. In
short, the viability of an EBDS1" rests on its capacity to reduce the
amount of hazardous substances to acceptable levels through biological
and chemical transformations, and control emissions of compounds from
the EBDS1" below levels that could cause a public health or
environmental hazard. Using the results of the laboratory and fields
experiments, in conjunction with transport and fate analysis of
particular constituents of the waste, and information on the toxicity
of these constituents, a preliminary evaluation of the EBDS" is
presented. A more extensive evaluation will be made as part of the
Feasibility Study for the Nashua, N. H. site.
This report is divided into five chapters. Chapter 2 presents a brief
description of the principles involved in the design, operation and
performance of an EBDS", and identifies the public health and
environmental issues that must be addressed in the evaluation of a full
scale EBDS". To obtain the data necessary to make this evaluation,
laboratory and field studies were conducted on soils from the Nashua
site, and chapter 3 discusses the design of these laboratory and field
experiments. Chapter 4 discusses the results of these experiments as
they relate to the public health and environmental Issues raised in
Chapter 2. The final chapter summarizes the findings of this study and
offers some conclusions.
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2.0 EBOS-: PRINCIPLES AMD ISSUES
An EBDS™ is a unit process for immobilizing and biologically
transforming compounds using soil as the medium for growing and
maintaining the necessary microorganisms. Two soil zones, the zone of
incorporation and the lower treatment zone, are the principal
components of an EBDS1". Figure 2-1 shows these two soil zones.
The lower treatment zone, which is typically 3 to 5 feet in depth, is a
graded bed of relatively clean soil upon which contaminated soil is
placed. This layer of contaminated soil, which is typically 6 to 12
inches in depth, forms the zone of incorporation. The initial level of
contamination in the zone of incorporation is achieved by mixing
appropriate quantities of soil containing relatively low concentrations
of contaminants with soil containing relatively high levels of
contaminants. Various amendments, such as lime, nutrients and organic
matter, can be added to soil in the zone of incorporation to decrease
the mobility of waste constituents and enhance their destruction by
microorganisms. In addition, this soil may also be periodically tilled
to increase soil oxygen levels and improve the mixing of constituents.
While most biological transformations will occur in the zone of
incorporation, biological transformations can also occur in the lower
treatment zone, if waste constituents move into this zone from the zone
of incorporation. As with the zone of incorporation, amendments can be
added to soil in the lower treatment zone to increase its assimilative
capacity for waste constituents.
In developing a design for an EBDS1", two key questions arise:
1. Public health and environmental question - Can an EBDS™ be
used to reduce the levels of wastes to acceptable levels
through microbial degradation, without generating
unacceptable emissions of waste constituents?
2. Engineering question - What is the most cost-effective com-
bination of soil treatment zone design, soil amendments and
operating procedures that also successfully addresses the
public health and environmental question?
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4--0"
ZONE OF
INCORPORATION
LOHER
TREATMENT ZONE
FIGURE 2-1
SOIL TREATMENT ZONES IN A TYPICAL BEDS
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These two questions are clearly interrelated, because the public health
and environmental concerns place constraints on the design of an EBDS™.
The public health and environmental concerns can be addressed by an-
swering the following questions:
1. Does chemical and biological transformation of waste
occur in an EBDS1"?
2. Are the transformation products of the treated waste toxic?
3. What are the emissions from an EBDS1"?
These include:
- emissions to air,
- emissions out of the zone of incorporation with leachate,
and
- emissions with surface runoff.
To provide the data needed to answer both the public health and en-
vironmental question and the engineering question, laboratory and field
experiments were conducted. The next chapter describes the procedures
used in these experiments. Chapter 4 discusses the results of these
experiments in the context of the three public health and environmental
questions identified previously. The use of these experimental results
to answer the engineering question, i.e. the design of a full scale
EBDS1", awaits the completion of the Feasibility Study for the Nashua,
N. H. site.
A properly designed EBOS" should include a Mechanise for
collecting surface runoff, and then using this water for soil
misture control, or treating and disposing of the water.
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3.0 DESIGN OF EXPERIMENTAL STUDIES
To obtain the data necessary to design and evaluate a full scale EBDS1",
laboratory and field experiments were conducted. The laboratory
experiments included soil pan and soil column studies, while the field
experiment utilized a pilot scale EBDS1". This chapter briefly
describes the procedures used in these studies. More detailed
descriptions can be found in the attachments to this report.
3.1 Bench-Scale Laboratory Studies
Soil Pan Study
In order to evaluate the influence on biodegradation of soil moisture,
nutrients and the level of waste application, soil pan studies were
conducted.
Eight pans were loaded with mixtures of "clean" and contaminated soils
from the site to vary the initial quantity of contaminants in the soil
to prespecified levels. Table 3-1 shows the initial conditions in each
pan.
Based on chemical analysis of the soils, Pennsylvania cow manure and
fertilizer were added to the soil to increase its organic matter
content and bring the ratio of carbon:nitrogen:phosphorous (C:N:P) to
50:2:1 in each pan.
Maintenance of the soil pans was performed on a weekly or monthly
basis, depending on the operation. Soil pH was maintained between 6.5
and 7.5 by weekly lime addition, if required. Soil moisture was
maintained at approximately 70% of field capacity by weekly additions
of tap water. Soil aeration was increased by weekly tilling. On a
monthly basis, fertilizer was added to maintain the C:N:P ratio at
50:2:1.
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TABLE 3-1
INITIAL CONDITIONS AND OPERATIONAL PROCEDURES FOR SOIL PAN STUDY
Pan *
1*
2+
3+
4
5
6
7
8
Soil
clean
contaminated
contaminated
contaminated
contaminated
contaminated
contaminated
contaminated
PCP
none
high
low
highest
2nd highest
3rd highest
2nd lowest
lowest
Operation
Condition
watering
no watering
no watering
watering
watering
watering
watering
watering
* clean soil control
+ contaminated soil control
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Soil samples were collected on a monthly basis and analyzed for the
parameters presented in Table 3-2.
Soil Column Study
To investigate the mobility of waste constituents in soil, air and
water, soil column studies were conducted. These studies also provided
sufficient data to compute mass balances on waste constituents.
A schematic diagram of the soil column is presented in Figure 3-1.
The top 6 inches of each soil column was packed with a mixture of
"clean" and contaminated soils. The initial conditions in each column
are shown in Table 3-3. The levels of contamination in the columns
have the following correspondence with soil pans: column C corresponds
with soil pan 1 (control); columns Al, A2 and C6 correspond with soil
pan 4; ajid columns Bl and 82 correspond with soil pan 7. Pennsylvania
cow manure and fertilizer were added to the soil in the surface layer
to increase its organic matter content and bring the ratio of C:N:P to
50:2:1 in each column.
As with the soil pans, maintenance of the soil columns was performed on
a weekly or monthly basis, depending on the operation. Soil pH was
maintained between 6 and 7 by weekly addition of lime. Soil moisture
was maintained at approximately 7Q% field capacity by weekly additions
of tap water. Soil aeration was increased by weekly tilling.
Samples were collected from the zone of incorporation at the beginning,
twice in the middle and at the end of the experiment. These samples
were subjected to chemical analysis for the parameters listed in Table
3-4.
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[CONFIDENTIAL
TABLE 3-2
SAMPLING FREQUENCY AND ANALYTICAL PARAMETERS FOR SOIL PAN STUDY
MONTH
PARAMETER
Initial 1
Final
PH
% Moisture
Conductivity
Chloride
Benzene Extractables
Freon Extractables
TKN
Total Phosphorus
NH.-N
% Volatile
Priority Metals
Pentachlorophenol
Phenol
PAH
Organics
Microtox
Daphnia
Dioxins/Furans
W.S.M
M
W.S.M
M
H.S.M
H.S.M
M
M
M
M
H.S.M
H.S.M
M
H.S.M
H.S.M
M
M
H.S.M
M
M
M
M
M
M
M
M
M
M
M
M
M
M
-
M
M
M
M
M
M
M
M
M
M
M
M
M
M
M
M
-
M
M
M
M
M
M
M
M
M
M
M
M
M
M
M
M
-
M
M
M
M
M
M
M
M
M
M
M
M
M
M
M
M
-
M
M
M
M
M
M
M
M
M
M
M
M
M
M
M
M
-
M
M
M
M
M
M
M
M
M
M
M
M
M
M
M
M
M
M
M
M
Note: Initial saaple corresponds to ti«e of waste application
M * As Is waste before Incorporation Into soil
S - Soil fro» land treatment deaonstratlon plot before waste
application
M = Soil and waste Mixture Including fertilizer
1,2 = Corresponds to the first two weeks and the last two weeks
In each respective Month
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(**0-2 SORBANT CANNISTER)
jr
VOLA TILES —
COLLECTION
U
-^
1
w
^
-r— *• TOP FITTING WITH
3 PORTS - l/4m O.O.
ZONE OF
INCORPORA TION -
NOTES:
if ALL TUBING CONNECTIONS ARE
BRASS COUPLINGS.
if USE TEFLON FERRULES IN UNIONS
FOR GLASS TUBING.
if USE BRASS FERRULES IN UNIONS
FOR TEFLON TUBING.
if TOP AND BOTTOM FITTINGS MADE
FROM 4' GLASS CAPS.
» THE COLLECTION FLASKS ARE
ALL CONTAINED IN A SAMPLE
REFRIGERATOR.
^4" I.D. GLASS PIPE
a RUBBER SEAL
TEFLON INNEf
a METAL CLAMP
4" BOTTOM FITTING WITH
TEFLON STOPCOCK
1/B' O.O. TEFLON TUBING
1/4' O.O. GLASS TUBING
VACUUM PORT
185 »J VACUUM COLLECTION FLASK
SAMPLE REFRIGERATOR
FIGURE 3-1
SOIL COLOMM DKSICT
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10
TABLE 3-3
INITIAL CONDITIONS AND OPERATIONAL PROCEDURES FOR SOIL COLUMN STUDY
Column f
Al
A2
Bl
B2
C
C6
Surface
Soil
Contaminated
Contaminated
Contaminated
Contaminated
Clean
Contaminated
PCP
high
high
low
low
0
high
Storm
Simulation
no
yes
no
yes
no
yes
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TABLE 3-4
SAMPLING FREQUENCY AND ANALYTICAL PARAMETERS FOR SOIL COLUMN STUDY
MONTH
PARAMETER
Initial
Final
PH
% Moisture
Conductivity
Chloride
Benzene Extractables
Freon Extractables
TKN
Total Phoshorus
NH,-N
% Volatile
Priority Metals
Pentachlorophenol
Phenol
PAH
Organics
Microtox
Oaphnia
Dioxin/Furan
z.c
Z
z.c
Z
z,c
z.c
Z
Z
Z
Z
z.c
Z.C.A
z.c
Z.C.A
z,c
z.c
z.c
z.c
Z Z Z
Z Z Z
Z
Z
Z
Z
Z
Z
Z
Z
Z
A A Z
Z
A A Z
Z
Z
Z
Z
Z
Z
Z
Z
Z
Z
Z
Z
Z
Z
Z
Z
Z
Z
Z
Z
Z Z.C.L
Z Z
Z.C.L
z.c
z.c
Z.C.L
Z
Z
Z
Z
z.c
Z.C.L
z.c
Z.C.L
z.c
Z.C.L
z.c
Z.C
NOTE: Initial sanple corresponds to tine of waste application
C - Soil core saoples collected fro* 0 to 5 feet
Z * Zone of Incorporation saaple
L * Leachate staple generated froa 24 hr/25 yr stora simulation
A * Air saaple
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12
To obtain the information necessary to perform a mass balance, volatile
emissions from columns Al, A2, 81 and B2 were measured during the
course of the experiment. In addition, soil cores were taken from
these columns at the conclusion of the experiment to measure the
vertical migration of chemicals with soil water.
Finally, three columns, A2, B2 and C6 were subjected to the equivalent
of a 25 year-24 hour rainstorm. The purpose of this storm simulation
was to investigate the movement of chemicals through the soil during an
extreme rainfall event. For columns A2 and B2 the storm was simulated
in the fifth month of operation. Assuming a startup of an actual EBDS"
in May, this corresponds to a rainstorm in September, which is the
month when the 25 year-24 hour rainstorm is expected to occur. To
capture the worst case possible, column C6, which was loaded with
relatively highly contaminated soil, was subjected to the storm
simulation immediately after application of the contaminated soil.
3.2 Pilot-Scale Field Study
While the laboratory provides the experimenter with an opportunity to
control environmental factors such as temperature, and moisture, an
actual EBDS" must operate in the field. To obtain data from an outdoor
setting for evaluating an EBDS", a field experiment was performed with
a p-lot scale EBDS".
The field experiment was performed on a portion of the Nashua, NH site.
Components of the demonstration area are presented in Figure 3-2.
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GROUNDWATER
FLOW
DIRECTION
DOWNGRADIENT
WELLS —
(DW1)
^KEYSTONE
\ENVIRONMENTALRESOURCES. INC.
FIGURE 3-2
COMPONENTS OF FIELD EXPERIMENT
UPGRADIENT
MONITORING
WELL
(UW)
.CONFIDENTIAL
.1
o
in
SAMPLING
SECTOR 1
SAMPLING
SECTOR 2
?nn •
SAMPLING
SECTOR 3
— ,. ,-,, r;-7 • ^
(DW2)
(DW3)
STOhM
RUNOFF
RETENTION
POND
CONTROL
PLOT
»—~ 34' —\
NOT TO SCALE
NOTE:
SAMPLING SECTORS 1. 2 AND 3 ARE DEFINED FOR
STATISTICALLY SAMPLING PURPOSES ONLY
M38B-1
-------
14
The treatment unit was loaded with one foot of contaminated soil. Cow
manure and fertilizer were added to both the control unit and treatment
unit to increase the organic matter content of the soil and to achieve
a C:N:P ratio of 50:2:1.
During the field experiment, soil pH was maintained between 6.5 and 7.0
by the addition of lime. The soil was sprayed periodically with water
to maintain a soil moisture content near 70% of field capacity. The
soil was also rototilled once a week to improve mixing of constituents
and increase aeration. Fertilizer was added at the beginning and
middle of the experiment to maintain the C:N:P ratio of the soil at
50:2:1.
During the course of the experiment, soil samples from the zone of
incorporation were collected from the treatment and control unit.
Three composited sampled were collected from each unit and analyzed for
the parameters listed in Table 3-5.
To obtain the information necessary to perform mass balances on waste
constituents, volatile emissions from the treatment unit were measured
during the course of the experiment. In addition, soil cores were
taken from both the treatment and control units at the middle and end
of the study. The cores collected at mid-season were put into cold
storage. The cores taken at the end of the study were subjected to a
priority pollutant scan. The results of this chemical analysis
provided a measure of the vertical migration of chemicals with soil
water.
To determine emissions from the treatment unit, air and groundwater
monitoring was carried out. Immediately after loading the treatment
unit, upwind and downwind air monitoring was performed. In addition,
groundwater wells, both up gradient and down gradient from the
treatment unit, were sampled twice during the study, once after three
months of operation and once at the end of the experiment.
-------
CONFIDENTIAL
Z,L
Z,L
Z,L
Z,L
Z
Z
c*,z,w,
c*,z,w
Z
Z
Z
Z
C.Z.W.S.L
C.Z.W.S.L
TABLE 3-5
SAMPLING FREQUENCY AND ANALYTICAL PARAMETERS FOR PILOT EBOS STUDY
May June July August September October November
pH
Conductivity
Benzene/Freon
Extractables Z Z Z C*,Z Z Z C,Z
TKN Z Z Z
NH3-N Z Z Z
Total Phosphorus
and Carbon Z Z Z
Base/Neutrals and
Acid Extractables Z C*,Z C.W.Z.S
PAH (GO L.Z.A L,A Z,A W, Z Z L,Z
Phenolics and PCP L.Z.A L,A Z,A W, Z Z L,Z
Daphm'a and Microtox
Biossays 2,1 C*,Z,W C.Z.W.S.L
Metals A A A C*,W C*,W,Z,S
Volatile Orgam'cs Z Z
1 Complete Base/Neutrals and Add Extractables, Method 625 Includes PAH
and phenol
C - Soil Core Samples samples collected from 0 to 5 feet); *-Frozen Cores
Z - Zone of Incorporation Soil Samples
L = Soil Pore Liquid Samples from Glass Block Lyslmeters (to be taken as
Indicated, provided sufficient sample water Is present in lysi meters)
M = Ground Mater Samples (upgradient Hell UM-1, downgradlent Hells DH-1,
OH-33 and OH-34)
S = Surface Hater Sample from the Merrlmack River
A » Air Samples (taken during construction and tilling operations, and
twice monthly during the first two months of operation)
-------
16
To determine the leaching potential of the soil, the toxicity
characteristic leaching procedure (TCLP) was performed on soil samples
at the mid point and end of the study. Finally, a trench lysimeter was
installed to collect leachate from the treatment unit.
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17
4.0 RESULTS AND DISCUSSION
This chapter presents the results of the laboratory and field
experiments. To help provide a meaningful context for these results,
they are presented in relation to the three public health and
environmental questions posed in chapter 2. These questions are:
1. Does chemical and biological transformations of waste occur
in an EBDS1"?
2. Are the transformation products of the treated waste toxic?
3. What are the emissions from an EBDS"?
These include:
- emissions to air,
- emissions out of the zone of incorporation with leachate,
and
- emissions with surface runoff.
Each of these questions is addressed in a separate section of this
chapter.
4.1 Haste Constituent Degradation
To answer the question, "Does chemical and biological transformations
of waste occur in an EBDS"1?", it is necessary to examine the fate of
individual compounds. The examination in this section is divided into
two parts. In the first part, a mass balance analysis is performed on
pentachlorophenol (PCP), naphthalene and polynuclear aromatic
hydrocarbons (PAHs). In the second part, the fate of dioxins and
furans in the soil is presented.
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18
Mass Balance Analysis of PCP, Naphthalene and PAHs
To perform an analyses of the fate of chemicals in the soil, it is
necessary to examine all pathways whereby contaminants may be removed
from the soil. In general, a chemical may degrade, either through
chemical or biological mechanisms, it may volatilize, or it may
dissolve in soil water and move when the water moves. Thus, if the
concentration of a compound in the soil is deceasing over time, this is
an indication that degradation may be occurring, but other removal
pathways must also be examined to determine the extent to which
degradation is responsible for the observed removal of this compound.
Examination of Removal Processes. Figure 4-1 shows the removal
processes that can act upon a compound initially placed in the zone of
incorporation. The variables used in Figure 4-1 are defined as
follows:
m.(t) = the mass of compound A in the zone of incorporation
A
e.(t) = the cumulative volatile emission of compound A from the
A soil (mg/nr)
s.(t) = the cumulative seepage of compound A from the zone of
incorporation with leachate (mg/m )
d.(t) = the mass of compound A that has been chemically/
biologically transformed (mg/m )
If m.(0) is the initial mass of the chemical in the zone of
incorporation, then mass conservation requires that at all later times:
mA(0)=mA(t)+eA(t)+sA(t)+dA(t) (4-1)
Since the mass of the compound is measured over time, m^(°) and mAl '
are known. Similarly, since the rate of volatile emissions was
measured in the soil column and pilot EBDS* studies, e^t) 1S known-
I f
-------
19
FIGURE 4-1
PROCESSES ACTING OH A CHEMICAL
SOIL SURFACE
CA(t)
VOLATILIZATION
_ ft. CHEMICAL/
A* ' BIOLOGICAL
LEACHING
dA(t)
TRANSFORMATION
ZONE
OF
INCORPORATION
SA(t)
-------
20
the mass of a chemical migrating out of the zone of incorporation with
leachate, sA(t), is negligible compared to the initial mass of the
compound in the soil, mA(0), then dA(t) may be estimated using
dA(t)=mA(0)-mA(t)-eA(t) (4-2)
Equation 4-2 is simply a rearrangement of equation 4-1. Thus, if sA(t)
is assumed to be negligibly small, the fate of a compound over time can
be quantitatively estimated, since mA(t) and «A(t) are measured, and
dA(t) can be determined using equation 4-2.
There are sound theoretical reasons for assuming that the mass of a
chemical migrating out of the zone of incorporation with leachate,
sA(t), is negligible. First, except for the storm simulations, which
were conducted once at the end of the experiment, water was added to
the soil columns essentially to maintain a minimum moisture content in
the soil. Consequently, the amount of water leaching out of the zone
of incorporation should have been minimal. Similarly, there was enough
evaporation in the field plot, which was operated during late spring,
summer and early fall, that there was so little soil water movement
that no leachate was collected in the lysimeters below the plot.
Second, even in the presence of substantial soil water movement,
pentachlorophenol (PCP), naphthalene and polynuclear aromatic
hydrocarbons (PAHs) are resistant to migration in soil water. The
higher (5 and up) ring PAH compounds are sparingly soluble in water and
tend to adsorb strongly to soil particles. Naphthalene and the lower
ring PAHs are more mobile than their higher ring cousins, but are by no
means highly mobile. The mobility of PCP is strongly influenced by the
pH of the soil water. In acidic environments, PCP remains nonionized,
has low solubility and strongly adsorbs to organic matter. As pH
increases, PCP becomes more mobile and is highly soluble in water at
high pH.
-------
21
These theoretical considerations are supported by the experimental data
obtained in the soil column and pilot EBDS" studies. Since only soil
in the zone of incorporation (surface 6 inches in the soil columns and
surface 12 inches in the pilot EBDS™ soil) contained significant
concentrations of waste constituents at the start of the study, the
extent to which chemicals move out of the zone of incorporation via
leaching can be ascertained by examining the distribution of chemical
concentrations through the soil profile over time. For the soil column
studies, chemical concentrations are available for selected depths at
the conclusion of the experiment, while for the pilot EBDS™ study
chemical concentrations are available at all depths.
Table 4-1 reports the concentration of oil and grease (04G), PCP, and
naphthalene and total PAHs as a function of depth in soil columns C
(control), Al, A2, Bl and B2 at the beginning and end of the
experiment. Table 4-2 reports the same information for soil in the
pilot EBDS"1. In both tables, O&G refers to the concentration of
chemicals extracted with freon. Since PCP, naphthalene and PAHs are
soluble in freon, these compounds should be removed by this extraction
procedure. Thus O&G levels are indicative of PCP, naphthalene and PAH
presence.
The most notable observation concerning these results is that no PCP,
naphthalene or PAHs were detected in soils below the zone of
incorporation in the pilot EBDS". Similarly, no PAHs were detected in
the soils below the zone of incorporation in any of the soil columns.
While PCP was detected in all soil columns at all depths, the
concentrations of PCP in the control column (C) are comparable to the
concentrations In the experimental columns (Al, A2, Bl and B2),
suggesting that the PCP in soils at lower depths originates from the
use of soil that was initially very slightly contaminated with PCP,
rather than the downward migration of PCP from the zone of
incorporation.
-------
TABLE 4-1
CONCENTRATIONS OF OIL AND GREASE (OK), PAH AND PCP
AS A FUNCTION OF DEPTH AND TIME IN SOIL COUMIS
Depth
(feet)
0- .5
.5-1.5
1.5-2.5
2.5-3.5
3.5-5
beg
end
beg
end
beg
end
beg
end
beg
end
Colum C
0*G PAH PCP
<50 <1.0 .05
<50 <1.32 .024
<50
<50 <.57 .013
<50
<50 <2.39 .014
Colum Al
(MG PAH PCP
9,033 1,193 153
1,740 346.7 8
1,493
223 <2.8 .025
247
427 <1.7 .029
Colum A2
OK PAH PCP
6,167 1,490 130
347 137.1 11
67
<50 <1.77 .002
<50
<50 <1.93 .021
Colum Bl Colum B2
04G PAH PCP 04G PAH PC
2,347 315.5
247 128.3
<50
<50 <1.43
<50
<50 <.274
59 3,170 450 6
3.9 1,120 200.5 1
53
.193 <50 <2.4 .01'
<50
.02 <50 <.4 .011-
All concentrations have units of ag/kg.
PAH includes naphthalene.
Dashed lines (—) indicate no Measurement was made at this depth.
The terns beg and end Indicate beginning and end of experinent, respectively.
The final results for col urns A2 and B2 follow the stom simulation.
NJ
NJ
-------
23
TABLE 4-2
CONCENTRATIONS OF OIL AND GREASE(04G), PAHs AND PCP AS A FUNCTION
OF DEPTH AND TIME IN THE PILOT EBDS"
Control Plot
Depth
(feet)
3-1 beg
end
1-2.5 beg
end
>.5-4 beg
end
t-5.5 beg
end
lepth
feet)
i-l beg
end
-2.5 beg
end
:.5-4 beg
end
t-5.5 beg
end
OAG
<50
67
73
<50
93
OAG
4,707
3,270
<50
140
Sector 1
PAH
2.17
ND
ND
ND
ND
Sector 1
PAH
651
3.0
ND
ND
ND
PCP OAG
.041 <50
<12 80
<12 <50
<12 100
<12 80
Experimental
PCP OAG
36 3,913
16.2 2,050
<12 167
<12 107
<12 <50
Sector 2
PAH PCP
1.12 .02
ND <12
ND <12
ND <12
Plot
Sector 2
PAH PCP
519 80
.35 13.0
ND <12
ND <12
ND <12
Sector 3
OAG
<50
147
<50
113
<50
OAG
7,707
2,430
60
<50
<50
PAH
1.15
ND
ND
ND
Sector
PAH
2,143
.35
ND
ND
ND
PCP
.019
~*shed lines (—) indicate no Measurement was made at this depth.
« terms beg and end indicate beginning and end of experiment, respectively.
-------
24
The oil and grease (O&G) data is somewhat more difficult to interpret.
Except for column Al, O&G levels in all soil columns and the field plot
are near or below the detection limit for each depth below the zone of
incorporation. For column Al, the relatively high level of oil and
grease at soil depths below the zone of incorporation could be due to
leaching migration of chemicals from the upper zone. However, because
Al is the only experimental system showing elevated levels of O&G at
depths below the zone of incorporation, these elevated O&G levels are
probably due to other causes such as mechanical mixing of soils in the
two zones during tilling. The relatively high concentrations of oil
and grease in the lower three zones are harder to explain. However,
since the 04G analytical procedure picks up anything soluble in freon,
the elevated O&G levels could reflect relatively high levels of organic
matter in the soil at these depths. It is worth noting that although
O&G levels are relatively high in these soil zones, the concentrations
of PAHs are below the detection limits.
To summarize, the theoretical and experimental evidence indicate that
the migration of PCP, naphthalene and PAHs out of the zone of
incorporation via leaching is negligible compared to the initial mass
of these chemicals in the zone of incorporation. Thus, the assumption
that s.(t) is close to zero and the use of equation 4-2 to estimate the
mass of chemically/biologically transformed chemical, dA(t), are
justified. The rest of this section discusses the results of
performing the mass balance analysis on soils in columns Al, Bl and the
pilot EBDS". Appendix B gives a complete description of the
methodology employed.
Soil Coluan Mass Balances. For soil columns Al and Bl, mass balances
were performed on the following compounds or groups of compounds:
PCP
0 naphthalene
0 noncarcinogenic PAH
0 carcinogenic PAH
-------
25
The classification of PAH into noncarcinogenic or carcinogenic
categories is shown in Table 4-3. The rationale for this
classification is presented in Appendix A.
Since the purpose of this analysis is to investigate the chemical/
biological transformations of chemicals in the soil, soil columns Al
and Bl were chosen because the storm simulation was not performed on
these columns. Although the amount of contaminant migration out of the
zone of incorporation with soil water is expected to be very low, the
likelihood of this migration is even lower in the columns which did not
undergo the storm simulation. Thus, the assumption that cumulative
contaminant migration with leachate, sA(t), is negligible and the use
of equation 4-2 to estimate the quantity of chemically/biologically
transformed chemical are best justified with columns Al and Bl.
Figure 4-2 graphically depicts the cumulative volatile emissions and
transformations of PCP, naphthalene, noncarcinogenic PAHs and
carcinogenic PAHs for soil column Al. Figure 4-3 depicts the same
information for soil column Bl.
Before the results are discussed in detail, it should be noted that
only one sample was analyzed at each time. The number of samples
collected was limited by the amount of soil in the columns, as well as
the laboratory analysis costs. Because only one sample was taken and
because soils are extremely heterogeneous, there could be significant
scatter in the results, which the plots reflect (see naphthalene data
in Figures 4-2 and 4-3). Thus, the results presented in Figures 4-2
and 4-3 should be examined for trends as opposed to precise
transformation rates.
-------
26
TABLE 4-3
CLASSIFICATION OF SELECTED PAHs BY THEIR CARCINOGENICITY
Noncarclnogenlc PAHs
Acenaphthylene
Acenaphthene
Fluorene
Phenanthrene
Anthracene
Fluoranthene
Pyrene
Carcinogenic PAHs
Benz(a)anthracene
Chrysene
Benzo(b)fluoranthene
Benzo(k)f1uoranthene
Benzo(a)pyrene
01benz(a,h)anthracene
Benzo(g,h,i)pery1ene
Indeno(l,2,3-c,d)pyrene
-------
Pentochlorophenol-Fata
Column fll
3 A 6
Month of Operation
Naphthalene Fate
Colutm fll
30
(
25
20
I '5
I
I
Of-
0
j>--o> DO-D-D---o- o o- a -g |
83-46
Month of Operation
Non-Careinogonic PRH Fata
Column fll
Month of Operation
Carcinogenic PflH Fate
Colunn Rl
Month of Operation
FIGURE 4-2
PATE OF CHEMICALS IM SOIL COLOMH M
to
-------
Pentochlorophenol Fate
Column Bl
2345
Month of Operation
Naphthalene Fate
Column 81
16
10
1
o remaining
degraded
a volatl11 zed
O-
2346
Month of Ope rail on
Non-Carcinogenic PflH Fate
Column Bl
SZBt
o> 200
I 176
o 136
y loo
J> 75
25
o remaining
degraded
a volatlIIzed
0An—tn-doo-a—o
0 I 2
-a-
4
346
Month of Operation
Carcinogenic PflH Fate
Column Bl
IOJ
? I00<
i
80
2 eo
y)
Q
.<: 40
8
fl1
20
oi
0
o remaining A degraded a volatl 1
^— ^^^
~~ °
A
^^ "
1 2 3 4.' 5 8
zed
1M
7
Month of Operation
FIGURE 4-3
to
00
FATE OF CHEMICALS IN SOIL COLUMN Bl
-------
29
The results for PCP suggest that the cumulative emissions via
volatilization are negligible compared to the initial mass of PCP in
*
the zone of incorporation. Both columns show significant removal of
PCP via chemical/biological degradation.
The results for naphthalene indicate that cumulative volatile emissions
are a small, but measurable, fraction (5 to 10 percent) of the initial
mass of naphthalene in the zone of incorporation. As for chemical/
biological transformations of naphthalene, the results are difficult to
interpret because there is such scatter in the data. However, other
investigators have obtained significant naphthalene removal in their
studies (Sims and Overcash, 1983; Santodonato, 1981; Koppers, 1985).
As with PCP, the cumulative emission of noncarcinogenic PAHs via
volatilization was negligible compared to the initial mass of these
compounds in the zone of incorporation. However, for some of the
lighter compounds in this class (such as acenaphthene), the cumulative
emission via this pathway was a small, but measurable, fraction (2 to
6%) of the initial mass of these compounds (see "Attachment II: Nashua,
NH Bench-Scale EBDS1" Air Quality Study" for a complete discussion).
Both columns show significant chemical/biological transformation of
these compounds. These results are consistent with the results of
other investigators that show the lower ring PAHs being susceptible to
biodegradation (Sims and Overcash, 1983; Koppers, 1985).
In the case of carcinogenic PAHs, there were no detectable emissions of
these compounds from either soil column, so volatilization is not an
important removal process. As for chemical/biological transformations,
sampling variability makes it difficult to make definitive conclusions.
However, it appears that there is some removal via chemical/biological
transformation, but it is not considerable. These results are
consistent with other investigators who have shown the higher ring PAHs
to be more resistant to degradation than the lower ring compounds (Sims
and Overcash, 1983; Koppers, 1985).
-------
30
Pilot EBOS* Mass Balances. Figure 4-4 shows graphically the cumulative
volatile emissions and transformations of PCP, naphthalene,
noncarcinogenic PAHs and carcinogenic PAHs for the pilot EBDS™. Unlike
the soil columns, where only one soil sample was taken at each time,
three soil samples were taken from the pilot EBDS1" at each time. Thus,
these results show less scatter than do the soil column data.
As with the soil column data, cumulative volatile emissions of PCP are
negligible compared to the initial mass of PCP in the zone of
incorporation. There also appears to be significant removal of PCP via
chemical/biological transformations.
The results for naphthalene are similar to the soil columns in that
cumulative volatile emissions are a small fraction (10 to 20 percent)
of the initial mass of naphthalene in the zone of incorporation.
Unlike the soil columns, there appears to be significant chemical/
biological transformation of naphthalene in the pilot EBDS™.
The cumulative volatile emission of noncarcinogenic PAHs was negligible
compared to the initial mass of these compounds in the zone of
incorporation. However, some of the lighter compounds in this class
had cumulative volatile emissions that were a small percentage of their
initial mass in the soil, which is the same behavior these compounds
exhibited in the soil column studies (see "Attachment IV: Nashua, NH
Pilot-Scale EBDS" Air Quality Study" for a complete discussion). As in
the soil column studies, there was significant chemical/biological
transformation of these compounds.
There were detectable, but very small, volatile emissions of
carcinogenic PAHs at the start of the pilot EBDS1" study, but their
cumulative effect was insignificant compared with the initial mass of
these compounds in the zone of incorporation. There appears to be
greater chemical/biological transformation of these compounds in the
pilot EBDS1" than there was in the soil column studies.
-------
100
O 75"
2
PEIIUCIILOROPHEIIOL FATE
O
LJ
O
QC
3
O
50 I
200
MONTH
NAPHTHALENE FATE
REMAINING
VOLATILIZED
DEGRADED
700 i
TOTAL NOII-CARCIIIOGEIIIC PAH FATE
RCUAINIIIG
VOLAIILIZtO
DEGRADED
300 B,
RCUAINIMC
vouriLizco
DECR1DEO
MONTH
TOTAL CARCINOGENIC PAH FATE
FIGURE 4-4
FATE OP CHEMICALS IN THE PILOT BBDS
-------
32
It is worth noting that the pilot EBDS1" provides, in many ways, a
better environment for biodegradation than the soil columns. In the
field, there is a more diverse population of microorganisms than in the
soil column because of the greater size of the field. Thus, there is a
higher probability of the field having the right microorganisms to
degrade the waste. In addition, the presence of wind should increase
the circulation of oxygen in the field plot as compared to the soil
columns, which operate in a relatively stagnant laboratory setting.
The fact that chemical/biological transformations were more pronounced
in the pilot EBDS" as compared with the soil columns provides evidence
for this hypothesis.
Dloxin and Furan Analysis
Soils from the soil pan study and soil column study were sampled and
analyzed for dioxins and furans. In the soil pan study, soils were
sampled from pans 1, 2, 3, 4 and 7 at the end of the experiment. In
the soil column study, soils were sampled from the zone of
incorporation in columns C, Al, A2, 81 and 82 at the beginning of the
experiment. The samples from Al and A2 were composited prior to
extraction and chemical analysis, as were the samples from 81 and 82.
At the end of the experiment, soils were sampled from the same columns
at depths of 0 to .5 feet (the zone of incorporation), .5 to 1.5 feet
and 3.5 to 5 feet.
The results of the dioxin and furan chemical analysis of the soil pan
samples are shown in Table 4-4. The results of the dioxin and furan
chemical analysis of the samples from the zone of incorporation in the
soil columns are shown in Table 4-5. Table 4-5 has the concentrations
of dioxins and furans at the beginning and end of the experiment. In
both tables, only hexa-, hepta-, and octa-dioxin and furan isomers are
listed, because these were the only isomers present at detectable
levels.
-------
33
TABLE 4-4
FINAL OIOXIN AND FURAN RESULTS FOR SOIL IN THE SOIL PANS
PAN 1 PAN 2 PAN 3 PAN 4 PAN 7
FURANS
HxCDF
HpCDF
OCDD
OIOXINS
HxCDD
HpCDD
OCDD
ND
ND
ND
ND
ND
1.5
18.0
164.0
262.0
4.2
250.0
1,250.0
6.5
71.9
116.0
ND
114.0
595.0
14.9
154.0
273.0
ND
210.0
958.0
ND
28.2
44.3
ND
43.7
205.0
NO indicates not detectable.
All concentrations nave units of ug/kg (ppb).
See Table 4-6 for definition of dioxin and furan isoners.
-------
TABLE 4-5
INITIAL AND FINAL OIOXIN AND FURAN RESULTS FOR
SOIL IN THE ZONE OF INCORPORATION IN THE SOIL COLUMNS
COLUMN C
INITIAL FINAL
FURANS
HxCDF
HpCDF
OCDF
NO
NO
NO
ND
ND
NO
COLUMN Al
INITIAL FINAL
COLUMN A2
INITIAL FINAL
COLUMN Bl
INITIAL FINAL
COLUMN B2
INITIAL FINAL
5.5
61.1
119.0
12.2
103.0
129.0
5.5
61.1
119.0
2.7
30.0
49.0
1.4
14.5
44.2
2.9
30.1
55.8
1.4
14.5
44.2
11.6
131.0
153.0
DIOXINS
HxCDO
HpCDO
OCOD
ND
ND
ND
NO
ND
.91
3.0
88.2
350.0
4.2
292.0
1410.0
3.0
88.2
350.0
ND
73.9
427.0
ND
37.8
227.0
ND
75.5
484.0
ND
37.8
227.0
ND
299.0
1560.0
NO Indicates not detectable.
All concentrations have units of ug/kg (ppb).
See Table 4-6 for definition of dioxin and furan isoaers.
-------
35
To place these results In a more meaningful context, the concentration
of the dioxin and furan isomers .were translated into an equivalent
concentration of 2,3,7,8 tetra-chlorodibenzo-p-dioxin (TCDO) using the
equivalency factors promulgated by the EPA (Federal Register, September
12, 1985). These equivalency factors are listed in Table 4-6. The
results for the soil pans are shown in Table 4-7 and for the soil
columns in Table 4-8.
The soil column data indicate that there were some dioxins and furans
in the layer beneath the zone of incorporation, but the concentrations
of these compounds were very low. Their presence in this layer is
probably due to mechanical mixing of soils in the upper and lower
layers during tilling.
Two observations are worth making about these results. First, these
equivalent concentrations of 2,3,7,8 TCDD are all below 1 part per
billion which Kimbrough et al (1983) of the Center for Disease Control
have suggested is a safe concentration in soils, based on their risk
assessment of 2,3,7,8 TCDO. Second, the equivalent concentrations of
2,3,7,8 TCDD reported in Tables 4-7 and 4-8 were computed assuming all
the isomers detected contained chlorine atoms in the 2,3,7,8 positions
on the dioxin or furan molecule. For isomers with chlorines hot in
these positions, the equivalency factors are 100 times less than those
listed in Table 4-6. Thus, the equivalent concentrations of 2,3,7,8
TCDD listed in Tables 4-7 and 4-8 are the highest values possible, and,
consequently, are conservative estimates.
Suaary
A good deal of information has been presented in this section,
permitting the statement of some general conclusions concerning the
transport and transformation of PCP, naphthalene and PAHs in an EBDS1".
-------
36
TABLE 4-6
TOXIC EQUIVALENCY FACTORS FOR
DIOXIN AND FURAN ISOMERS
Isoraer TEF
2,3,7,8 TCDD 1.0
2,3,7,8 PCDD .2
2,3,7,8 HxCDD .04
2,3,7,8 HpCDO .001
2,3,7,8 OCDD 0
2,3,7,8 TCDF .1
2,3,7,8 PCDF .1
2,3,7,8 HxCDF .01
2,3,7,8 HpCDF .0001
2,3,7,8 OCOF 0
NOTE:
TEF = Toxic Equivalency Factor. Divide above TEF's by
100 for Isomers without chlorines In one or more
of the 2,3,7 or 8 positions.
The prefixes on the above compounds are abbreviations for
T =
P =
Hx =
Hp =
0 =
tetra
penta
hexa
hepta
octa
The suffixes on the above compounds are abbreviations for
CDF * chlorinated dlbenzofuran
COD - chlorinated dibenzo-p-d1ox1n
Source: Federal Register, September 12, 1985.
VoluK 50. No. 177, pg. 340.
-------
37
TABLE 4-7
EQUIVALENT CONCENTRATIONS OF 2,3,7,8 TCDO
IN THE SOIL PANS
Pan 1 Pan 2 Pan 3 Pan 4 Pan 7
0 0.614 0.186 0.374 0.0465
All concentrations have units of ug/kg (ppb),
-------
TABLE 4-8
EQUIVALENT CONCENTRATIONS OF 2,3,7,8 TCDD AS A
FUNCTION OF DEPTH AND TINE IN THE SOIL COLUMNS
DEPTH
(ft)
0 - .5
.5 - 1.5
3.5 - 5
COLUMN C
INITIAL FINAL
0
0
0
0
0
0
COLUMN Al
INITIAL
0.269
0
0
FINAL
0.592
0.0059
0
COLUMN A2
INITIAL
0.269
0
0
FINAL
0.104
0
0
COLUMN 81
INITIAL
0.0533
0
0
FINAL
0.108
0.001
0
COLUMN B2
INITIAL
0.0533
0
0
FINAL
0.428
0.0057
0
All concentrations have units of ug/kg (ppb).
u>
00
-------
39
0 First, the downward movement of chemicals with leachate was
not an important process for removing a measurable fraction
of the initial mass of PCP, naphthalene or PAHs from the zone
of incorporation.
8 Second, volatile emissions were a small, but measurable,
removal process (representing 1 to 1Q% of the initial mass in
the soil) only for naphthalene and a few noncarcinogenic
PAHs. For PCP, the other noncarcinogenic PAHs and all
carcinogenic PAHs, volatile emissions were extremely low or
non existent.
0 Third, chemical/biological transformations were a significant
removal process for PCP, naphthalene and PAHs. In the soil
columns, significant chemical/biological transformation of
PCP and non carcinogenic PAHs occurred, while less extensive
transformation of naphthalene and carcinogenic PAHs took
place. However, in the pilot EBDS", PCP, naphthalene,
noncarcinogenic PAHs and carcinogenic PAHs all showed
significant chemical/biological transformation.
In conclusion, chemical/biological transformation of compounds occurred
in both the soil columns and pilot EBDS", but the evidence was
particularly striking in the pilot EBDS"1. In this system, over 80% of
PCP and naphthalene, and over 90% of PAHs were chemically/biologically
degraded. This transformation was evident from visual inspection of
the soil. At the start of treatment, the soil was visibly contaminated
with oil and grease. By the end of the study, the soil had the
consistency of garden soil and could conceivably be used as fill in
construction projects.
As for the dioxin and furan results, these compounds were detected in
soils in the soil pan and soil columns at the beginning and end of the
experiment. However, when the observed concentrations were converted
to equivalent concentrations of the most toxic dioxin isomer, 2,3,7,8
-------
40
TCDD, the cumulative equivalent concentration was below 1 part per
billion in all cases. The analysis of Kimbrough et al (1983) for the
Center for Disease Control suggests that concentrations of 2,3,7,8 TCDD
below 1 part per billion do not pose a health hazard.
4.2 Toxicity of Transformation Products
To answer the question "Are the transformation products of the treated
waste toxic?", acute toxicity tests were performed during the soil
column and pilot EBDS" studies. In both studies, soils were sampled
and subjected to daphnia and microtox bioassays. For both bioassays,
the standard protocol for conducting the test with soil samples was
used.
Table 4-9 shows the results of daphnia and microtox bioassays for soils
from the pilot EBDS™. In general, the results indicated that the soil
was relatively not toxic to daphnia at the beginning of the experiment.
In those instances where there was some toxicity at the beginning of
the experiment, the toxicity decreased by the end of the experiment.
On the other hand, the microtox bioassay indicates the soil was
relatively highly toxic to the luminescent bacteria at the beginning of
the experiment, but the toxicity declined with time.
The conflicting results of the two bioassays, which indicates the soil
is relatively nontoxic to daphnia and relatively toxic to microtox
bacteria, can be explained, to some extent, by differences in the
experimental protocols employed in the two test procedures. In the
microtox bioassay, soil is mixed with distilled water in a 1 to 4 ratio
(250,000 mg-soil/L-water), shaken for 22 hours, settled, and
centrifuged, and the liquid extract decanted. Different dilutions of
this extract, ranging from 100% to 21 or lower, are used in the
microtox assay to determine the EC5Q value. The percentages recorded
in Table 4-9 are the percentages of the extract that induced the EC.
-------
41
TABLE 4-9
RESULTS OF DAPHNIA AND MlCROTOX BIOASSAYS
ON SOILS FROM PILOT EBOS"
Mlcrotox EC50-15 minute (I)
Month Sector 1 Sector 2 Sector 3
2
16.9
39.0
0
3
6
4
18.7
19.0
3
37.2
56.0
Values are percent of liquid extract froa a mixture of
250,000 •g-soil/L-water.
Daphnia LC5Q (mg-soil/L-water)
Month Sector 1 Sector 2 Sector 3
0
3
6
>2,500
>2,500
>2,500
2,416
>2,500
>2,500
1,748
>2,500
>2,500
-------
42
In the daphnia bioassay, different ratios of soil to water are
combined, then the mixture is shaken for 20 minutes, allowed to settle
and the liquid extract decanted. This procedure yields extracts with
differing dilutions of chemicals which are used in the daphnia assay to
determine the LC5Q value. The highest ratio of soil to water in this
procedure is 1 to 400 (2500 mg-soil/l-water).
Two major differences between the daphnia and microtox assay are
evident from this discussion. First, the liquid extract used in the
microtox assay is derived from a 1 to 4 ratio of soil to water, which
is 100 times more concentrated than the 1 to 400 ratio used to generate
the liquid extract in the daphnia assay. Second, the soil-water
mixture used in the microtox assay is shaken for 22 hours which is 60
times longer than the 20 minutes used in the daphnia procedure. With
these extreme differences in testing protocols, it is not surprising
that the soil was much more toxic to the luminescent bacteria in the
microtox assay than to the daphnia water fleas in the daphnia assay.
What then, if anything, can be said about the toxicity of the
transformation products of the treated waste? In general, as waste
disappears from the soil, the toxicity, by either daphnia or microtox,
decreases. Figures 4-5 and 4-6 illustrate this point by showing the
change in daphnia and microtox results over time, along with the change
in oil and grease concentrations in the zone of incorporation over this
same time period. Figure 4-5 demonstrates this trend for soils in the
pilot EBDS" and Figure 4-6 presents the same information for soils in
the soil columns. Since acute toxicity tends to decrease as the waste
disappears from the soil, the transformation products do not appear to
be acutely toxic.
-------
Microtox EC50
Sol I Columns
j
8
o
2600
2346
Month of Operation
Oophnia LC50
Sol I Columns
2345
Month of Operation
Freon Extractablee
So iI Co Iumns
1234587
Month of Operation
FIGURE 4-5
ACUTE TOXICITY AND FRBON KXTRACTABLES IN SOIL COLPMliS
43
o Column C
A Co I urn V\\
a Colum tflZ
• Colum *BI
* Colum 182
-------
MICROTOX FATE
o
I—
o
at
1000-
500-
10000
StCTOR 1
SECTOR 2
SECTOR 3
CONTROL
44
O
in
0 1 2 3 4 3
MONTH
6 7
FREOM EXTRACTABLES
FIGURE 4-6
ACUTE TOXICITY AMD FREOH KXTRACTABLBS IH PILOT EBDS
-------
45
4.3 Emissions of Waste Constituents
To answer the question, "What are the emissions of waste constituents
from an EBDS1"?", each potential emission pathway must be examined.
These include:
e emissions to air,
0 emissions out of the zone of incorporation with leachate, and
0 emissions with stormwater runoff.
Emissions to Air
The results of the soil column and field studies indicate that
volatilization of contaminants from the soil will occur. The more
significant question is whether or not these emissions pose a public
health or environmental hazard.
Table 4-10 shows the ambient air concentrations measured during the
field study. Samples were taken at one upwind and two downwind
locations (see Figure 4-7) on each of the first three days of operating
the pilot EBDS". The table shows the ambient air concentrations
measured at the upwind location and the maximum ambient concentration
measured at the downwind location. In addition, the multimedia
environmental goals (MEG) (Cleland and Kingsbury, 1977) and New
Hampshire acceptable ambient air levels (AAL) (NHARA, 1985) are listed
for selected compounds.
Several things are worth noting about this data. First, for all
compounds except PCP, the ambient concentrations on each day are below
their respective MEG or AAL. In the case of PCP, the upwind
concentrations are as high or higher than the downwind concentration.
This suggests that background sources and not the pilot EBDS1" are
responsible for the levels of PCP in excess of the New Hampshire AAL.
-------
TABLE 4-10 46
AMBIENT AIR CONCENTRATIONS UPWIND AND DOWNWIND OF
THE PILOT EBDS-
DAY 1 DAY 2 DAY 3 MEG AAL
PHENOLS
PENTACHLOROPHENOL
NAPHTHALENE
ACENAPHTHYLENE
ACENAPHTHENE
FLUORENE
PHENANTHRENE
ANTHRACENE
FLUORANTHENE
PYRENE
.82
1.2
5.5
5.6
3.8
85.0
NO
1.3
1.5
16.0
1.1
6.2
3.7
9.3
.6
1.6
1.2
1.9
.45
1.4
.23
.59
3.8
3.6
.17
53.7
ND
.54
.4
7.4
.14
3.1
.38
4.37
.06
.14
.05
.26
.05
.2
.46 45 63
.38
3.9 1.7
3.04
1.3 119 166
16.9
ND
ND
1.1
1.43
.1
.47
.4 57
2.7
ND 133
ND
.12
.13
.23 556
.22
CHRYSENE
BENZO(A)ANTHRACENE
BENZO(B)FLUORANTHENE
BENZO(K) FLUORANTHENE
BENZO(A)PYRENE
DIBENZO(A.H)
ANTHRACENE
BENZO(G,H,I)
PERYLENE
INDENO(1,2,3-C,D)
PYRENE
.1
.17
.19
.2
.06
.12
.04
.05
.06
.12
NO
ND
.03
.04
ND
.05
.03
.04
.03
.04
.03
.05
ND
.03
.03
.05
ND
ND
ND
.03
.03
ND
.046 5.3
.044
.046 .81
.04
ND 2.1
.03
ND
ND
ND 4.1
.03
ND .81
ND
.046
ND
ND 3.0
ND
Top nuaber is upwind concentration. Bottoa nuaber is aaxiaua downwind
concentration. _
All concentrations have units of ug/a .
ND indicates not detectable.
-------
WIND DIRECTION
UPWIND
AIR MONITOR
PIGURB 4-7
LOCATION OF AIR MONITORS IH FIELD EXPERIMENT
O
•~50'
JETSTONE
\ENVIRONMENTALRESOURCES. INC.
in
•DOWNWIND
AIR MONITORS
1
1
o
in
I
t
SAMPLING
SECTOR 1
SAMPLING
SECTOR 2
onn •
t
SAMPLING
SECTOR 3
1
in
»H
*
STORM
RUNOFF
RETENTION
POND
CONTROL
PLOT
•DOWNWIND
AIR MONITORS
NOT TO SCALE
-------
48
Second, for all compounds, the ambient concentration decreases with
time. This is consistent with measurements taken in both the soil
column study and the pilot EBDS" study, that indicate volatile
emissions peak immediately after application of the contaminated soil
to the EBDS1" and decrease considerably thereafter (see Figure 4-8).
Thus, the concentrations displayed in Table 4-10 reflect the worst case
conditions for the pilot EBDS1" study.
Finally, it should be emphasized that the ambient air concentrations in
Table 4-10 are from locations immediately downwind of the treatment
plot. The actual exposure experienced by a worker or local resident
would be lower, and could be considerably lower, depending on the
actual location of the worker or resident with respect to the pilot
EBDS1".
In conclusion, the results of the ambient air monitoring of the pilot
EBDS1" indicate that the ambient air concentrations after loading the
pilot EBDS1" are below New Hampshire acceptable ambient air levels
(AALs) and multimedia environmental goals (MEGs) for those compounds
that have them. The emissions experiments on both the soil columns and
pilot EBDS1" suggest that volatile emissions will drop dramatically
following the initial loading of the EBDS1" and, consequently, ambient
air concentrations should likewise decrease.
Emissions With Subsurface Leachate
The extent to which chemicals were emitted with leachate from the EBDS1"
was investigated several ways. The maximum rainfall expected in a 25
year period at Nashua, NH was simulated on three of the laboratory soil
columns; TCLP leachate tests were performed on soil samples from the
pilot EBDS"; lysimeters were installed under the pilot EBDS" to collect
leachate; and monitoring wells upgradient and downgradient of the pilot
EBDS" were sampled and analyzed for waste constituents.
-------
FIGURE 4-8
EMISSIONS FROM THE PILOT BBDs"
49
NAPHTHALENE
ACENPHTHENE
a ACENAPHTHYLENE
-. METHYLNAPTHALENES
CL 1E-U
1E-2
15 22 29 36
DAYS OF OPERATION
-------
50
Storm Simulation. The twenty five year storm was simulated on soil
columns A2, B2 and C6 to estimate the Impact of surface contamination
on leaching resulting from an extreme storm event. The storm
simulation on A2 and 82 was performed at the end of the soil column
study, which corresponds to the time during the year when the maximum
25 year storm is expected. The storm simulation on C6 was performed
immediately after loading to simulate the worst conditions possible.
Table 4-11 displays the results of the storm simulation on columns 82
and C6. The storm simulation on column A2 did not yield any leachate.
This table includes the concentration of various chemicals in the soil,
as well as the concentration of these chemicals in the leachate. The
initial concentration of chemicals in the soil in column C6 were not
available, so the initial concentrations of chemicals in columns Al and
A2 were averaged and presented in Table 4-11. The initial
concentrations of chemicals in columns Al and A2 were used because
these columns received the same initial loading of waste as column C6.
It should be noted that soil concentrations are in parts per million
(ppm) while the leachate concentrations are in parts per billion (ppb),
so the concentrations in the leachate are less than the concentrations
in the soil by factors of 1,000 to 100,000 or more.
As in the case of air emissions, the relevant issue is whether or not
these concentrations pose a public health or environmental hazard.
Table 4-12 lists the maximum concentration of each chemical in either
leachate and relevant water quality criteria for those chemicals that
have them (USEPA, 1986). The water quality standards include values
for protecting both aquatic life and human health. The human health
level for naphthalene is based on a preliminary allowable daily intake
(ADI) value recently proposed by EPA, and, consequently, is not a
federal water quality standard (USEPA, 1984). All measured
-------
51
TABLE 4-11
CONCENTRATION OF CONSTITUENTS IN SOIL AND LEACHATE FROM
SOIL COLUMN STORM SIMULATIONS
COLUMN 82
COLUMN C6
pentachlorophenol
naphthalene
acenaphthylene
acenaphthene
fluorene
phenanthrene
anthracene
fluoranthene
pyrene
benz(a)anthracene
chrysene
benzo(b)fluoranthene
benzo(k)f1uoran thene
benzo(a)pyrene
dibenz(a,h)anthracene
benzo(g,h,i Jperylene
i ndeno(1,2,3-c,d)pyrene
— sun —
(•g/kg)
62.0
18.0
<.3
4.3
10.0
21.0
38.0
25.0
28.0
5.6
10.0
41.0
13.0
35.0
2.8
12.0
14.0
— LEACHATE
(ug/L)
42.00
<2,00
<.20
.70
.90
2.30
.12
.60
.47
<.04
<.04
<.04
<.04
<.04
<.04
<.04
<.04
SOIL
(mg/kg)
147.0
30.5
2.8
19.0
44.5
62.5
165.0
395.0
265.0
92.0
98.0
53.5
32.5
45.0
4.0
17.5
18.5
LEACHATE
(ug/L)
20.00
<2.00
<.20
.35
.85
1.00
.13
4.70
.65
<.04
.058
<.04
<.04
<.04
<.04
<.04
<.04
LAB BLANK
(ug/L)
1.80
<1.00
<.10
<.10
.09
.27
<.05
.12
.092
<.02
<.02
<.02
<.02
<.02
<.02
<.02
<.02
-------
52
TABLE 4-12
COMPARISON OF MAXIMUM LEACHATE CONCENTRATIONS
WITH MATER QUALITY STANDARDS
MAX CONC
(ug/L)
HUMAN HEALTH
(ug/L)
AQUATIC LIFE
(ug/L)
pentachlorophenol 42.00
naphthalene <2.00
acenaphthylene <.20
acenaphthene .70
fluorene .90
phenanthrene 2.30
anthracene .13
fluoranthene 4.70
pyrene .65
benz(a)anthracene <.04
chrysene .058
benzo(b)fluoranthene <.04
benzo(k)fluoranthene <.04
benzo(a)pyrene <.04
dibenz(a,h)anthracene <.04
benzo(g,h,i)perylene <.04
indeno(l,2,3-c,d)pyrene <.04
1010 3.2 to 55
1800
1700
188
3980
<.310
300
Source: US EPA Aablent Mater Quality Criteria (US EPA, 1986) for all
values except naphthalene. The naphthalene htman health criteria
Is based on a draft allowable dally Intake (ADI) published by the
EPA (US EPA, 1984).
-------
53
concentrations of.chemicals are either below the detection limit or
below the human health criterion.. In addition, all compounds but PCP
are below the water quality criteria for protection of aquatic life.
The PCP concentration was above the chronic toxicity level but below
the acute toxicity level.
Of the carcinogenic PAH, only chrysene appears in the leachate at
detectable levels. For carcinogenic PAH, the drinking water criteria,
which is based on the carcinogenic potency of benzo(a)pyrene, is .310,
.031 and .0031 ug/L for excess lifetime cancer risk levels of 10 ,
10 and 10 respectively. The concentration of chrysene falls in
this range, which is considered acceptable by EPA (Thomas, 1984). It
should be emphasized that this drinking water criterion is based on the
carcinogenicity of benzo(a)pyrene which is a considerably more potent
carcinogen than chrysene. A recent petition to EPA for deli sting a
RCRA waste proposed chrysene concentrations of 150, 15 and 1.5 ug/L for
excess lifetime cancer risk levels of 10 , 10 and 10 respectively
(Stern e.t al, 1985). These concentrations were developed based on the
carcinogenic potency of chrysene relative to benzo(a)pyrene. The EPA
gave preliminary sanction to using this level for chrysene. The
measured level of chrysene, .058 ug/L, is well below these
concentrations.
It should be remembered that the storm simulation represents a worst
case situation. Under normal weather conditions, the movement of water
through the soil is much slower than it was in the storm simulation.
As water moves out of the zone of incorporation, contaminants dissolved
in the water will adsorb onto soil surfaces. Thus, the relatively
clean soil below the zone of incorporation acts as a filter to purify
soil water as it migrates towards ground water. Also, compounds in the
dissolved phase are more amenable to microbial assimilation and
destruction.
-------
54
In the case of the storm simulation, the water may move principally
through soil macropores which offer too small a surface area for
appreciable adsorption reactions to occur. The flow of water in the
storm simulation is clearly too fast for significant biodegradation to
occur.
It is also worth noting that the pilot EBDS" was constructed with a
surface slope so that a substantial fraction of an extreme rainfall
event would run off into the stormwater detention pond. Thus, even if
an extremely heavy rain fell on the pilot EBDS", the ponding
experienced in the storm simulation would not occur.
To summarize, the storm simulation should yield the highest
concentrations of compounds that should ever be seen in the leachate.
Under normal weather conditions, the concentrations should be much
lower because of the filtering effect of the soil in the lower
treatment zone. Since the concentration of compounds in leachate from
the storm simulation should not pose a public health or environmental
hazard, leachate from normal weather conditions should also not pose a
problem.
TCLP Tests. To gauge the capacity of the treated soil to leach
chemicals, the toxicity characteristic leaching procedure (TCLP) was
performed. TCLP is a leaching test where water and soil are mixed
together in a ratio of 20 to 1, allowed to equilibrate, and the liquid
phase is extracted and subjected to chemical analysis. TCLP was
performed twice during the pilot EBDS1": once after three months and
once at the end of the study. In the first instance, TCLP was
performed on three samples from the experimental plots. In the second
instance, three samples from the control and three samples from the
experimental plot were composited and TCLP was performed on the
composite samples.
The TCLP results at the three month mark are shown in Table 4-13. The
extracts from two of the samples had concentrations of all chemicals
below the detection limit. The extract from the third sample had
-------
55
TABLE 4-13
TCLP Results for Pilot EBOS" After Three Months
Sector 1 Sector 2 Sector 3
PCP <1.00 <1.00 14,300.00
naphthalene <.50 <.50 145.00
acenaphthylene <.25 <.25 <.25
acenaphthene <.25 <.25 <.25
fluorene <.25 <.25 <.25
phenanthrene <.25 <.25 <.25
anthracene <.25 <.25 <.25
fluoranthene <.25 <.25 .807
pyrene <.25 <.25 <.25
chrysene <.25 <.25 <.25
benz(a)anthracene <.25 <.25 <.25
benzo(b)fluoranthene <.25 <.25 <.25
benzo(k)fluoranthene <.25 <.25 <.25
benzo(a)pyrene <.25 <.25 <.25
dibenzo(a,h)anthracene <.25 <.25 <.25
benzo(g,h,i)perylene <.25 <.25 <.25
indeno(1,2,3-c,d)pyrene <.25 <.25 <.25
carbazole <.25 <.25 .365
All concentrations have units of ug/L.
-------
56
detectable concentrations of four chemicals: carbazole, fluoranthene,
PCP and naphthalene. The concentrations of carbazole and fluoranthene
were very close to their detection limits and, consequently, may
reflect interference. At any rate, the concentration of fluoranthene
is well below its water quality criteria of 188 ug/L for protection of
human health and 3980 ug/L for protection of aquatic life (USEPA,
1986).
The concentrations of naphthalene and PCP are anomalous. The
naphthalene concentration is at least 300 times greater than the
naphthalene concentrations in the extracts from the other two samples.
However, it is still more than 10 times less than the human health
concentration of 1800 ug/L based on an allowable daily intake proposed
by EPA (USEPA, 1984).
The concentration of PCP is more perplexing. At 14.3 mg/L, it is
almost 15,000 times greater than the detection limit, which the other
two sample extracts were below. This is a huge discrepancy and the
value of 14.3 mg/L is much higher than one would expect based on the
initial concentration of PCP in the soils. At the three month mark in
the pilot EBDS1" study, the recorded concentration of PCP in the soil in
sampling sector 3 was about 40 mg/kg. In order for the leachate to
have a concentration of 14.3 mg/L, the soil had to have a concentration
of at least 286 mg/kg, based on the 20 to 1 ratio of water to soil in
the TCLP procedure and assuming all the PCP leaches off the soil and
into the water. This high level of PCP suggests that the soil sample
from the third sampling sector either had abnormally high
concentrations of PCP or an error occured in the sampling or laboratory
analysis.
The TCLP results at the conclusion of the pilot EBDS1" study for
phenolics, PCP, naphthalene and PAHs are presented in Table 4-14. For
all parameters except phenolics, concentrations were below the
detection limits for extracts from both the composited control and
composited experimental samples. The phenolics level was essentially
the same in the two extracts. Table 4-15 presents the results of
-------
57
TABLE 4-14
TCLP Results for Pilot EBDS" After Six Months
Control Experiment
Phenolics (4AAP) 595.00 455.00
PCP <1.00 <1.00
naphthalene <.50 <.50
acenaphthylene <.25 <.25
acenaphthene <.25 <.25
fluorene <.25 <.25
phenanthrene <.25 <.25
anthracene <.25 <.25
fluoranthene <.25 <.25
pyrene <.25 <.25
chrysene <.25 <.25
benz(a)anthracene <.25 <.25
benzo(b)fluoranthene <.25 <.25
benzo(k)fluoranthene <.25 <.25
benzo(a)pyrene <.25 <.25
dibenzo(a,h)anthracene <.25 <.25
benzo(g,h,i)perylene <.25 <.25
indeno(l,2,3-c,d)pyrene <.25 <.25
carbazole <.25 <.2S
All concentrations have units of ug/L.
-------
58
TABLE 4-15
TCLP Dloxln and Furan Results For Pilot EBOS" After 6 Months
Control Experiment
Furans
TCDF <.088 <.061
PCDF <.45 <.32
HxCDF <.28 <.23
HpCOF <.53 <.39
OCDF <1.40 <.92
Dioxins
TCDD <.22 <.15
PCDD <.48 <.35
HxCDO <.54 <.47
HpCDD <.61 <.48
OCDO <1.30 <1.10
All concentrations have units of ng/L.
-------
59
dioxin and furan analyses on extracts from these samples. The
concentrations of all dioxin and furan isomers were below the detection
limit.
Outdoor Lyslaeters. While the storm simulation gives a measure of
leachate concentrations that could arise under worst case weather
conditions, the outdoor lysimeter collects leachate from long term,
periodic rainfall events which should reflect the concentrations being
delivered to ground water under the normal operating conditions of an
EBDS™. However, during the course of the pilot EBDS1" study, which ran
from late spring to early fall, so little leachate occurred that
laboratory extraction and analysis was not possible.
Monitoring Wells. Since no leachate was collected in the lysimeter, no
contamination of ground water from the pilot EBDS1" is expected. To
check this contention, monitoring wells up gradient and down gradient
from the field plot were sampled and subjected to chemical analysis.
Figure 4-9 shows the location of the monitoring wells relative to the
pilot EBDS™. Table 4-16 displays the concentrations of various
chemicals in samples taken in August, 1986 and Table 4-17 displays the
same information for samples collected in November, 1986.
The August results indicated the concentration of phenolics and
naphthalene were below the detection limits in all wells. The results
for PCP showed levels just above the detection limits at the up
gradient well, but below detection limits at the down gradient wells.
The reading at the up gradient well, being close to the detection
limit, may be the result of interference. As for the PAHs, detectable
levels of fluoranthene, chrysene, benzo(a)anthracene, benzo(a)pyrene,
benzo(b)fluoranthene and benzo(k)flouranthene appeared in at least one
well. Of these, flouranthene, chrysene and benzo(a)pyrene appeared in
both the trip blank and field blank, and benzo(a)anthracene appeared in
the trip blank. This suggests that cross contamination occurred
somewhere in the sampling and analysis procedure. As for benzo(b)
fluoranthene and benzo(k)fluoranthene, they appeared only in the up
gradient well, so their presence cannot be due to the pilot EBDS".
-------
FIGURE 4-9
LOCATION OP GROUNDHATER MONITORING NELLS IN FIELD EXPERIMENT
GROUNDWATER
FLOW
DIRECTION
DOWNGRADIENT
WELLS
(DW1)
^KEYSTONE
\ ENVIRONMENTAL RESOURCES. INC.
UPGRADIENT
MONITORING
WELL
(UW)
1
o
in
1
SAMPLING
SECTOR 1
SAMPLING
SECTOR 2
SAMPLING
SECTOR 3
— J-LT R7 ' m-
MM °nn ' -j -
(DW2)
(DW3)
•ft&f/A
STORM
RUNOFF
RETENTION
POND
/x/64*
CONTROL
PLOT
NOT TO SCALE
NOTE
SAMPLING SECTORS 1, 2 AND 3 ARE DEFINED FOR
STATISTICALLY SAMPLING PURPOSES ONLY
-------
61
TABLE 4-16
NASHUA, NEW HAMPSHIRE
OUTDOOR EBDS" SOIL TREATMENT PILOT STUDY
MONITORING WELL SAMPLING RESULTS
(AUGUST, 1986)
CONCENTRATION, ug/L (ppb)
PARAMETER
PHENOLS (4-AAP)
PENTACHLOROPHENOL
NAPHTHALENE
ACENAPHTHYLENE
ACENAPHTHENE
FLUORENE
PHENANTHRENE
ANTHRACENE
FLUORANTHENE
PYRENE
BENZO( A) ANTHRACENE
CHRYSENE
BENZO(B) FLUORANTHENE
BENZO(K) FLUORANTHENE
BENZO(A)PYRENE
DIBENZ(A,H)ANTHRACENE
BENZO(G,H,I)PERYLENE
INDENO{1,2,3-C,D)PYRENE
MICROTOX,EC,n 15 MIN.Z
UN
<5.0
1.3
<0.5
<0.25
<0.25
<0.25
<0.25
<0.25
1.25
<0.25
<0.25
4.05
1.48
2.27
5.23
<0.25
<0.25
<0.25
>100(NT)
DW1
<5.0
<1.0
<0.5
<0.25
<0.25
<0.25
<0.25
<0.25
1.05
<0.25
<0.25
.83
<0.25
<0.25
<0.25
<0.25
<0.25
<0.25
>100(NT)
DM2
<5.0
<1.0
<0.5
<0.25
<0.25
<0.25
<0.25
<0.25
1.19
<0.25
.39
.78
<0.25
<0.25
2.00
<0.25
<0.25
<0.25
>100{NT)
DU3
<5.0
<1.0
<0.5
<0.25
<0.25
<0.25
<0.25
<0.25
1.19
<0.25
.37
.90
<0.25
<0.25
<0.25
<0.25
<0.25
<0.25
>100(NT)
TB
<5.0
<1.0
<0.5
<0.25
<0.25
<0.25
<0.25
<0.25
.91
<0.25
.50
.70
<0.25
<0.25
1.6
<0.25
<0.25
<0.25
FB*
<5.0
<1.0
<25.0
<25.0
<25.0
<25.0
<25.0
<25.0
72.7
<25.0
<25.0
44.7
<25.0
<25.0
456.0
<25.0
<25.0
<25.0
NOTES:
(a) UN denotes upgradient well, and DU1, DU2, DU3 denote downgradient wells.
(b) TB denotes trip blank and FB denotes field blank.
(c) * indicates that the detection 11«1t for the FB was increased to 25 ug/1.
(d) Indicated below detection limits.
(e) NT indicates nontoxic.
-------
TABLE 4-17
. NASHUA, NEW HAMPSHIRE
OUTDOOR EBOS" SOIL TREATMENT PILOT STUDY
MONITORING HELL SAMPLING RESULTS
(NOVEMBER 1986)
62
CONCENTRATION, ug/L
PARAMETER
PHENOLS (4-AAP)
PENTACHLOROPHENOL
NAPHTHALENE
ACENAPHTHYLENE
ACENAPHTHENE
FLUORENE
PHENANTHRENE
ANTHRACENE
FLUORANTHENE
PYRENE
BENZ(A)ANTHRACENE
CHRYSENE
BENZO(B)FLUORANTHENE
BENZO(K)FLUORANTHENE
BENZO(A)PYRENE
DIBONZ(A,H)ANTHRACENE
BENZO(G,H,I)PERYLENE
INDENO(1,2,3-C,D)PYRENE
MICROTOX,EC50 15MIN,(%)
NOTES:
UM
<5.0
1.8
<0.5
<0.25
<0.25
<0.25
<0.25
<0.25
<0.25
<0.25
<0.25
<0.25
<0.25
<0.25
<0.25
<0.25
<0.25
<0.25
>100(NT)
DU1
<5.0
1.2
<0.5
<0.25
<0.25
<0.25
<0.25
<0.25
<0.25
<0.25
<0.25
<0.25
<0.25
<0.25
<0.25
<0.25
<0.25
<0.25
>100(NT)
(ppb)
DH2
<5.0
1.6
<0.5
<0.25
<0.25
<0.25
<0.25
<0.25
<0.25
<0.25
<0.25
<0.25
<0.25
<0.25
<0.25
<0.25
<0.25
<0.25
>100(NT)
TB
<5.0
2.0
<0.5
<0.25
<0.25
<0.25
<0.25
<0.25
<0.25
<0.25
<0.25
<0.25
<0.25
<0.25
<0.25
<0.25
<0.25
<0.25
>100(NT)
FB
<5.0
1.7
<25.0*
<0.25
<0.25
<0.25
<0.25
<0.25
<0.25
<0.25
<0.25
<0.25
<0.25
<0.25
<0.25
<0.25
<0.25
<0.25
(a) UU denotes upgradlent well and DU1, DH2, DM3 denotes downgradlent wells.
(b) TB denotes trip blank and FB denotes field blank.
(c) * Indicates that the detection Halt for the FB was Increased to 25 ug/1
(d)
-------
63
Like the August results, the November results showed no detectable
levels of phenolics or naphthalene. However, PCP appeared in all the
wells. PCP also appeared in both the trip blank and field blank,
suggesting, once again, cross contamination during the sampling and
analysis procedure. For PAH's, all concentrations were below the
detection limits.
In conclusion, the results of the storm simulation on the soil columns
suggest that even under extremely adverse weather conditions, emissions
of contaminants with subsurface leachate should not pose a public
health or environmental problem. The emissions under more normal
weather conditions are expected to be much less than those during the
storm simulation, but these emissions cannot be conclusively assessed
at this time because the outdoor lysimeter did not collect enough
leachate. However, the TCLP leachate tests at the conclusion of the
pilot EBDS1", which failed to detect PCP, naphthalene, PAHs, dioxins or
furans in the liquid extract, suggest that contaminant emissions with
soil water leachate should not be a problem. This contention is
supported by the results of sampling ground water downgradient from the
pilot EBDS1" which indicates there is no contamination of ground water
from the EBDS"1.
Emissions With Storaxater Runoff
As noted previously, a properly designed EBDS1" should provide storm-
water management. In the case of the pilot EBDS™, all rainwater
falling on the treatment plot and subsequently running off, was
collected and stored in a lined stormwater retention pond. This water
was used to maintain soil moisture in the treatment plot. In a full-
scale EBDS™, a similar strategy could be employed, and any excess water
could be treated by the onsite wastewater treatment plant.
-------
64
5.0 SUMMARY AND CONCLUSIONS
This report discussed the results of laboratory and field studies
undertaken to evaluate the full scale implementation of an Engineered
Biodegradation System (EBDS™) for treating wood preservative residues
in soils. These results were presented in relation to three public
health and environmental questions posed in Chapter 2. The responses
to these questions form the major conclusions of this report and are
summarized below.
Does biodegradatlon of waste occur In an EBDS"? To answer this
question it was necessary to investigate the pathways whereby
constituents could either migrate from the zone of incorporation or be
transformed: leachate emissions, volatile emissions and
chemical/biological transformation. This investigation concluded with
three major findings.
0 . First, the downward movement of PCP, naphthalene and PAHs
with leachate was not an important process for removing a
measurable fraction of the initial mass of these chemicals
from the zone of incorporation.
0 Second, volatile emissions were a small, but measurable,
removal process (representing 1 to 10% of the initial mass in
the soil) only for naphthalene and a few noncarcinogenic
PAHs. For PCP, the other noncarcinogenic PAHs and all
carcinogenic PAHs, volatile emissions were extremely low or
non existent.
8 Third, chemical/biological transformations were a significant
removal process for PCP, naphthalene and PAHs. In the soil
columns, significant chemical/biological transformation of
PCP and noncarcinogenic PAHs occurred, while less extensive
transformation of naphthalene and carcinogenic PAHs took
place. However, in the pilot EBDS", PCP, naphthalene,
noncarcinogenic PAHs and carcinogenic PAHs all showed
significant chemical/biological transformation.
-------
65
In conclusion, chemical/biological transformation of compounds occurred
in both the soil columns and pilot EBDS1", but the evidence was
particularly striking in the pilot EBDS™. In this system, over 80% of
PCP and naphthalene, and over 90% of PAHs were chemically/biologically
degraded. This transformation of the soil was evident from visual
inspection. At the start of treatment, the soil was visibly
contaminated with oil and grease. By the end of the study, the soil
had the consistency of garden soil and could conceivably be used as
fill in construction projects.
As for the dioxin and furan results, these compounds were detected in
soils in the soil pan and soil columns at the beginning and end of the
experiment. However, when the observed concentrations were converted
to equivalent concentrations of the most toxic dioxin isomer, 2,3,7,8
TCDD, the cumulative equivalent concentration was below 1 part per
billion in all cases. The analysis of Kimbrough et al (1983) for the
Center for Disease Control suggests that concentrations of 2,3,7,8 TCDD
below 1 part per billion do not pose a health hazard.
Are the transformation products of the treated waste toxic? The
experimental results indicate that as waste disappears from the soil,
the acute toxicity by both daphnia and microtox decreases. Thus, any
transformation products created during the chemical/biological
transformation of the waste do not appear to be toxic.
What are the emissions of waste constituents fro* an EBOS"? To answer
this question it was necessary to examine the emissions from each
potential exposure pathway.
0 Emissions to air - The results of ambient air monitoring of
the pilot EBDS1" indicates that the ambient air concentrations
after loading the pilot EBDS" are below New Hampshire
acceptable ambient air levels (AALs) and multimedia
-------
66
environmental goals (MEGs). The emissions experiments on
both the soil columns and pilot EBDS™ suggest that volatile
emissions will drop dramatically following the initial
loading of the EBDS™ and, consequently, ambient air
concentrations should likewise decrease.
Emissions with subsurface leachate - The results of the storm
simulation on the soil columns suggest that even under
extremely adverse weather conditions, emissions of
contaminants with subsurface leachate should not pose a
public health or environmental problem. The emissions under
more normal weather conditions are expected to be much less
than those during the storm simulation, but these emissions
cannot be conclusively assessed at this time because the
outdoor lysimeter did not collect enough leachate. However,
the TCLP leachate tests at the conclusion of the pilot EBDS",
which failed to detect PCP, naphthalene, PAHs, dioxins or
furans in the liquid extract, suggest that contaminant
emissions with soil water leachate should not be a problem.
This contention is supported by the results of sampling
groundwater downgradient from the pilot EBDS™ which indicates
there is no contamination of groundwater from the EBDS1".
Emissions with stormwater runoff - Since a properly designed
EBDS"1 should provide stormwater management, emissions with
stormwater runoff should not occur.
157098-00
-------
67
Reference
ACGIH, 1986. "Threshold Limit Values and Biological Exposure Indices."
America! Conference of Governmental Industrial Hygienists,
Cincinnati, OH.
Cleland, J.G and G.L. Kingsbury, 1977. Multimedia Environmental Goals
for Environmental Assessment. Volume I and II. EPA/600/13,
November, 1977.
Federal Register; September 12, 1985; vol 50, no 177, pg 340.
Kimbrough, R.D., H. Falk, P. Stehr, C. Portier and G. Fries. Risk
Assessment Document on 2,3,7,8 Tetrachlorodibenzo-dioxin
(TCDD) Levels in Soil. Center for Environmental Health,
Centers for Disease Control, National Institute of
Environmental Health Sciences, USDA, Beltsville, MD; 1983.
Koppers Co., 1985; The Land Treatability of Creosote/Pentachlorophenol
Wastes; prepared by EnvironmentalResearch and Technology,
Inc.; August, 1985.
NHARA; Air Toxics Program Guideline (Draft). New Hampshire Air
Resources Agency, July 1985.
Santodonato, J., P. Howard and 0. Basu; Health and Ecological
Assessment of Polynuclear Aromatic Hydrocarbons; Journal of
Environmental Pathology and Toxicology; vol 5(l):l-364.
Sims, R.C. and M.R. Overcash; Fate of Polynuclear Aromatic Compounds
(PNAs) in Soil-Plant Systems; Residue Reviews; Vol. 88: pgs
1-68; 1983.
Thomas, Lee, 1984. EPA Memorandum on Determining Acceptable Risk
Levels for Carcinogens in Setting Alternate Concentration
Levels Under RCRA. Nov. 19, 1984.
US EPA, 1984. Personal communication from the Office of Research and
Development to Carlos Stern Associates concerning ADIs (with
enclosures); Cincinnati, OH; Dec. 28, 1984.
US EPA, 1986; Quality Criteria For Water, 1986; EPA 440/5-86-001.
-------
APPENDIX A; TOX1CITY ASSESSMENT
This appendix provides a toxicity assessment of selected chemicals found in the
soils at the Nashua site. These chemicals are:
phenolics,
pentachlorophenoi (PCP),
naphthalene,
polynuclear aromatic hydrocarbons (PAH).
A brief description of the human health and environmental effects of these
compounds or classes of compounds is provided in subsequent sections. First,
however, the classification of PAH compounds as carcinogenic versus
noncarcinogenic is discussed.
1.0 TOXICITY CLASSIFICATION OF PAH COMPOUNDS
For PAH compounds, the EPA has provided carcinogenic rankings in two separate
documents, .the EPA Superfund Public Health Evaluation Manual (SPHEM) and the
EPA Chemical Profiles document. These rankings are reproduced in Table A-l for
the PAH compounds analyzed for during the land treatment studies. In general, the
rankings from the two sources agree, although some compounds are ranked in only
one document.
Table A-l also contains the rankings developed for the purposes of this report. If
there was any evidence of carcinogenicity in animals, the compound was classified
as a carcinogen. If the experimental data suggest the compound is not
carcinogenic, it was classified as a noncarcinogen. For three compounds,
acenaphthyJene, acenaphthene, and fluorene which have insufficient data to make a
classification, these compounds were classified as noncarcinogenic because they
are low ring PAH and low ring PAH are not believed to be carcinogenic. The other
compound which had insufficient data to make a classification,
benzo(g,h,i)perylene, is a higher ring PAH and was classified as a carcinogen since
the higher ring PAH often can be carcinogenic.
Ai-1
-------
TABLE A-l
CARCINOGENIC RANKING OF SELECTED PAHs
Acenaphthylene
Acenaphthene
Fluorene
Phenanthrene
Anthracene
Fluoranthene
Pyrene
Benz(a)anthracene
Chrysene
Benzo(b)fluoranthene
Benzo(k)fluoranthene
Benzo(a)pyrene
Dibenz(a,h)anthracene
Benzo(g,h,i)perylene
Indeno(l,2,3-c,d)pyrene
EPAl
SPHEM
U
U
U
D
U
U
U
B2
B2
B2
D
B2
B2
U
C
EPA2
Chem. Prof
U
U
I
I
N
N
N
C
L
C
C
C
C
I
C
Ranking^
for this Study
N
N
N
N
N
N
N
C
C
C
C
C
C
C
C
1 Source: EPA Superfund Public Health Evaluation Manual, ratings follow EPA weight-
of-evidence categories given in Table A-2.
2 Source: EPA Chemical Profiles. Ratings follow categories given in Table A-3.
3 Rating follows categories given in Table A-3.
Al-2
-------
TABLE A-2
EPA WEIGHT-OF^EVIDENCE
CATEGORIES FOR POTENTIAL CARCINOGENS
EPA
Category
Description
of Category
Description of Evidence
Human Carcinogen
Bl Probable Human
Carcinogen
B2 Probable Human
Carcinogen
C Possible Human
Carcinogen
D Not Classified
E No evidence of
Carcinogenicity
in Humans
U No rating given
Sufficient evidence from epidemiologic studies
to support a casual association between exposure
and cancer.
Limited evidence of carcinogenicity in humans
from epidemiologic studies.
Sufficient evidence of carcinogenicity in
animals, inadequate evidence of carcinogenicity
in humans.
Limited evidence of carcinogenicity in animals.
Inadequate evidence of carcinogenicity in
animals.
No evidence for carcinogenicity in at least two
adequate animal tests or in both epidemiologic
and animal studies.
Al-3
-------
TABLE A-3
EPA CATEGORIES USED TO CLASSIFY
CARCINOGENICITY OF PAH COMPOUNDS IN
CHEMICAL PROFILES DOCUMENT
Category Description
N Available data provides no evidence that chemical is carcinogenic in
animals.
L Available data provides limited evidence that chemical is carcinogenic
in animals.
C Available data provides sufficient evidence that chemical is carcinogenic
in animals.
I Available data is inadequate to characterize the carcinogenicity of these
chemicals.
U No rating given to this chemical.
A1-
-------
2.0 SUMMARY OF HUMAN HEALTH EFFECTS
Phenolics
The major benzene-derived hydroxyaromatic compounds of toxicologic interest are
phenol, cresols, and xylenols. The human health effects of primary concern are
similar for all three types of substances. None of these compounds are generally
regarded as carcinogenic per se, yet all of them present a significant acute
poisoning hazard.
Concentrated solutions of phenol rapidly penetrate the skin of humans, and can
result in death in less than 10 minutes (NIOSH, 1976). Skin or eye contact with
phenol, even in very small amounts, has led to serious irreversible tissue damage.
Ingestion of as little as a few grams of phenol is also sufficient to cause death in
humans. Experiments with several species of laboratory animals have confirmed
the local effects of phenol to skin and eyes, and also have demonstrated severe
systemic effects such as necrosis of the myocardium, lobular pneumonia, vascular
damage, and hepatic and renal damage.
There are numerous case reports of human poisoning resulting from acute exposure
to ortho, meta and para-cresols. The skin is considered to be the primary route of
occupational exposure to cresols. Skin contact with cresols has resulted in skin
peeling on the hands, facial peripheral neuritis, severe facial burns, and damage to
the liver, kidneys, pancreas, and vascular system (NIOSH, 1978). In most respects,
the toxicity of cresols is the same as for phenol, although some evidence suggests
that creosol is more toxic by the inhalation route. There are no reports in the
literature describing the human health effects resulting from chronic low-level
exposure to cresols.
Limited toxicity information is available for the six possible isomers of xylenol.
The xylenols are all moderately toxic by acute exposure; oral LD50 values fall in
the range of 383-980 mg/kg for mice and 296-3200 mg/Kg for rats (Uzhdavini et al,
1974; Maazik, 1968; Larionov, 1976; Veldre and Janes, 1979). Symptoms of acute
poisoning in experimental animals include dyspnea, disturbance of motor
coordination, clonic spasms, and paralysis. Inhalation of xylenol by animals causes
irritation of the mucous membranes and affects respiratory activity. The xylenols
A2-1
-------
are rapidly absorbed through the skin and cause moderate skin irritation. Effects
on the central nervous system and tissue damage in the liver, spleen, and kidney
have been observed in acute animal bioassays, but the effects are not as severe as
with phenol and cresol. There are no detailed reports available concerning the
toxic effects of xylenols to humans.
There exists limited evidence to suggest that phenol, cresol, and xylenol may act as
tumor promoters when applied to the skin of mice that was previously treated with
a carcinogenic PAH (Boutwell and Bosch, 1959; Wynder and Hoffman, 1961; Van
Duuren et al., 1968). There is also a suggestion that phenol and xylenol by
themselves are weak skin carcinogens in mice when applied individually (Boutwell
and Bosch, 1959; Wynder and Hoffman 1961). The relevance of these observations
to human health under realistic conditions of exposure has not been established.
This section has been adapted from Koppers et al (1985).
Pentachlorophenol
The toxicity of pentachlorophenol is centered largely on its potential as a
metabolic poison. The fatal dose of this material in animals is listed by Arena
(1976) as being from 30 to 100 mg/kg. Thus, the material should be regarded as
highly to moderately toxic by acute exposures. The compound is a skin irritant and
produces an elevation of body temperature, that is, a fever. Additionally,
tachycardia (increased heart rate), sweating and shortness of breath are reported
as acute signs and symptoms. The toxic signs of pentachlorophenol intoxication
following multiple exposures within a short time exposure are similar to those that
occur acutely after a single excessive exposure. The TLV documentation (ACGIH,
1985) reports that acute exposure by inhalation leads to adverse circulatory system
effect with accompanying heart failure. The TLV documentation indicates that
workers do become tolerant to the material. There is little difference, acute
versus chronic, in the reportable signs when toxic effects are seen (Tsapakos and
Wetterhahn, 1983). While opinions may differ, it appears that PCP is not a
cumulative toxicant in the way that other chlorinated pesticides like DDT, etc. are
cumulative. In cases of excess exposure with prominent clinical signs,
alkalinization of the urine by treatment with bicarbonate results in increased
excretion of the unchanged PCP. Such a therapeutic regimen is suggested after
A2-2
-------
acute exposure (Haley, 1977). In the world literature where acute intoxication has
been reported, 31 of the 50 cases reported have been fatal. Survivors of PCP
intoxication are reported to suffer from impairment of autonomic function,
circulation defects, visual damage, and an acute type of scotoma, a loss of vision in
a particular area of the visual field (Imaizum). Thus, the material should be
regarded as a highly acutely toxic substance when encountered in concentrated
form. At lower concentrations, where no overt toxic effects are noted, while not
without effect, the material appears to be excreted rapidly and does not
accumulate in the body.
Even though PCP is highly water soluble, metabolism in man and animals does
occur (Ahlborg et al, 1978). Quinone compounds and hydroquinones are among the
metabolites. However, as noted above, a substantial amount of the exposure dose
is excreted as PCP per se. Urine and blood samples from exposed persons have
been shown to contain PCP (Begley et al, 1977). Normal persons who live in areas
where PCP is used for wood treatment, i.e. the south as well as Hawaii, have PCP
in their urine (Bevenue et al, 1967). Among exposed persons who were followed
over a vacation period (Begley et al, 1977; Bevenue et al, 1967; Kalman and
Horstman, 1983), urinary concentrations of PCP as well as other chlorinated
compounds were found to decline. Dechlorinated metabolites as well as
conjugation products have been reported (Ahlborg et al, 1978). A role of the
compound as an uncoupler of oxidative phosphorylation (a metabolic energy-
generating process) has been suggested (Arrhenius et al, 1977). It is also suggested
that PCP may inhibit microsomal metabolism and, thus, it may alter its own
pattern of bio-transformation. Such effects are likely only at elevated exposure
concentrations (such as occupational exposure) and may have little likelihood of
occurrence at environmental levels. Among workers exposed to PCP, slight
changes in kidney function were noted but recovery occurred after a vacation
period (Begley et al, 1977). Whether these kidney effects were due to PCP or a
metabolite is uncertain. The authors do not provide any data on the exposure
concentration or the concentration of chlorinated contaminants. Epidemiologic
studies do not indicate substantial morbidity (illness) among workers exposed to
PCP in addition to other wood preservation chemicals (Gilbert et al, 1983).
Exposure concentrations are poorly documented in this industry. Most industry
exposure occurs because of skin contact.
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The National Academy of Sciences (NAS, 1977) stated that, as of the date of their
review, there were no data suggesting the carcinogenicity of pentachlorophenol.
Since the time of that review, neither the National Cancer Institute (NCI) nor the
National Toxicology Program (NTP) has conducted an animal bioassay of the
carcinogenic potential of PCP per se in either rats or mice. Studies conducted by
Boutwell and Bosch (1959) showed that dermally applied PCP lacked a promoting
action when dimethylbenzanthracene was used as the initiator. An initiator is a
chemical which begins or invokes a malignant change in cells. In contrast, a
promoter is an agent which makes the appearance of tumors more likely. These
results suggest that carcinogenic risks due to PCP exposure are unlikely.
It has been reported that workers in a PCP production facility in Germany were
found to have an elevated number of abnormal chromosomes (Bauchinger et al,
1982). Exposures are not known. However, in this population, the PCP workers
were all smokers. When the control population was adjusted to include only
smokers, the previously observed increase in chromosome abnormality was no
longer significant. It should be noted that the observation of chromosome
abnormalities is not known to be associated with a disease process. Such
clastogenic (chromosome damaging) effects are thought to be adverse but their
etiology and outcome are uncertain. Thus, they indica*-? biologic potential, but in
this case they appear to be related to cigarettes and not PCP.
The reproductive effects of PCP on humans are not well studied. Few females
work in the industry, making studies of reproductive history difficult. In studies on
animals (Schwetz et al (1974) investigated the effects of PCP on fetal growth and
development. Both purified and commercial grades of PCP were tested at doses of
5, 15, 30, and 50 mg/kg (pure grade), while the technical grade was given at 5.8 and
34.7 mg/kg to rats. The maximum tolerated dose tested was 50 mg/kg for 10 days.
Daily doses were given to pregnant rats from day 6 through day 15 of gestation
(inclusive). Fetal resorption occurred at the higher doses, a result indicative of
fetotoxicity (damage or injury to the fetus) and lower doses were associated with a
dose-related decrease in the resorption rate. At elevated doses of both technical-
grade and purified PCP, developmental abnormalities were seen. Because of this
finding, the EPA has expressed concern over pentachlorophenol's ability to cause
birth defects and has concluded that PCP is teratogenic (US EPA, 1984a).
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Based upon the toxicology described and the relatively simple toxic effects
produced, pentachlorophenol can be regarded as a relatively uncomplicated toxic
substance of moderate acute risk. While available evidence was not sufficient to
conclude that PCP is not a teratogen, this view was adopted by the EPA as a
conservative assumption. The available data indicates that PCP is not a
carcinogen.
This section has been adapted from Koppers et al (1985).
Naphthalene
There are no epidemiological or case studies available suggesting that naphthalene
is carcinogenic in humans. This compound is not generally considered to be
carcinogenic in experimental animals. However, there is equivocal evidence
suggesting weak carcinogenic activity in rats after subcutaneous injection.
Naphthalene is reported to produce DNA damage in mice after intraperitoneal
injection. Retarded cranial ossification and heart development are reported among
offspring of rats injected intraperitoneally with naphthalene on days 1 to 15 of
gestation.
Little information concerning acute and chronic toxic effects is available.
Inhalation exposure to naphthalene may cause headache, loss of appetite, nausea,
and kidney damage in humans and experimental animals. Acute hemolytic effects
are reportedly caused by ingestion or inhalation of relatively large quantities of
naphthalene. Optical neuritis, injuries to the cornea, and opacities of the lens also
may result after inhalation exposure or ingestion. Naphthalene is a mild eye
irritant in rabbits, and cataracts can be induced after oral administration.
Application to the skin produces erythema and slight edema in rabbits. Somnolence
and changes in motor activity are observed after ingestion of naphthalene by rats
and mice. Oral LD^n values of 1,250 mg/kg and 580 mg/kg are reported for the rat
and the mouse, respectively.
This section has been adapted from the US EPA (1985).
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Noncarcinogenic PAHs -
Acenaphthylene
There are no epidemiological or case studies suggesting that acenaphthylene is
carcinogenic in humans. There are no reports of carcinogenic, teratogenic, or
reproductive effects in experimental animals. Acenaphthylene is reported to have
weak mutagenic activity in a Salmonella typhimurium test system (Kaden et al,
1979).
No information concerning acute or chronic toxicity is available. Like many other
PAHs, acenaphthylene may be a skin irritant, but little specific information is
available.
This section has been adapted from the US EPA (1985).
Phenanthrene
There are no epidemiological or case studies available suggesting that
phenanthrene is carcinogenic in humans. This compound generally is not considered
to be carcinogenic in experimental animals. However, at least two skin painting
studies report development of tumors at the site of application in mice.
Phenanthrene exhibits mutagenic activity in some test systems, but not in others.
There are no reports of teratogenic or reproductive effects due to phenanthrene
exposure.
Little information concerning acute and chronic toxic effects is available.
Although specific data concerning exposure to phenanthrene are not available,
workers exposed to materials containing this compound may exhibit chronic
dermatitis, hyperkeratoses, and other skin disorders.
This section has been adapted from the US EPA (1985).
Anthracene
There are no epidemiologic studies available suggesting that anthracene is
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carcinogenic in humans. This compound generally is not considered to be
carcinogenic in experimental animals (IARC, 1983). However, there is equivocal
evidence suggesting weak carcinogenic potential. In rats, tumors were reported to
develop at the injection site after subcutaneous administration, and in the liver
after oral administration. Anthracene exhibits mutagenic activity in some test
systems but not in others. There are no reports of teratogenic or reproductive
effects due to exposure.
Little information concerning acute and chronic toxic effects is available. Specific
data concerning exposure to anthracene are not available, but workers exposed to
materials containing this compound may exhibit dermatitis, hyperkeratosess, and
other skin disorders. Anthracene produces mild erythema and edema after
application to the skin of mice. An intraperitoneal LD^Q of 430 mg/kg is reported.
This section has been adapted from the US EPA (1985).
Fluoranthene
There is no information concerning the carcinogenicity of fluoranthene in humans,
and fluoranthene shows no activity as a complete carcinogen in experimental
animals. However, fluoranthene appears to possess potent cocarcinogenic activity
in test animals. Fluoranthene has displayed no mutagenic activity in in-vitro
bacterial test systems. No other information is available concerning its potential
mutagenic or teratogenic effects, nor with regard to its acute or chronic toxicity
to humans. Results from animal studies indicate that fluoranthene has relatively
low acute toxicity. Where deaths of experimental animals have occurred, no
information concerning target organs or specific causes of death has been reported.
Descriptions of chronic toxicity are limited to reports of mortality produced in
mice by repeated dermal application or subcutaneous injection.
This section has been adapted from the US EPA (1985).
Acenaphthene
The effects on humans of acute or chronic exposure to acenaphthene are poorly
understood. It is irritating to skin and mucous membranes and may cause vomiting
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if swallowed in large amounts (Sax, 1975). Neither a human health criterion nor an
acceptable daily intake (ADI) has been established for acenaphthene. There are no
case reports nor any epidemiologic studies on the carcinogenicity of acenaphthene.
Epidemiological studies that analyze human exposure to PAHs will inevitably also
cover exposure to acenaphthene, but it is impossible to determine the specific
effect of any one member of the PAH group.
Acenaphthene is a minor constituent of the PAHs found in water. Only one study
(Onuska et al, 1976) has found the occurrence of acenaphthene in foods (level
exceeded 3.1 mg/kg in shellfish). The amount of acenaphthene relative to other
PAHs was small (EPA, 1980). There are very limited data on human exposure to
acenaphthene. EPA estimates that exposure through ingestion is 0.4 ng/day from
water, 60 ng/day through food, and 4-180 ng per day from inhalation (based on data
in urban areas). Thus, the average intake is estimated to be about 60-240 ng/day,
with water supplying only a very small proportion. Acenaphthene has been
measured in cooking oil, shucked oysters, charcoal broiled beef, and smoked meats,
such as pork and sausage. Acenaphthene is not one of the compounds on the
Appendix VIII list.
Although acenaphthene by itself has not been subjected to rigorous toxicity testing,
the EPA has proposed an ambient water quality criterion for acenaphthene based
on its organoleptic properties of 20 ug/L. This was the lowest concentration at
which any of 14 judges could detect the odor (Liliard and Powers, 1975). The EPA
has not proposed an ambient water quality criterion for acenaphthene based on the
protection of human health. The level based on organoleptic property is probably
far lower than could be justified for the protection of health since the substance is
apparently neither carcinogenic nor particularly toxic, based on the limited
available data.
There is no evidence to suggest that acenaphthene is carcinogenic. No tumor
promoting activity was noted when acenaphthene was tested in combination with
other PAHs extracted from cigarette smoke condensate (Akin, 1976).
values of 10 g/kg and 2 g/kg have been noted in rats and mice respectively
(Knobloch et al, 1969). Based on animal feeding studies, an oral dose of 300 mg/kg
diet of acenaphthene is considered to be the NOEL (No Observable Effect Level).
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This section has been adapted from Stern et al (1985).
Pyrene
Inadequate data exist to assess the effects on humans of acute or chronic exposure
to pyrene. No human health criteria has been established for pyrene; neither has
an acceptable daily intake (ADI). There are no case reports or epidemiologic
studies on the carcinogenicity of pyrene per se, because it almost always occurs in
combination with several other PAHs.
Pyrene has not been found to be carcinogenic in animal studies (IARC, 1983). Skin
applications of pyrene at various concentrations for 1-2 years did not cause tumors
in mice. The addition of n-dodecane to decalin containing 0.5 percent pyrene
applied twice weekly to mice did not demonstrate co-carcinogenic or carcinogen
enhancement (Horton and Christian, 1974). Pyrene was found to enhance the
carcinogenic effect of benzo(a)pyrene (Van Duuren and Goldschmidt, 1976). It has
been concluded by IARC (1983) that based on animal studies, there is no evidence
that pyrene is carcinogenic.
Oral LD^QS for pyrene fed to mice fall in the range of 500-700 mg/kg body weight
(Salamone, 1981).
This section has been adapted from Stern et al (1985).
Carcinogenic PAHs
Chrysene
The potential for polycyclic aromatic hydrocarbons to induce malignant trans-
formation dominates the consideration given to health hazards resulting from
exposure. This is because overt signs of toxicity are often not produced until the
dose is sufficient to produce a high tumor incidence.
No case reports or epidemiological studies on the significance of chrysene exposure
to humans are available. However, coal tar and other materials known to be
carcinogenic to humans may contain chrysene. Chrysene produces skin tumors in
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mice following repeated dermal application. High subcutaneous doses are reported
to result in a low incidence of tumors with a long induction time in mice. Chrysene
is considered to have weak carcinogenic activity compared to benzo(a)pyrene.
Chrysene is reported to be mutagenic in a variety of test systems. No information
concerning the teratogenic effects of chrysene in humans or experimental animals
is available.
Although there is little information concerning other toxic effects of chrysene, it
is reported that applying the carcinogenic PAHs to mouse skin leads to the
destruction of sebaceous glands, hyperplasia, hyperkeratosis, and ulceration.
Workers exposed to materials containing these compounds may exhibit chronic
dermatitis, hyperkeratoses, and other skin disorders. Although specific results with
chrysene are not reported, it has been shown that many carcinogenic PAHs have an
immunosuppressive effect.
This section has been adapted from the US EPA (1985).
Benzo(a)anthracene
There are no studies of the effects on humans of short-term or long-term exposures
to benzo(a)anthracene per se. Epidemiologic studies to which benzo(a)anthracene
may have contributed have all been concerned with exposure to a mixture of PAHs.
Thus, specific impacts of benzo(a)anthracene exposure cannot be distinguished
from those of other compounds. Human exposure to benzo(a)anthracene occurs
together with exposure to other PAHs; for example, from cigarette smoke or air,
water, or food contaminated with combustion products. Because of the lack of
data, neither a human health criterion nor an acceptable daily intake (ADI) has
been established for benzo(a)anthracene.
IARC (1983) concluded from various animal studies that benzo(a)anthracene is
carcinogenic in mice when administered orally and dermally. A positive dose-
response relationship was observed following a mouse skin-painting study using
benzo(a)anthracene in toluene; tumor incidence increased when dodecane was used
as the carrier, indicating a co-carcinogenic effect (Bingham and Falk, 1969).
Neither acute nor chronic exposures to benzo(a)anthracene appear to produce
significant toxic effects.
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This section has been adapted from Stern et al (1985).
Benzo(b)fluoranthene
Adequate data do not exist to assess the effects on humans of acute or chronic
exposure to benzo(b)fluoranthene. Neither a human health criterion nor an
acceptable daily intake (ADI) have been established for benzo(b)fluoranthene.
Mouse skin-painting studies indicate that benzo(b)fluoranthene is a complete
carcinogen (Habs and Schmahl, 1980), and that it can act as a tumor initiator.
IARC (1983) concluded that sufficient evidence exists to consider
benzo(b)fluoranthene carcinogenic in experimental animals.
The noncarcinogenic effects produced by chronic exposure to benzo(b)fluoranthene
are not known. No data were found on teratogenicity or other reproductive effects
of this compound.
This section has been adapted from Stern et al (1985).
Benzo(k)f luoranthene
There are no studies of the effects on humans of acute or chronic exposures to
benzo(k)fluoranthene per se. In addition, there are no case reports or
epidemiologic studies on the carcinogenicity of benzo(k)fluoranthene per se.
Human exposure to benzo(k)fluoranthene always occurs together with exposure to
other PAHs either directly from cigarette smoke or indirectly from air, water, or
food contaminated by combustion effluents. No human health criteria or
acceptable daily intake (ADI) levels for benzo(k)f luoranthene have been
established.
Benzo(k)fluoranthene is currently not classified as carcinogenic or noncarcinogenic.
The lowest published dose at which a toxic effect has been observed in mice is
2,820 mg/kg administered percutaneously at intermittent periods over 47 weeks
and 72 mg/kg administered subcutaneously at intermittent periods over 9 weeks
(NIOSH, RTECS, 1985). No papillomas or carcinomas were observed in mice skin-
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painted with 0.5 percent benzo(k)fluoranthene for 47 weeks (Wynder and Hoffman,
1959).
This section has been adapted from Stern et al (1985).
Dibenzo(ath)anthracene
There are no studies of the effects on humans of acute or chronic exposures to
dibenzo(a,h)anthracene per se. Epidemiologic studies to which
dibenzo(a,h)anthracene may have contributed have all been concerned with
exposures to a mixture of PAHs. Thus, any specific impact from
dibenzo(a,h)anthracene exposure cannot be distinguished from those of other
compounds. Human exposure to dibenzo(a,h)anthracene occurs together with
exposure to other PAHs; for example, from cigarette smoke or air, water, or food
contaminated with combustion products. Dibenzo(a,h)anthracene is a minor
component of the polynuclear aromatic hydrocarbons present in the ambient
environment. Because of the lack of data, neither a human health criterion nor an
acceptable daily intake (ADI) has been established for dibenzo(a,h)anthracene.
Very large oral doses of dibenzo(a,h)anthracene, 4520 mg/kg, have been necessary
to elicit a toxic effect in mice. Daily subcutaneous injections of 25 mg/kg/day
have caused fetal death and resorption in mice (Wolfe and Bryan, 1939).
Dibenzo(a,h)anthracene was the first pure chemical compound shown to be
carcinogenic (Kennaway, 1930). This compound can act as a local or systemic
carcinogen in several animal species (NTP, 1983). Orally administered
dibenzo(a,h)anthracene has produced tumors and carcinomas in the forestomach,
lung, heart, intestine, and mammary gland of mice (Lorenz and Stewart, 1947; Snell
and Stewart, 1962; Biancifiori and Caschera, 1962). Dibenzo(a,h)anthracene
produced more injection site sarcomas than did benzo(a)pyrene. When applied
topically to mouse skin, the compound acts as a tumor initiator or complete
carcinogen (Klein, 1960). Skin painting studies indicate that its carcinogenic
potency is of the same general order of magnitude as that of benzo(a)pyrene
(Wynder and Hoffman, 1959).
This section has been adapted from Stern et al (1985).
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Benzo(g.h,i)perylene
The human effects of acute or chronic exposure to benzo(g,h,i)perylene are
unknown. Neither a human health criterion nor an acceptable daily intake (ADI)
has been established for benzo(g,h,i)perylene. There are no case reports or
epidemiologic studies on the carcinogenicity of benzo(g,h,i)perylene per se because
it only occurs in combination with other PAHs. Epidemiological studies that
analyze exposure to PAHs will inevitably also cover exposure to
benzo(g,h,i)perylene, but it is impossible to determine the net effect of any one
member of the PAH group.
There is very limited data on human exposure to benzo(g,h,i)perylene. EPA
estimates that exposure through ingestion is 0.4 ng/day for water and 60 ng/day
through food. Based on data in urban areas, inhalation is estimated to be 4-180 ng
per day. Benzo(g,h,i)perylene has been measured in charcoal broiled beef, smoked
meats such as pork and sausage, cooking oil and shucked oysters.
Benzo(g,h,i)perylene does not induce tumors when administered repeatedly to
mouse skin (Hoffman and Wynder, 1966). Van Duuren et al (1970) showed that the
compound can act as a mild tumor initiator but not as a complete carcinogen. In a
1973 study, Van Duuren reported that benzo(g,h,i)perylene may be a co-carcinogen.
It has been determined by IARC that insufficient data exists to classify the
compound as carcinogenic or noncarcinogenic. IARC also found no data sufficient
to evaluate reproductive, toxic or perinatal effects in experimental animals.
Muller (1968) reported that biweekly subcutaneous injections of
benzo(g,h,i)perylene into mice over a 6-month period failed to produce any toxic
effects.
This section has been adapted from Stern et al (1985).
Indeno(l ,2.3-c,d)pyrene
Adequate data do not exist for the assessment of the effects on humans of acute or
chronic exposure to indeno(l,2,3-c,d)pyrene. No human health criterion has been
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established; neither has an acceptable daily inake (ADI). There are no case reports
or epidemiologic studies on the carcinogenicity of indeno(l,2,3-c,d)pyrene per se,
because it always occurs in combination wi-th other PAHs.
Indeno(l,2,3-c,d)pyrene induced tumors in a dose-related manner when painted on
mouse skin three times a week for 12 months. The compound was an active tumor
initiator when 0.25 ug was applied every other day for 20 days to mouse skin
followed by repeated treatment of croton oil (Hoffman and Wynder, 1966).
Injection site sarcomas were produced by three subcutaneous injections of 0.6 mg
indeno(l,2,3-c,d)pyrene in 10 or 14 male mice and 1 of 14 female mice (Lacassagne,
et al, 1963). The compound has been classified by EPA (1979) as a weak
carcinogen.
The noncarcinogenic toxic effects produced by chronic or acute exposure to
indeno(l,2,3-c,d)pyrene are not known. The teratogenic potential of indeno(l,2,3-
c,d)pyrene has not been studied.
This section has been adapted from Stern et al (1985).
Benzo(a)pyrene
Benzo(a)pyrene (BaP) has been shown to affect the immune system by suppressing
the ability of the B lymphocytes to develop into antibody secreting plasma cells.
This effect requires moderate doses of up to 400 mg/kg body weight. T cell
activity and tumor suppression do not seem to be affected much. Carcinogenic
effects of PAHs in general, however, occur at levels far lower than those affecting
the immune system.
Intraperitoneal injection of BaP affected sperm production in rats. Dietary BaP
did not have reproductive effects in female rats.
BaP represents only a small percentage of the total PAHs found in industrial
environments containing these compounds. No epidemiologic studies of persons
exposed to a single PAH, such as BaP, have been conducted.
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PAHs are activated by the hepatic microsomal enzyme system to carcinogenic
forms that bind covalently to DNA. The PAH forms are metabolized by aryl
hydrocarbon hydroxylase (AHH), an enzyme located in the endoplasmic reticulum
or microsomes of various tissues. DNA adducts of BaP diol-epoxides can be found
in many tissues, but the amount does not correlate with the carcinogenicity of the
tissues.
N
Application of PAH mixtures to the skin of mice is a standard method for the
induction of papillomas and some carcinomas, but the relationship to individual
PAHs is complex. Automobile exhaust condensate (AEC) was found to be twice as
potent as cigarette smoke. BaP is a common positive control in these studies.
However, the distribution of the carcinogenic potential does not follow the
distribution of BaP, which is nearly 200 times more potent than AEC. BaP is a
potent agent in the initiation promotion skin carcinogenesis studies in the Sencar
(sensitive for cancer) mouse. BaP, 3-MC and DMBA are effective tumor initiators,
and phorbal esters (for example, TPA) are effective promoting agents.
BaP has been introduced orally, through inhalation, and dermally to various strains
of rodents. .Dermal application to C/57L mice was the only method that produced
any form of cancer (skin). Increasingly high doses induced malignancies in 100
percent of BaP-treated animals in progressively shorter time periods. At
increasingly lower doses, fewer cancers were observed and lifespans equalled or
exceeded control animals.
Although there is a clear-cut dose-responsiveness with indications of a threshold
for the carcinogenic response from topical application of BaP to C/57L mice, these
findings are not easily generalizable in view of the wide range of contrasting
findings for skin tumor induction in other strains of mice, the resistance of other
species to BaP carcinogenicity, and the total lack of neoplastic response in some
species.
Certain PAHs, like 3MC'A or DMBA, or BaP, can induce mammary carcinomas, but
pretreatment with one chemical will inhibit either chemical from causing cancer.
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Interactions between PAHs, since these compounds normally occur in mixtures with
one another, are extremely complex. A single compound does not act in a linear
fashion.
This section has been adapted from Stern et al (1985).
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3.0 SUMMARY OF ENVIRONMENTAL EFFECTIS
Phenolics
Effects on Aquatic Ecosystems
There is an abundance of data on the acute toxicity of phenols to freshwater fish
and invertebrates. The chronic toxicity data base appears limited, however. The
acute toxicity data is also limited for saltwater aquatic species. In addition, there
appears to be no chronic toxicity data for saltwater species for phenols.
Fish exposed to phenolic compounds have been known to exhibit paralysis,
equilibrium loss, and increased respiration and swimming rates (Gehrs, 1978). The
acute toxicity data for phenols appears to be highly variable and related to water
quality influences.
Parameters sch as pH, hardness, and temperature are known to be important
factors affecting the toxicity of phenolics to aquatic organisms (US EPA, 1980g).
Acute phenolic toxicity is inversely related to dissolved oxygen content and water
hardness, and directly related to water temperature (Gehrs, 1978). In general, the
coldwater fishes (Salmonidae in particular) have been shown to be more sensitive to
phenolics than have their warm water counterparts (Centrarcids, etc.) (US EPA,
1980g). The acute toxicity of phenolics to freshwater fish exhibits a range of one
to two orders of magnitude. Freshwater fish acute LC-50 values range from 67.6
mg/1 to 5.02 mg/1 for phenol. Daphnia magna. a freshwater cladocern, had an
acute EC 50 of 5.0 mg/1 for phenol. Saltwater fish species have a similar range of
acute LC 50 values with the lowest reported as 5.8 mg/1 for phenol (ibid.).
A chronic toxicity test with fathead minnows (Pimephales promelas) in early-life
stages (embryo-larval) resulted in a chronic value of 2.56 mg/1 phenol. The
resultant ratio of acute to chronic values was 14, indicating that phenols could be a
chronic toxicant of concern in a long-term exposure. However, there are not other
reported chronic exposures tests to validate this concern (ibid.).
There are only limited studies on the residue accumulation of phenolics in
freshwater aquatic organisms. In three studies with goldfish (Carassius auratus), a
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whole body tissue residue bioconcentration factor (BCF) of 1.2 to 2.3 was found.
From these studies, it appears that bioaccumulation of phenol is not a concern
(ibid.).
Effects on Terrestrial Ecosystems
There is little information available on the terrestrial effects of phenolics because
they strongly tend to partition into aquatic systems due to their high solubility.
Phenol is moderately toxic to animals by acute exposures. Acute oral LD50 values
for various small mammals (cat, dog, mouse, rabbit, rat) range from 100 to 500
mg/kg. As for phytotoxic effects, Wilson and Stevens (1981) report that 160 ppm
phenol in soil had no adverse effect on the growth of radishes or mixed grass and
produced no detectable odor. They also cite other studies, however, which report
the odor detection limit in soil as 4 ppm, and that vegetables and fruit can be
tainted when grown up to 1 mile downwind of a 4 ppm airborne source.
This section has been adapted from Koppers et al (1985).
Pentachlorophenol
Effects on Aquatic Ecosystems
Pentachlorophenol (PCP) and sodium pentachlorophenate (Na-PCP) are extremely
toxic to aquatic organisms when substantial amounts reach the receiving water.
The susceptibility of different fish species to PCP toxicity varies. The biochemical
mechanism of PCP toxicity to aquatic organisms likely involves its ability to
uncouple oxidative phosphorylation and at higher concentrations to inactivate
glycolytic enzymes. PCP is ubiqutious in the aquatic environment (USDA, 1981),
with sources including degradation of other compounds, chlorination of water, and
pollution by PCP itself. After introduction into water, PCP may be removed by
volatilization, photodegradation, adsorption, and biodegradation. However, PCP is
moderately persistent in aquatic systems and has been detected in lake water and
fish tissues six months after a spill (ibid.). As a result of their toxic nature,
accumulation in tissues, and widespread industrial and agricultural applications,
both PCP and Na-PCP pose a potential threat to aquatic life.
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For all freshwater fish tested (nine species) the range of acute LC50 values is 48
mg/1 PCP for rainbow trout to 330 mg/1 PCP for bluegill sunfish (US EPA, 1980q).
For freshwater invertebrate organisms, a limited set of toxicity data exists. At a
pH of 7.5 the tubified worm (Tubifex tubifex) had a 24-hour LC50 of 310 mg/1 PCP.
For the Cladocern Daphnia magna, a 48-hour LC50 of 680 mg/1 PCP was calculated
(US EPA, 1980q). Freshwater plant values range from 7.5 mg/1 PCP, which
produced chlorosis to the alga (Chlorella pyrenoidosa), to 800 mg/1 PCP, which
produced chlorosis to duckweed (Lemna minor) (ibid.). The acute toxicity value for
the protection of freshwater aquatic life is 55 mg/1 PCP (ibid.).
There is a general lack of data in regard to chronic toxicity of PCP to freshwater
aquatic life. The ambient water quality criterion for PCP (US EPA, 1980q)
provides a value of 3.2 mg/1 PCP as a chronic toxicity value.
In acute toxicity tests with saltwater fish, LC50 values range from 38 mg/1 PCP
for pinfish (Lagodon rhomboides) to 442 mg/1 PCP for juvenile sheepshead minnows
(Cyprinodon variegatus) (US EPA, 1980q). For saltwater invertebrate organisms,
the acute LC50 values range from 40 mg/1 PCP for eastern oyster (Crassostrea
virginicus) to 5,600 mg/1 PCP for pink shrimp (Penaeus duorarum) (ibid.). Saltwater
plant values range from 293 mg/1 PCP, which produced 58 percent reduction in cell
numbers in alga (Monochrysis lutheri), to 300 mg/1 PCP, which produced a 50
percent inactivation of photosynthesis in the kelp (Macrocystis pyrifera) in four
days (ibid.). The acute toxicity value for the protection of saltwater aquatic life is
53 mg/1 PCP (ibid.).
In a saltwater chronic toxicity test with the sheepshead minnow, a chronic value of
64 mg/1 was calculated after a life-cycle study (US EPA, 1980q). The ambient
water quality criterion for the protection of saltwater life (ibid.) provides a chronic
toxicity concentration of 34 mg/1 PCP. The results of two bioconcentration studies
with PCP and the freshwater goldfish (Carassius auratus) and bluegills (Lepomis
macrochirus) gave bioconcentration factors (BCF) of 1,000 and 13 respectively
(ibid.). The BCF of 13 was a measure of PCP in muscle tissue only. In four
bioconcentration studies with saltwater species, BCFs ranged from 13 for
sheepshead minnows to 78 for eastern oysters (ibid.). Whereas the log
octanol/water partition coefficient indicates that PCP should be bioaccumulated
significantly in the aquatic environment, depuration in aquatic species also appears
A3-3
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to be significant. This, along with demonstrated detoxification mechanisms in fish,
probably accounts for the relatively low bioconcentration factors seen in the
literature.
Effects on Terrestrial Ecosystems
Studies on the uptake and translocation of PCP in plants indicate that little or no
translocation takes place (USDA, 1981). When solutions of PCP were administered
to roots of plants, no uptake or translocation was demonstrated (ibid.).
While the toxicity data base for terrestrial mammals and birds is limited,
inferences from the toxicity testing performed on laboratory animals is useful.
Poisoning of farm animals from PCP has been reported. Pathways include dermal
exposure through direct contact with treated wood, oral ingestion via food
contained in treated food bins, and inhalation of air-borne PCP from wood in barns.
Acute toxicity data for PCP exposures are rare; this may be a result of animal
rejection of food with high PCP levels. LD50 values for sheep and cattle are 120
and 140 mg/kg PCP respectively (ibid.).
This section has been adapted from Koppers et al (1985).
Naphthalene
The median effective concentrations for freshwater invertebrate species and three
fish species are all reported to be greater than 2,300 ug/liter. Acute values
reported for saltwater polychaetes, oysters, and shrimp species are all greater than
2,350 ug/liter. A chronic value of 620 ug/liter and an acute-chronic ratio of 11 is
reported for the fathead minnow, a freshwater species. No chronic values are
available for saltwater species. Freshwater algae appear to be less sensitive to the
effects of naphthalene than animal species. No information concerning saltwater
plant species is available. The weighted average bioconcentration factor for the
edible portion of all freshwater and estuarine aquatic organisms consumed by
Americans is 10.5.
This section has been adapted from the US EPA (1985).
A 3-4
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NONCARCINOGEN1C PAHs
Acenaphthylene
Adequate data for characterization of toxicity to domestic animals and wildlife are
not available. The weighted average bioconcentration factor for the edible portion
of all freshwater and estuarine aquatic organisms consumed by Americans is 119
(US EPA, 1985).
Phenanthrene
Adequate data for characterization of toxicity to domestic animals and wildlife are
not available. A 96-hour LC^n value of 600 ug/liter is reported for a saltwater
polychaete worm exposed to a crude oil fraction containing phenanthrene. The
weighted average bioconcentration factor for the edible portion of all freshwater
and estuarine aquatic organisms consumed by Americans is 486 (US EPA, 1985).
Anthracene
Adequate data for characterization of toxicity to domestic animals and wildlife are
not available. A 1-hour 90 percent lethal photodynamic response concentration of
0.1 ug/liter is reported for the freshwater protozoan, Paramecium caudatum. The
weighted average bioconcentration factor for the edible portion of all freshwater
and estuarine aquatic organisms consumed by Americans is 478 (US EPA, 1985).
Fluoranthene
Among freshwater species, the bluegill, with a 96-hour LC^n value of 3,980
ug/liter, is more sensitive to fluoranthene than the cladoceran Daphnia magna,
with a 48-hour EC5Q value of 325,000 ug/liter. No chronic data are available for
freshwater organisms. Among saltwater species, the 96-hour LC$Q values for the
mysid shrimp and polychaete are 40 and 500 ug/liter, respectively. The 96-hour
LC5Q value for the sheepshead minnow is greater than 560,000 ug/liter. The
chronic value and acute-chronic ratio for the mysid shrimp are 16 ug/liter and 2.5,
respectively. The freshwater and saltwater algal species tested exhibit similar
A 3-5
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sensitivities to fluoranthene, with EC^Q values of about 50,000 ug/liter. There is
evidence of fluoranthene accumulation in edible aquatic organisms, although no
measured, steady-state bioconcentration-factors are available for freshwater or
saltwater organisms.
This section has been adapted from the US EPA (1985).
Acenaphthene
The data on the acute and chronic toxicity of acenaphthene to freshwater
organisms are very limited. The EC^n (48 hour) for Daphnia magna is 41.2 mg/1
and the LC^n (96 hour) for bluegill is 1.7 mg/1 (the most sensitive freshwater
animal species tested). Freshwater algae are sensitive to acenaphthene levels of
about 0.5 mg/1 (EPA, 1980). EPA has not calculated a final acute value freshwater
criterion as it considers that the minimum data base requirements have not been
met (EPA, 1980).
This section has been adapted from Stern et al (1985).
Pyrene
Little is known about the impact that dilute pyrene can have on aquatic organisms.
An EPA report (1980) concluded that at the low levels typically encountered in
ambient waters, it is unlikely that the anthracene group of PAHs (which includes
pyrene) would have a significant impact on the aquatic biota. Because these PAHs
adsorb strongly to particulate matter, they will be found mostly in the bottom
sediments of rivers and lakes. The major source of pyrene in the streams near
urban areas is from runoff of particulate fallout from combustion products and
municipal sewage treatment plants.
No information was found that related pyrene exposures to a specific
environmental effect. EPA Has not developed a criterion for this compound, and
there is no information to suggest that it should be of special concern.
This section has been adapted from Stern et al (1985).
A 3-6
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Carcinogenic PAHs
Chrysene
Adequate data for characterization of the toxicity of chrysene to domestic animals
and wildlife are not available (US EPA, 1985).
Benz(a)anthracene
A concentration of 1,000 mg/1 of benzo(a)anthracene has been reported to produce
an 87 percent mortality in freshwater bluegill sunfish after six months exposure
(Brown, 1975). However, this concentration of benzo(a)anthracene is far above the
normal saturation level in water and thus probably represents either a suspension of
particulates in water or the presence of a cosolvent. It is probably not
representative of naturally occurring conditions in the ambient environment.
There are no data on the effects of benzo(a)anthracene to either aquatic or
terrestrial plants. Many of the other PAHs are not particularly toxic to plants, and
some plants use the compounds as a source of carbon (EPA, 1980). In laboratory
tests, benzo(a)anthracene promoted the growth of freshwater algae and bacteria
(EPA, 1980). Studies that have been conducted on test animals were directed at
the carcinogenic potential of some members of the PAH group, rather than at the
risk of adverse impact on wildlife.
Similar to other PAHs, benzo(a)anthracene has a low solubility in water.
Biodegradation rates are highly dependent on the presence of other PAHs (which
accelerate the process) and on the type of conditions being evaluated. As a class,
the PAHs are fairly stable with half-lives in the environment between a few days
and a few weeks.
This section has been adapted from Stern et al (1985).
Benzo(b)fluoranthene
Data on the toxicity of benzo(b)fluoranthene to aquatic and terrestrial organisms
are not available. Therefore, EPA has not developed environmental criteria for
this compound (Stern et al, 1985).
A 3-7
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BenzoQQfluoranthene
Toxicity data for benzo(k)fluoranthene are not available to assess the impact on
either freshwater species, or on other environmental parameters (Stern et al,
1985).
Dibenzo(ath)anthracene
The toxic effects of dibenzo(a,h)anthracene on aquatic and terrestrial organisms
are not known. As far as could be ascertained, toxicologic studies of the effects of
dibenzo(a,h)anthracene on freshwater ecology have not been published. EPA Has
not promulgated any criterion for dibenzo(a,h)anthracene, based on known
environmental effects.
This section has been adapted from Stern et al (1985).
Benzo(g,h,i)perylene
No data on environmental effects specific to benzo(g,h,i)perylene were identified.
It has been studied only in combination with other PAHs. No information on the
environmental half-life of benzo(g,h,i)perylene was found. The lack of information
on its environmental effects has prevented EPA from developing an environmental
criterion for benzo(g,h,i)perylene.
This section has been adapted from Stern et al (1985).
IndenoQ ,2,3-c,d)pyrene
Data on the toxicity of indeno(l,2,3-c,d)pyrene to aquatic and terrestrial organisms
are not available. Therefore, EPA has not developed environmental criteria for
this compound (Stern et al, 1985).
Benzo(a)pyrene
Santodonato et al (1981) state that the family of polynuclear aromatic
hydrocarbons (PAHs), of which benzo(a)pyrene (BaP) is a member, is ubiquitous in
A 3-8
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the environment, arising both from human activity, such as fuel combustion and
spillage, and from natural resources such as biosynthesis by plants, algae, and
bacteria. A satisfactory assessment of the ecological impacts potentially caused
by PAHs is therefore complicated by the uncertainty about their role in the natural
environment.
Relatively little information is available on the phytotoxicity of BaP. Most of the
literature deals with PAHs as a class, rather than with a single constituent such as
BaP. The overall conclusion is that, despite numerous studies showing high lipid
solubility, PAHs appear to have little tendency to bioaccumulate in the fatty
tissues of vertebrate animals.
Apparently, organisms having well developed mixed function oxidase (MFO) enzyme
systems, which function generally in the breakdown of foreign compounds, are able
to metabolize PAHs, thereby preventing their accumulation. High bioconcentra-
tion factors are found only for PAHs in those freshwater and marine invertebrates
lacking or having poorly developed MFO systems. Many of the organisms not
readily able to metabolize PAHs are filter feeders, and thus would tend to
accumulate the particulate matter on which the PAHs are absorbed. Experiments
in which these organisms are removed to contamination-free environments, have
shown that the PAH concentrations in these filter-feeding organisms are rapidly
reduced. For these reasons, there should be little or no bioaccumulation let alone
biomagnification, of PAHs up the food chain.
Under highly controlled laboratory conditions, BaP is very stable with a half life of
9900 days (Santodonato et al, 1981). However, in solution and exposed to ultra-
violet (UV) light of similar characteristics to solar radiation, the half-life was
reduced to between 76 and 2.4 hours, depending on the intensity of the light. The
decomposition is caused by photo-oxygenation. The environmental fate of BaP in
water will depend on a number of variables in addition to sunlight, such as
temperature and the presence of other compounds. For example, BaP will
decompose more rapidly when oxidizing agents such as chlorine and ozone are
present, and when ambient temperatures are relatively warm, as is the case in the
Gulf Coast area near Wiggins.
A 3-9
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According to Radding et al (1976), some PAH compounds and their decomposition
products may be relatively toxic to leafy plants when the solutions are sprayed
directly on the leaves. Unfortunately, -this study did not separately test BaP.
However, some of the PAHs, including BaP, have been shown to promote the
growth of cultures of tobacco, rye, and radish. Radding et al (ibid.), suggest that
"the degree of effectiveness in promoting plant growth appeared to correspond
with increased carcinogenic potency." Similar mixed results are found when
bacteria and freshwater algae are exposed to various PAHs (ibid.). Some
compounds including BaP stimulate growth in some cultures, while others inhibit it.
Only a small fraction of the BaP exposure of plants and other biota probably comes
through the groundwater. While BaP is present in most soils, little would be taken
up because of its strong absorption on organic material in the soil. Also, a
significant amount of plant exposure would result from the deposition of airborne
PAH particles on leaves. In two studies where higher plants were grown on
nutrient media containing BaP, the compound was found to be distributed
throughout the plant, indicating uptake by the root (ibid.). Other similar studies
found insignificant root uptake of BaP (Santodonato et al, 1981). In general,
however, more PAHs appear to be deposited on leaves in airborne particles, since
the researchers found that washing removed a significant amount of the compound.
Furthermore, the probable exposure to humans from eating the portions of the
plants contaminated this way would be a small fraction of the exposure in a typical
diet. Soil microorganisms appear to be capable of metabolizing many of the PAHs,
and in that regard they are probably more efficient than aquatic organisms.
Unfortunately, as far as can be determined, BaP has not been separately tested.
Little information is available on the uptake and metabolism of PAH compounds by
aquatic organisms. Some of the higher algae appear to be capable of
bioconcentrating several of the PAHs. It must be pointed out that there is strong
evidence that PAHs, including BaP, occur naturally in the environment. Even
ancient sediments of limestone and boghead have been shown to contain 20 and 40
ug/kg. Their origin is thought to be due to natural processes such as plant and
bacterial synthesis, and not due to pollution (Radding et al, 1979). Plant seedlings
grown in a PAH-free environment were found to contain BaP at levels of 10-20
ug/kg of dried material (ibid.). Higher amounts have been detected in tissues of
other plants, but these were grown outdoors, and therefore it may not be possible
A3-10
-------
to separate the relative contribution from bacterial synthesis versus that received
from the soil and the atmosphere as a result of human activities. Most unprocessed
cereals, fruits, and vegetables that have been tested have shown BaP levels of from
0.25 to 58.5 ug/kg.
The 1980 Water Quality Criteria for Polynuclear Aromatic Hydrocarbons states
that researchers found bioconcentration factors for BaP ranging between 930 for
the mosquitofish and 134,248 for Daphnia pulex, although no mention is made of
the effect, if any, that the levels had on the species. The criteria document points
out that for freshwater aquatic organisms, "the limited freshwater data base
available for polynuclear aromatic hydrocarbons...does not permit a statement
concerning acute or chronic toxicity." Santodonato et al (1981) reached the
following conclusion:
Although POM (= Polycyclic Organic Matter = PNA) are found nearly
everywhere in man's environment, it is not clear whether these
agents may affect the ecological balance. Adverse effects on plants,
microorganisms, fish, or other wildlife cannot be clearly shown.
However, there are data to indicate that POM may bioaccumulate in
some invertebrate species, although it is not known if transfer of
POM through the food chain may occur. Indeed, animal studies
showing hat POM are rapidly metabolized and excreted support the
contention that biomagnification is an unlikely possibility.
This section has been adapted from Stern et al (1985).
A3-11
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MAJOR REFERENCES
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Environmental Research and Technology, Inc., Pittsburgh, PA.
Chemical, Physical, and Biological Properties of Compounds Present at Hazardous
Waste Sites. US EPA September 1985. Clement Associates, Inc., Arlington,
VA.
Alternate Concentration Levels and Acceptable Exposure Levels. September 1985.
Seminar: 3ames L. Grant <5c Assoc. and Carlos Stern Assoc., Inc., Dallas, TX.
The description of benzo(a)pyrene in this document contains a general
discussion of the effects of PAH in the environment.
R-l
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MINOR REFERENCES
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Pentachlorophenol in Vivo and In Vitro. Arch. Toxicol. 40: 45-53. (MC
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Akin, F. J. et al. 1976. Identification of polynuclear aromatic hydrocarbons in
cigarette smoke and their importance as tumorigens. Journal of the National
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Arrhenius, E., L. Renberg, and L. Johansson. 1977. Subcellular Distribution, A
Factor in Risk Evaluation of Pentachlorophenol. Chem-Biol. Interactions 18:
23-24. (MC 8/4/84).
Bauchinger, M., J. Dresp, E. Schmid, and R. Hauf. 1982. Chromosome Changes in
Lymphocytes after Occupational Exposure to Pentachlorophenol (PCP). Mut.
Res. 102: 83-88. (MC 8/4/84).
Begley, 3., E. L. Reichert, M. N. Rashad, and W. H. Kelmmer. 1977. Association
Between Renal Function Tests and Pentachlorophenol Exposure. Clin.
Toxicol. 11: 97-106. (MC 8/4/84).
Bevenue, A., T. J. Haley, and W. H. Klemmer. 1967. A Note on the Effects of a
Temporary Exposure of an Individual to Pentachlorophenol. Bull. Environ.
Contam. Toxicol. 2: 293-296.
Bevenue, A. J., J. Wilson, L. J. Casarett, and W. H. Klemmer. 1967. A Survey of
Pentachlorophenol Content in Human Urine. Bull. Environ. Contam. Toxicol.
2: 319-332.
Biancifiori, C. and F. Caschera. 1962. The relation between pseudopregnancy and
the chemical induction by four carcinogens of mammary and ovarian tumors
in BALB/C mice. Br J Cancer 16: 772.
Bingham, E. and H. L. Falk. 1969. Environmental carcinogens: The modifying
effect of cocarcinogens on the threshold response. Arch Environ. Health 19:
779-783.
Boutwell, R. K., and K. K. Bosch. 1959. The Tumor-Promoting Action of Phenol
and Related Compounds for Mouse Skin. Cancer Res. 19: 413-424. (SCE
VISALIA PCP).
Brown, E. R. et al. 1975. Tumors in fish caught in polluted waters: possible
explanations. Comparative Leukemia Research. University Tokyo
Press/Karger, Basel.
Gehrs, C. W. 1978. Environmental Implications of Coal-Conversion Technologies;
Organic/Contaminants. In: Energy and Environmental Stress in Aquatic
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MINOR REFERENCES
Gilbert, F. I., C. E. Minn, R. C. Duncan, T. Aldrich, W. H. D. Lederer, and E. J.
Wilkinson. 1983. Effects of Chemical Preservatives on the Health of Wood
Treating Workers in Hawaii, 1981 - Clinical and Chemical Profiles and
Historical Prospective Study - July, 1983. American Wood Preservers Inst.
(MC
Habs, M. and D. Schmahl 1980. Local carcinogenicity of environmentally relevant
polycyclic aromatic hydrocarbons after lifelong topical application to mouse
skin. Arch. Geschwulstforsch. 50(3): 266-274.
Haley, T. J. 1977. Human Poisoning with Pentachlorophenol and Its Treatment.
Ecotoxicol. Environ. Safety 1: 343-347. (MC 8/4/84).
Hoffman, D., and E. L. Wynder. 1966. On the carcinogenic activity of
dibenzopyrenes. Zeitschfift fur Krebsforschung. 68: 137-149.
Horton, A. W., and G. M. Christian. 1974. Cocarcinogenic versus incomplete
carcinogenic activity among aromatic hydrocarbons: Contrast between
chrysene and benzo(b)triphenylene. Journal of the National Cancer Institute.
53(4): 1017-1020.
IARC. 1983. Polynuclear aromatic compounds, chemical, environmental and
experimental data (IARC Monographs on the Evaluation of the Carcinogenic
Risk of Chemicals to Humans, Vol. 32). International Agency for Research on
Cancer, World Health Organization, Lyon, pp. 174-154.
Kaden, D. A., R. A. Hites, and W. G. Thilly. 1979. Mutagenicity of soot and
associated polycyclic aromatic hydrocarbons to Salmonella typhimurium.
Cancer Research 39: 4152-4149.
Kalman, D. A., and W. S. Horstman. W. S. 1983. Persistence of Tetrachlorophenol
and Pentachlorophenol in Exposed Woodworkers. 3. Toxicol.-Clin. Toxicol.
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Kennaway, E. L. 1930. Further experiments on cancer producing substances.
Biochem 3. 24: 497.
Klein, M. 1960. A comparison of the initiating and promoting actions of 9,10-
dimethyl-l,2-benzanthracene and 1,2,5,6-dibenzanthracene in skin
tumorigenesis. Cancer Res. 20: 1 179.
Knoblock, K. et al. 1969. The investigations of acute and subacute toxic action of
acenaphthene and acenaphthylene. Medycyma Pracy 3: 210-222.
Lacassagne, A. et al. 1963. Carcinogenic activity of polyclic aromatic
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490-496.
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MINOR REFERENCES
Larionov, A. G. 1976. Experimental data on assessing the toxicity of 2,6-
dimethylphenol. Gig. Tr. Prof. Zabol. b: 43-46. (In Russ.) Taken from:
Abstract, Medlars II, National Library of Medicine's National Interactive
Retrieval System.
Lillard, D. A., and J. J. Powers. 1975. Aqueous odor thresholds of organic
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Lorenz, E., and H. L. Stewart. 1947. Tumors of alimentary tract induced in mice
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Maazik, I. Kh. 1968. Standards for dimethylphenol isomers in water bodies. Hyg.
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Muller, E. 1968. Carcinogenic substances in water and soils. Studies on the
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National Toxicology Program. 1983. Third annual report on carcinogens (NTP 82-
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NAS (National Academy of Sciences). 1977. Drinking water and Health. National
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NIOSH (National Institute for Occupational Safety and Health). 1976. Criteria for
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NIOSH (National Institute for Occupational Safety and Health). 1978. Criteria for
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NIOSH (National Institute of Occupational Safety and Health). 1985. Registry of
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Onuska, R. I. et al. Gas chromatographic analysis of polynuclear aromatic
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Radding, S. B. et al. 1976. The Environmental Fate of Selected Polynuclear
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APPENDIX B; PROCEDURE FOR COMPUTING MASS BALANCES
This appendix outlines the procedure used-to estimate the fate of chemicals in the
soil columns and pilot EBDS™. The fate estimates were made on the following
compounds or groups of compounds.
o Pentachlorophenol (PCP)
o Naphthalene
o Noncarcinogenic polynuclear aromatic hydrocarbons (PAH)
o Carcinogenic polynuclear aromatic hydrocarbons (PAH)
The classification of PAH into noncarcinogenic or carcinogenic categories is shown
in Table B-l. The rationale for this classification is presented in Appendix A.
For reasons outlined in Chapter 4, the migration of chemicals from the zone of
incorporation into the soil beneath was assumed to be insignificant. This
assumption was supported by laboratory analysis which failed to detect PCP,
naphthalene, or any PAHs in soils below the zone of incorporation in either the
TM
soils columns or pilot EBDS .
If migration downward is not a significant avenue of chemical movement, then the
disappearance of the compound from the soil is due to either volatilization or
chemical/biological transformations. Figure B-l shows the fate of a compound in
the zone of incorporation. In the figure, the following quantities are defined.
ma(t) = mass of chemical A/surface area (mg/m2)
da(t) = mass of chemical A degradation product/surface area
(mg/m2)
ea(t) = cumulative volatile emissions of chemical A/surface area
(mg/m2).
Each of these quantities is a function of time. Mass conservation requires
ma(0) = m,(t) + ea(t) + da(t) (B-l)
B-l
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TABLE B-l
CLASSIFICATION OF SELECTED PAHs BY THEIR CARCINOGENICITY
Noncarcinogenic PAHs
Acenaphthylene
Acenaphthene
Fluorene
Phenanthrene
Anthracene
Fluoranthene
Pyrene
Carcinogenic PAHs
Benz(a)anthracene
Chrysene
Benzo(b)fluoranthene
Benzo(k)fluoranthene
Benzo(a)pyrene
Dibenz(a,h)anthracene
Benzo(g,h,i)perylene
Indeno(l ,2,3-c,d)pyrene
B-2
-------
ZONE
OF
INCORPORATION
FIGURE B-l
PATE OF A CHEMICAL IN THE ZONE OF INCORPORATIOH
B-3
-------
The variable t indicates time and ma(0) is the mass per unit surface area of
chemical A in the zone of incorporation at the start of the experiment.
In the soil column and EBDS studies, the mass of the compound was measured at
the start of the experiments, ma(0), and at various times throughout the studies,
ma(t). In addition, rates of volatile emissions of the compund from the soil, qa(t),
were measured at various times during the course of both studies. The
cummulative emissions of compound A at any time t can be found from:
ea(t) = qa(x)dx (B-2)
Once ea(t) has been determined, the amount of the chemical that is chemically or
biologically transformed is given by
da(t) = ma(0) - ma(t) - ea(t) (B-3)
Equation B-3 is simply a rearrangement of equation B-l.
Before equation B-3 can be solved, two calculations must be made. First, the level
of a chemical is reported as the concentration in the soil on a mg/kg basis. To
convert these concentrations into mass per unit surface area in the zone of
incorporation, the following equation must be solved.
ma(t) = pB cs.a(t) zu (B-4)
In this expression, pjj is the soil bulk density (kg/m^), cs_a(t) is the concentration of
the chemical in the soil (mg/kg), and zu is the depth of the zone of incorporation
(m) (see Figure B-l). Table B-2 lists the values of these parameters for the soil
nt
column and pilot EBDS .
Second, the surface flux rates were measured for only the first two months of the
IM
soil column and pilot EBDS studies. In order to estimate the emissions during the
last four months, a curve was fit through the emission rate data for each compound
or group of compounds, and the emission rate at the two-month mark, qa_2> was
estimated and assumed to hold for the next four months. This procedure should
over estimate slightly the volatile emissions of the compounds. In most cases, the
B-4
-------
TABLE B-2
VALUES OF BULK DENSITY (PB)
AND DEPTH OF ZONE OF INCORPORATION (zu)
FOR SOIL COLUMN AND PILOT EBDS STUDIES
zu
kg/m3 g/cm3 m ft
Soil Column 2.205x 103 2.205 .152 .5
Pilot EBDS™ 2.205x103 2.205 .305 1.0
B-5
-------
emission rate at the end of two months is substantially lower than the rate at the
start of the experiment and appears to be leveling off. Thus, the overestimation of
volatile emissions should not be excessive..
The cumulative volatile emissions, ea(t), were estimated by solving equation B-2
with the actual emission rates, qa(t), for the first two months. The solution was
accomplished by numerical integration using the trapezoidal method. For times
beyond the first two months, the emission rate at the end of two months, qa_2, was
used. Thus, if eaO"2) is the cumulative emission at the end of two months (T2 is
two months time), the cumulative emissions at any time greater than T2 is given
by:
ea(t) = ea (T2) + qa_2 • (t-T2) (B-5)
Figures B-2 through B-4 show the emission rates of PCP, naphthalene, and
noncarcinogenic PAH over time for soil columns Al and Bl, and the pilot EBDS™ .
Table B-3 lists the emission rates estimated at the two-month mark, qa_2, with this
procedure. It should be noted that the emissions of carcinogenic PAH at the end of
two months was not detectable for either the soil columns or pilot EBDS .
Tables B-4 through B-6 show the calculations of ma, ea, and da over time for PCP,
naphthalene, noncarcinogenic PAHs and carcinogenic PAHs in the soil columns and
pilot EBDS . These values are reported in units of mass per unit surface area
(mg/m2). To convert these values to units of mass of compound per unit mass of
contaminated soil (mg/kg), the reported numbers must be divided by PBZU- Tne
mass balance graphs in Chapter <4 report these quantities on a mass per unit mass
basis.
B-6
-------
TABLE B3
ESTIMATED VOLATILE EMISSION RATES OF PCP
NAPHTHALENE AND NONCARCINOGENIC PAH
Column Al
Column Bl
Pilot EBDS™
PCP
(mg/m2/day)
5. x 10-3
*. x 10-3
0.5
Naphthalene
(mg/m2/day)
0.7
0.55
9.0
Noncarci no genie
PAH
Gng/m2/day)
3.0
2.0
if. 5
B-7
-------
TABLE B*
MASS BALANCE CALCULATIONS FOR COLUMN Al
Pentachlorophenol
Time
(Month)
0
0.006
0.071
0.138
0.572
0.672
0.938
1.0
1.06*
1.272
1.50
1.51
2.0
3.0
*.o
5.0
6.0
ma ea
(mg/m2) (mg/rn2)
51,41* 0
0.003
0.02*
0.029
0.029
0.035
0.07*
-
0.110
0.165
0.212
0.21*
0.28*
5,713 0.*28
10,*17 0.572
0.716
3,02* 0.860
da
(mg/rn2)
0
*5,701
*0,996
*8,389
B-8
-------
TABLE B4 (Cont.)
MASS BALANCE CALCULATIONS FOR COLUMN Al
Naphthalene
Time
(Month)
0
0.006
0.071
0.138
0.572
0.672
0.938
1.064
1.272
1.50
1.51
2.0
3.0
4.0
5.0
6.0
(mg/m2) (mg/rn2)
9,073 0
47
333
341
360
363
370
373
379
387
387
378
5,041 419
7,057 470
461
8,300 482
(mg/m2)
0
3,614
1,577
292
B-9
-------
TABLE B4 (Cont.)
MASS BALANCE CALCULATIONS FOR COLUMN Al
Noncarcinogenic PAHs
Time ma
(Month) (mg/m2)
0 285,332
0.006
0.071
0.138
0.572
0.672
0.938
1.06*
1.272
1.50
1.51
2.0
3.0 43,349
4.0 96,307
5.0
6.0 58,544
(mg/rn2)
0
4
39
55
83
89
101
104
112
125
125
169
259
349
439
527
(mg/m2)
0
241,723
188,673
226,257
B-10
-------
TABLE B« (Cont.)
MASS BALANCE CALCULATIONS FOR COLUMN Al
Carcinogenic PAHs
Time ma ea da
(Month) (mg/m2) (mg/m2) (mg/m2)
0 106,491 0 0
3 47,31* 0 59,177
* 54,002 0 52,489
6 83,136 0 23,355
B-ll
-------
TABLE B5
MASS BALANCE CALCULATIONS FOR COLUMN Bl
Pentachlorophenol
Time ma
(Month) (mg/m2)
0 19,826
0.006
0.071
0.138
0..572
0.672
0.938
1.0
1.06*
1.272
1.50
1.51
2.0
3.0 3,360
*.0 2,92*
5.0
6.0 1,311
(^2)
0
0.002
0.016
0.016
0.100
0.125
0.159
-
0.179
0.210
0.2*0
0.2*1
0.303
0.*29
0.555
0.681
0.807
(mg/rn2)
0
16,*66
16,902
18,515
B-12
-------
TABLE B5 (Cont.)
MASS BALANCE CALCULATIONS FOR COLUMN Bl
Naphthalene
Time
(Month)
0
0.006
0.071
0.138
0.572
0.672
0.938
1.064
1.272
1.5
1.51
2.0
3.0
4.0
5.0
6.0
ma «a
(mg/m^) (mg/m2)
3,360 0
41
292
296
307
309
311
313
318
325
325
333
3,360 350
370 366
383
3,038 399
(mg/rn2)
0
-350
2,624
-77
B-13
-------
TABLE B5 (Cont.)
MASS BALANCE CALCULATIONS FOR COLUMN Bl
Noncarcinogenic PAHs
Time
(Month)
0
0.006
0.071
0.138
0.572
0.672
0.938
1.06*
1.272
1.50
1.51
2.0
3.0
4.0
5.0
6.0
ma ^a
(mg/m2) (mg/m2)
69,654 0
3
31
39
56
59
67
70
74
80
SO
110
41,266 170
11,358 230
290
14,074 350
(mg/m2)
0
28,219
58,067
55,231
B-14
-------
TABLE B5 (Cont.)
MASS BALANCE CALCULATIONS FOR COLUMN Bl
Carcinogenic PAHs
Time ma ea da
(Month) (mg/m2) (mg/m2) (mg/m2)
i
0 32,999 0 0
3 26,850 0 6,150
* 25,640 0 7,359
6 25,990 0 7,009
B-15
-------
TABLE B6
MASS BALANCE CALCULATIONS FOR PILOT EBDS
Pentachlorophenol
Time
(Month)
.000
.003
.036
.069
.469
.703
.936
1.0
1.936
1.939
2.0
3.0
5.0
6.0
(mg/m2) (mg/rn2)
55,776 0
1
9
13
67
93
96
110
111
14,560 112
14,045 127
12,768 158
11,133 174
(mg/rn2)
0
41,104
41,604
42,850
44,469
B-16
-------
TABLE B6 (Cont.)
MASS BALANCE CALCULATIONS FOR PILOT EBDS"
Naphthalene
Time
(Month)
.000
.003
.036
.069
.469
.703
.936
1.0
1.936
1.939
2.0
3.0
5.0
6.0
7.0
Hlf! Ca
(mg/m2) (mg/m2)
130,144 0
1,155
8,267
8,499
14,307
17,558
18,062
20,114
20,119
21,997 20,135
27,261 20,405
13,955 20,945
34 21,215
(mg/m 2)
0
88,012
82,478
95 , 244
108,895
B-17
-------
TABLE B6 (Cont.)
MASS BALANCE CALCULATIONS FOR PILOT EBDS
Noncarcinogenic PAHs
Time
(Month)
.000
.003
.036
.069
.469
.703
.936
1.0
1.936
1.939
2.0
3.0
5.0
6.0
ma ea
(mg/m2) (mg/m2)
527,881 0
111
803
835
1,218
1,412
1,465
1,683
1,684
76,185 1,692
56,538 1,827
90,944 2,097
444 2,232
(mg/m2)
0
450 , 004
469,516
434,840
525,205
B-18
-------
TABLE B6 (Cont.)
MASS BALANCE CALCULATIONS FOR PILOT EBDS™
Carcinogenic PAHs
Time
(Month)
0
.003
.036
.069
.469
.703
.936
1.0
1.936
1.939
2.0
3.0
4.0
5.0
6.0
ma _ ea
(mg/m2) (mg/m2)
84,222 0
.002
.015
.022
.115
.169
.203
.288
.288
38,660 .288
33,712 .288
28,045 .288
340 .288
(mg/m 2)
0
45,561
50,509
56,177
83,881
B-19
-------
FIGURE B-2
EMISSION RATES OF COMPOUNDS FROM SOIL COLUMN Al
IE 1-
-------
EVOLUTION RATE |mg/mx2/day)
EVOLUTION RATE (mg/m*2/day)
EVOLUTION RATE (ug/niX2/day)
ca
i
ho
CO
a
o
-a
m
S
5 I
§
M
CO
CO
l-l
§
CO
o
I Q
IS
5«
1
CO
O
O
o
-------
EVOLUTION RATE (mg/m*2/day)
EVOLUTION RATE (mg/mx2/day)
EVOLUTION RATE |r«g/in*2/day)
•J)
ro
M
w
en
o
2!
H
M
01
O
O
a
en
**]
O
t-1
O
H
PI
Cxi
O
S
«
i
4>
-------
EPA/540/2-89/022
SUPERFUND TREATABILITY
CLEARINGHOUSE
Document Reference:
Smith,, D.L. and I.H. Sabberwal. "On-site Remediation of Gasoline-Contaminated Soil."
15 pp. Technical paper presented at the International Congress on Hazardous Materials
Management, Chattanooga, TN, June 8-12,1987.
EPA LIBRARY NUMBER:
Super-fund Treatability Clearinghouse -EWF2
-------
SUPERFUND TREATABILITY CLEARINGHOUSE ABSTRACT
Treatment Process:
Media:
Document Reference:
Document type:
Contact:
Site Name:
Location of Test:
Physical/Chemical - Reduction/Oxidation
Soil/Generic
Smith,, D.L. and I.H. Sabberwal. "On-site
Remediation of Gasoline-Contaminated Soil." 15 pp.
Technical paper presented at the International
Congress on Hazardous Materials Management,
Chattanooga, TN, June 8-12, 1987.
Conference Paper
Ronald E. Lewis
Associate Waste Management Engineer
State of California Dept. of Health Services
Toxic Substances Control Division
714-744 P Street
Sacramento, CA 95814
916-322-3670
Soil Treatment Project, Southern California
(Non-NPL)
Los Angeles, CA
BACKGROUND; This treatability study reports on the results of tests aimed
at treating gasoline contaminated soils at seven different sites using
hydrogen peroxide to oxidize gasoline constitutents to C02 and H20 in the
presence of a proprietary synthetic polysilicate catalyst.
OPERATIONAL INFORMATION; The author reviews the magnitude of the contami-
nation problems associated with leaking underground storage tanks with
emphasis on problems in California. The use of hydrogen peroxide to
oxidize hydrocarbons is then discussed along with its attributes (no
hazardous residue formation) and its drawbacks (slow reaction time oxidiz-
ing saturated hydrocarbons). A table showing the ability of H^O* to react
with various classes of compounds is included in the document along with a
table shoving the various types of organic constitutents present in gaso-
line. The authors discuss the mechanism whereby a patented synthetic
polysilicate named "Landtreat" is used to enhance the HjO, oxidation of
soils contaainated with gasoline. Basically the polysilicate acts as a
catalyst to enhance the oxidation of the organic species. Through a high-
temperature, high-vacuum process, Frankel defects are created in the matrix
of the polysilicate. These defects become active sites which increase the
absorptive capacity of the "Landtreat". UV light also enhances the
reaction rate. Furthermore, the active sites on the "Landtreat" react with
cations, specifically heavy metals, converting them to metal silicates
which pass the EP toxicity test.
The soil to be treated is excavated, mixed with "Landtreat" and sprayed
with a solution of H-O, in water. The soil is mixed with a backhoe, front-
loader or similar eartn mover to ensure adequate contact. QA/QC and Health
3/89-25 Document Number: EWFZ
NOTE: Quality assurance of data may not be appropriate for all uses.
-------
and Safety procedures are discussed in the document. Cost for treating the
soil ranges from $70-$130 per cubic yard.
PERFORMANCE! The information presented in the report are from actual soil
treatment projects performed in southern California. In general, between
300 and 1500 cubic yards of soil were treated. Dry sandy and sandy clay
soils were reported. Project completion time took from 3 to 7 days work on
site excluding excavation, lab analysis, and backfilling. Average treat-
ment efficiencies for total petroleum hydrocarbons (TPH) ranged from 962 to
in excess of 99% depending on the site characteristics. The results of a
seven day test at one site and the amount of total petroleum hydrocarbons
removed is shown in Table 1. The results indicate that the oxidation of
hydrocarbon contaminated soils by Rj®? in the presence of a synthetic
catalyst is a technically viable soil remediation method.
CONTAMINANTS;
Analytical data is provided in the treatability study report,
breakdown of the contaminants by treatability group is:
The
Treatability Group
WOl-Halogenated Nonpolar
Aromatic Compounds
V04-Halogenated Aliphatic
Compounds
V07-Simple Nonpolar
Aromatics and
Heterocyclic
Wll-Volatile Metals
W13-0ther Organics
CAS Number
108-90-7
106-93-4
71-43-2
108-88-3
95-47-6
100-41-4
108-38-3
7439-92-1
TOT-PETROL
Contaminants
Chlorobenzene
Ethylene dibromide
Benzene
Toluene
O&P-Xylene
Ethylbenzene
M-Xylene
Lead
Total Petroleum Hydro-
carbons
3/89-25 Document Number: EWFZ
NOTE: Quality assurance of data may not be appropriate for all uses.
-------
TABLE 1
TOTAL PETROLEUM HYDROCARBON CONCENTRATIONS AT SITE 6
BEFORE AND AFTER TREATMENT
Untreated Soil (ppm) Treated Soil* (ppm)
6,700 6.9
4,300 <2.0
1,803 15.8
8,884 15.2
1,663 <2
40,302 6
71.7 4
* There is no direct correlation between treated and untreated soil for the
results shown above. Untreated soil samples were taken at various depths
during excavation and the treated samples were taken from various parts
of the treatment pile subsequent to mixing and treatment.
Note: This is a partial listing of data. Refer to the document for more
information.
3/89-25 Document Number: EWFZ
NOTE: Quality assurance of data nay not be appropriate for all uses.
-------
'—"*\
"Am
ON-SITE REMEDIATION OF GASOLINE-CONTAMINATED SOIL
Douglas L. Smith, Technical Services,
and I.E. Sabherwal, Ph.D., President
Ensotech, Inc.
11300 Hartland St.
North Hollywood, CA 91605
(818) 760-8622
I. INTRODUCTION
Gasoline leaking from service station tanks
threatens groundwater supplies in many areas of the
nation. California and other states have underground
storage tank monitoring programs, with mandatory
replacement of leaking tanks. The scope of the problem
nationwide is still unknown. However, discussions with the
California Water Quality Control Board indicate that an
unlined gasoline tank underground for five years has a 50%
probability of leaking. Thn probability of leakage
approximates 100".' after a decade of service. A 'VQCB
official estimated that there are about 500 sites in Los
Angeles and Ventura counties where groundwater nas bwc-n
affected. Another 1500 sites have significant tank leaks
which have not effected ground water.
The WOCB has found that inventory reconciliation by
its^.'f is insufficient to detect many leaks. Product
delivery records and dipstick measurements are generally
Dad- in hundred-gallon increments. Fifty or sixty gallons
..;i' gasoline can be lost without showing up on daily
inventories. At this rate of loss, 2,1,900 gallons of
gasoline would enter the. soil in a year from a single
tank. Even in smaller stations using weekly inventories,
fifteen gallons could be lest per day without
discrepancies occuring. This is equivalent to spilling
5,475 gallons of gasoline per tank per year. A typical
gas station has three or four underground tanks.
Substantial quantities of soil can be contaminated if the
leakage is allowed to continue for years. At one site
a gasoline station was demolished in the early sixties.
(See Site A in site Histories, b»iow). The storage tanks
were removed, and the tank cavity backfilled. The tank
removal report, noted a pronounced gasoline odor at the
bottom of the cavity, a depth of fifteen feet. .No-action
was taken. In 1S86. over twenty years later, while digging
the foundation for a multistory office building on the
site, the old tank cavity was reopened. The gasoline odor
was still prevalent, and construction was halted. The
area had to be excavated to a depth of thirty-two feet
before background Total Petroleum Hydrocarbon (TPK) levels
were reached. Eleven hundred cubic yards of soil had to
be treated and backfilled before construction could
resune.
"Jo be published in the proceedings of the I nr.erneit ional Congress on Hazardous
Materials Management, Chattanooga, Tennessee, June 8-12, 1987
-------
II. PAST USES OF HYDROGEN PEROXIDE
Hydrogen peroxide has long been known-to oxidize many
classes of noxious organic compounds. These compounds are
shown in Table I.
Hydrogen peroxide has several advantages over other
oxidants: it is readily available, inexpensive, and its
liquid state makes it easy to use in field conditions.
Peroxide cleaves aromatic ring structures, and oxidizes
the resulting straight- or branched- chain alkenes.
Oxidation proceeds through a series of progressively
shorter hydrocarbon chains, eventually resulting in carbon
dioxde and water. Peroxide's primary advantage, however,
is that it leaves no hazardous residue itself. This
compares favorably with oxidants such as chlorine, which
can be acutely toxic. Chlorination can also produce toxic
chlorinated hydrocarbons. Unreacted peroxide spontaneously
decomposes to water and oxygen. The released oxygen
enriches the soil, promoting aerobic bacterial activity.
Aerobic bacteria destroys sulfides and other noxious odor-
producing chemicals. Oxygen also inhibits anaerobic
bacteria, which produce sulfides, and filamentous
, bacteria, which produce other foul-smelling byproducts.
Peroxide treatment by itself has several crippling
disadvantages. Under normal conditions, hydrogen peroxide
reacts very slowly with saturated alkanes, and the
reactions do not go to completion. Saturated alkanes make
' up nearly two-thirds of a typical unleaded gasoline (see
Table II). Direct peroxide addition to soil gives an
uncontrolled, highly exothermic reaction. The heat
. evolved volatizes most of the gasoline before it can be
destroyed. The heat also drives off the intermediate
decomposition products, which are more volatile due to
their lower molecular weight. The intermediate breakdown
products, especially mercaptans, can be more noxious than
the original compounds. Both these factors constitute an
air pollution problem which precludes peroxide treatment
in the open air. Additionally, the heat of reaction
facilitates hydrogen peroxide's autocatalytic
decomposition to water and oxygen. Adding additional
peroxide to compensate for decomposition losses gives a
hotter reaction and faster peroxide loss.
-------
TABLE I
WASTE CHEMICAL CLASSES ABILITY
TO REACT 'WITH HYDROGEN PEROXIDE
Chemical Compound Yes No Unknown
Aliphatic Hydrocarbons (1) x x
Alkyl Halides x
Ethers x
Halogenated Ethers and Epoxides x
Alcohols (2) x
Glycols, Expoxides x
Aldehydes, Ketones (3) x
Carboxylic Acids x
Amides x
Esters x
Nitriles ' x
Amines x
Azo Compounds, Hydrazine Derivatives x
Nitrosamines x
Thiols (3) x
Sulfides, Disufides (3) x
Sulfonic Acids, Sulfoxides x
Benzene and Substituted Benzene (2) x
Halogenated Aromatic Compounds x
Nitrophenolic Compounds x
Fused Polycyclic Hydrocarbons x
Fused Non-Alterant Folycyclic Hydrocarbon x
Heterocyclic Nitrogen Compounds x
Heterocyclic Oxygen Compounds x
Heterocyclic Sulfur Compounds • " x
Organophosphorus Compounds x
(1) Saturated alkanes unreactive; unsaturated compounds
form epoxides and poly-hydroxy compounds.
(2) Requires catalyst
(3) May require catalyst
SOURCE: Remedial Action of Waste Disposal Sites. (Revised)
EPA/625/6-85/006, USEPA Office of Research and
Development, Hazardous Waste Engineering Research
Laboratory, Cincinnation, OH, October, 1985,
p 9-55.
-------
TABLE II
LIQUID GASOLINE COMPONENTS IN UNLEADED GASOLINE
COMPOUNDS VOLUME PERCENT
1. Butane
2. Butane, 2-raethyl
3. Pentane
4. 2-Pentene (trans)
5. 2-Butene, 2-methyl
6. Butene, 2, 3-dimethyl
7. Pentane, 2-methyl
8. Pentane, 3-methyl
9. Hexane
10. Cyclopentane , methyl
11. Pentane, 2, 2-dimethyl
12. Benzene
13. Hexane, 2-methyl
14. Cyclopentane, 1, 1-dimethyl
15. Hexane, 3-methyl
16. Pentane, 2, 2, 4-trimethyl
17. Heptane
18. Toluene
19. Benzene, ethyl
20. Xylene, para and met a
21. Xylene, ortho
22. Toluene, para and meta ethyl
23. Benzene, 1, 3, 5-trimethyl
24. Benzene, 1, 2, 4-trimethyl
TOTAL
Total branched-chain alkanes: 61.1%
Total branched-chain alkenes: 6.5%
Total substituted aromatics: 32.4%
3.85
9.26
3.42
1.02
1.76
1.34
3.70
2.31
2.37
1.88
1.13
1.57
2.20
1.61
1.80
4.00
1.45
7.20
1.18
3.50
1.62
2.00
1.25
2.36
63.78%
As analyzed by capillary gas chromatography. The
remaining 36.22% consists of 116 minor components, each
less than 1.00 % by volume. The same 2:1 approximate
ratio of branched-chain aliphatic to substituted aromatic
compounds is retained among the minor constituents. The
gasoline used for this analysis was a typical unleaded
gasoline. Percentages may vary depending on the
crude source, blending composition and gasoline grade.
-------
III. THE LANDTREAT PROCESS
LANDTREAT is a patented synthetic polysilicate. (U..
S. Patent Nos. 4,440,867 and 4,530,765.) It is used in a
finely divided, high-surface-area powder. The silicate
matrix has been expanded by a high-temperature, high-
vacuum process, creating Frankel defects. These defects
become active sites where hydrogen peroxide and gasoline
components can be adsorbed. The active sites facilitate
peroxide decomposition to singlet oxygen, a highly
reactive species. Singlet oxygen attacks saturated
alkanes as well as unsaturated and aromatic species.
LANDTREAT resorbs the intermediate decomposition products.
These partially broken down species are attacked again,
and the process continues until essentially complete
decomposition to carbon dioxide and water is achieved.
Reaction rates are further enhanced by the ultraviolet
light in sunlight.
The general reaction sequence can be written as
follows:
RCH2CH3 + LANDTREAT > RCHaCHa (adsorbed)
Ha02 + LANDTREAT > HaOa (adsorbed)
HaOa (adsorbed) > HzO (desorbed) + :0 (desorbed)
CATALYST
2:0 + CHsCHzR (adsorbed) > Ha 0 + HCO-CHaR (adsorbed)
:0 + HCO-CHaR (adsorbed) > HOOCCHzR (adsorbed)
«
2:0 + HOOCCHiR (adsorbed) > HaO (desorbed)
+ COz.(desorbed)
+ HCO-R (adsorbed)
R is alkyl, branched or straight-chained. The process is
also being applied to other fuels, including kerosine and
diesel; and to a variety of industrial solvents, including
ketones, aldehydes, and alcohols.
The stoichiometry and kinetics of the reaction
sequence are still under investigation. Field experience
indicates that TPH reductions of up to 30% can be obtained
within hours of peroxide addition in threefold excess of
assumed stoichiometric amounts.
As a side reaction, the active sites on the LANDTREAT
also react with cations, specifically heavy metals. The
metals are converted into metal silicates. The silicates
pass the USEPA's E.P. Toxicity test, as well as
California's CAM test, a similar but more stringent
procedure. Metal contamination from leaded gasoline,
waste motor oil, or other sources is therefore treated at
the same time.
-------
Ensotech has developed a different fixation process
where extensive heavy metal contamination exists at
elevated levels. An extended discussion*of this process
is outside the scope of the present paper, however.
IV. TREATMENT PROTOCOL
The treatment protocol is quite simple. The Site
Supervisor surveys the area and marks off the treatment
area, decontamination area, and treated and untreated soil
storage areas. These areas are then roped off and
placarded appropriately. Appropriate precautions are
taken in the treatment area to protect the paving, if any,
and the underlying soil. An earthern berm is created
around the treatment area to prevent runoff. The minimum
berm height is six inches, with proportionate thickness.
The decontamination area is located with the berm. The
only decontamination residues are unreacted peroxide and
water, which are allowed to mix into the treated soil.
Splash barriers and windbreaks are erected to guard
against windborne aerosol formation if site conditions
dictate.
The soil may have been stockpiled in advance, or may
be excavated at the time of treatment. The soil is
treated sectionally. 'Each section is spread over the
treatment area to form a layer of uniform thickness. Layer
thickness is not critical. LANDTREAT is mixed into the
soil. The soil is manipulated with a backhoe, frontloader,
or s.imilar type of earthmover.
The soil-LANDTREAT mixture is sprayed with a solution
of hydrogen peroxide in water. Peroxide is diluted in a
premix tank on board the spray unit. The unit is entirely
self-contained on a small trailer which includes the
premix tank, gasoline-powered compressor, and 100' to 300'
of hose. The unit is operated from the spray gun via an
electric control circuit.
Quality control during the treatment is maintained by
on-site testing. Successive peroxide applications
continue until, on-site results are satisfactory. On-site
testing consists of exposing standardized soil samples to
a TLV sniffer or photoionization detector. Calibration
curves have been developed using soil samples spiked with
predetermined levels of gasoline. Different curves are
required for different soil types, but all show gopd
reproductibility when sniffer readings are made according
to the standard handling procedure. The sniffer is also
used to monitor ambient air quality around the treatment
site.
V. SAFETY PRECAUTIONS
-------
Site safety procedures are in accordance with normal
industry practice for peroxide use. All personnel handling
the peroxide solution are equipped with Level II
protection: protective rubber clothing, including gloves
and boots, as well as a face shield and respiratory
protection. Lesser levels of protection are sufficient
for supervisory personnel or bystanders not in the
treatment area.
A portable eyewash kit, a first aid kit, and a fire
extinguisher are kept on-hand in a site safety cart. A
water hose from the nearest city water connection is kept
near the treatment area at all times to serve as an
emergency safety shower, if needed. The hose is also used
to decontaminate all protective clothing at the end of the
day, using the predesignated decontamination area.
Personal tools (shovels, etc.) are decontaminated at
the end of each working day, and removed from the jobsite.
Major treatment equipment is left in the treatment area
overnight until the project is completed, and is then
decontaminated at the end of the job.
VI. SITE CLOSURE AND REGULATORY CONSIDERATIONS
Closure requirements are minimal. Once laboratory
analysis confirms complete treatment (usually defined as
TPH < 100 mg/kg and total Benzene-Toluene-Xylene-Ethyl
Benzene (BTXE) < 10 mg/kg), the soil can be backfilled on-
site, sent to a Class III (sanitary) landfill, or used as
clean fill for landscaping. The gas station resumes
operation.
Final samples are generally spli-t with the lead
regulatory agency for independent verification. Analyses
commonly performed include USEPA methods 7420 (lead), 8010
(Ethylene Dibromide [EDB], an antiknock additive commonly
found in unleaded gasoline), 8015 (TPH), and 8020 (BTXE).
Some agencies also require method 9040, pH. To date, no
treated soil has been rejected by a regulatory agency or
by a sanitary landfill. Groundwater monitoring wells are
not generally required unless groundwater contamination
already exists. A separate groundwater treatment system
may be required in some cases. Even without treatment,
groundwater quality will gradually improve with time after
the contamination source is removed.
Permitting requirements vary with the lead agency,
which in turn varies with the geographical area and the
presence or potential of groundwater contamination. In
general a variance must be obtained to perform on-site
treatment at each specific site. At this writing, the
process has been used under the jurisdiction of the
California Department of Health Services, the Los Angeles
County Department of Health Services, the Los Angeles City
-------
Department of Public Works, the Los Angeles Regional Water
Quality Control Board, the Santa Ana Regional Water
Quality Control Board, the Orange County Health Care
Agency, and the Riverside County Health Department.
Because the process is virtually emission-free, no
air pollution permits are required. In the case of an
operating gas station, ambient gasoline vapors at the pump
islands are orders of magnitude higher than at the
periphery of the treatment area.
VI. SITE HISTORIES
The data presented below comes from actual soil
treatment projects performed in Southern California. In
general, between 300 to 1500 cubic yards of soil were
treated at each site. Treatment costs ranged from $70.00
to $130.00 per cubic yard. This compares favorably with
the total disposal cost at a Class I dumpsite. Transport
and disposal of the untreated soil would cost
approximately $250.00 to $330.00 per cubic yard. Treatment
cost is site-specific, varying with the volume of soil,
extent of contamination, and other factors.
Each project took approximately three to seven days
of work on-site. This does not include permitting,
excavation, backfilling, or the laboratory analyses
required to certify complete treatment.
Note on sample reporting: the site characterizations
from, which these data were derived were performed under
varying circumstances in conjunction with any of several
different agencies. Sample location and numbering schemes
therefore vary from site to site as do the quantity and
type analyses performed. In some cases, specific
analytical data gathered by other firms was not approved
for publication, so general TPH and BTXE ranges have been
given instead.
8
-------
SITE A
Gas station abandoned and tanks removed in early
1960's. Original depth of tank cavity: 15'. Depth
excavated to reach background: 32'. Depth to groundwater:
200'+. Dry sandy clay soil. Approximately 1100 cubic
yards treated in four working days. Treated soil was
backfilled.
UNTREATED SOIL AS EXCAVATED
Sample
Depth/loc
V-399-1 30 ft
V-399-2 22 ft
V-399-3 18 ft
V-399-4 15 ft
V-399-5 untreated
excavated soil
V-399-6 Background
soil
Pb
9.3
9.3
20.00
20.00
9.3
20.00
TREATED SOIL AS BACKFILLED
Sample Depth/loc Pb
V-465-1
V-465-2
V-465-3
V-465-4
24-32 ft
16-23 ft
9-22 ft
0-8 ft
9.3
9.3
15.00
15.00
TPH
20
196
425
798
211
35
TPH
31
25
45
43
EDB
NA
NA
NA
0.17
NA
EDB
<0.1
<0.1
<0.1
Note: The following abreviations are usfed throughout the
site histories:
TPH = Total Petroleum Hydrocarbon
B = Benzene
T = Toluene
m-X = meta-Xylene
o&p-X = ortho- and para-Xylene
EB = Ethylbenzene
CB = Chlorobenzene
EDB = Ethylene Dibromide
Pb = Lead
NA = Not Analyzed
All results are reported in milligrams per kilogram
of soil unless otherwise noted. .
-------
SITE B
Gas station demolished and tanks removed. Treatment
performed immediately after demolition. Depth of
excavation: 12-14'. Groundwater perched and variable,
with highest recorded level at 15'. Monitoring well
installed during site characterization found no perch
water contamination. Monitoring well removed upon
conclusion of treatment. Moist, fine silty clay and sand.
1215 cubic yards of soil excavated and treated in ten
working days. Treated soil was backfilled.
UNTREATED SOIL
Sample
W-453
W-462
W-463
Depth/ TPH
Loc
m-X o&p-X
EB
CB
14ft
14ft
15ft
TREATED SOIL
Sample TPH
1010
193
174
B
4.75
1.88
0.73
33.90 47.90
5.44 6.38
3.22 6.18
m-X o&p-X
W-491
W-492
W-493
8.4 0.16
<2 0.40
9.9 <0.08
<0.08
<0.'08
<0.08
<0.08
<0.08
<0.08
<0.08
<0.08
<0.08
7.31
9.95
7.42
EB
<0.08
<0.08
<0.08
2.16 1.94
5.01 0.50
2.67 0.29
pH*
CB
9.0 <0.08
8.4 <0.08
8.6 0.23
* Of a 10* solution
10
-------
SITE C
Depth of excavation approximately 20*. No groundwater
in vicinity of site. Dry, sandy soil. Nine hundred cubic
yards treated in three working days. Limited space
available, due to large soil stockpiles, so treatment area
located between pump islands. Treated soil was sent to a
Class III landfill.
Before treatment, soil samples showed average TPH 191
to 1,350 mg/kg, with some values as high as 8,900 mg/kg.
The highest total BTXE (Benzene-Toluene-Xylene-
Ethylbenzene) recorded was 782 mg/kg.
TREATED SOIL
Sample TPH B
m-X o&p-X
EB
EDB
Pb
1
2
3
4
5
6
7
<2 <
<2 <
<2 <
<2 <
<2 <
<2 <
<2 <
:o.os
:o.oa
:o.os
:o.os
:o.os
co. 08
:o.os
<0
<0
<0
<0
<0
<0
<0
.08 <
.08 <
.08 <
.08 <
.08 <
.08 <
.08 <
:o.os <
CO. 08 <
co. 08 <
CO. 08 <
CO. 08 <
CO. 08 <
CO. 08 <
:o.oa
CO. 08
CO. 08
CO. 08
CO. 08
CO. 08
CO. 08
<0.
<0.
<0.
<0.
<0.
<0.
<0.
08
08
08
08
08
08
08
<0.
<0.
<0.
<0.
<0.
<0.
<0.
08
08
08
08
08
08
08
<2.5
<2.5
<2.5
<2.5
<2.5
<2.5
<2.5
11
-------
SITE D
Excavation in excess of thirty feet. Depth to
groundwater: 140*. Soil was sandy, • unconsolidated
alluvium. Treatment proceeded while new tanks were being
installed. Approximately 480 cubic yards treated in four
working days. Treated soil was used for landscaping on-
site.
UNTREATED TANK CAVITY SOIL
Sample
1
2
3
4
5
6
Sample
1-A1
2-A2
3-D
U-DU
Sample
7
•8
9
SP-1
SP-2
TREATED
Sample
V-950-1
V-950-2
V-950-3
Depth
(ft)
14-G
18-G
14-G
18-G
8-W 1,
12-W
Depth
(ft)
20-G
24-G
10-W
14-W
Depth
(ft)
32-G
25-G
12-W
NA-G
NA-G
SOIL
TPH
<8
<8
<8
TPH
4
10
40
6
820
15
TPH
2,530
1,960
2
880
TPH
4,980
< 10
98
1,390
97
B*
<10
<10
< 10
B
<0.
<0.
<0.
<0.
<0.
<0.
B
<0.
<0.
<0.
<0.
<
<
<
02
02
02
02
02
02
01
01
01
01
Pb
0.1
<0 . 1
<0. 1
NA
NA
T*
10
10
10
T
<0.02
<0.02
<0.02
<0.02
0.04
<0.02
T
7.3
9.6
<0.01
0.02
m-X*
<10
<10
< 10
EB
Pb
<0.02
<0.02
<0.02
<0.02
0.33
<0.02
X
920
820
0.01
2.7
<0.02
<0.02
<0.02
<0.02
0.05
<0.02
EB
57
60
<0.01
0.05
3.0
7.1
25
3.7
45
5.8
Pb
<0.01
<0.01
<0. 1
1.5
o&p-X* EB* Pb
<20 <10 7.6
<20 <10 <2
<20 <10 <2
Values given are micrograms per kilogram of soil
12
-------
SITE E
Excavated to 22*. No groundwater
Clayey silt alluvial deposits to 50'. Six
yards treated in three working days. Treated
to Class III landfill.
in vicinity.
hundred cubic
soil was sent
UNTREATED SOIL
Sample
SE
SM
SW
CE
CM
CW
NE
NM
NW
Depth into pile
8"
8"
8"
5'
5'
5'
8"
8"
8"
TPH
76
148
105
1040
1250
980
35
29
48
Composite of nine samples of untreated soil
pile.
Sample
V-737-1
through
V-737-9
TREATED SOIL
Sample TPH
1A <1
2A <1
3A <1
4A <1
5A <1
TPH
860
B*
<5
<5
<5
<5
<5
B
2.1
T*
<5
<5
<5
<5
<5
T
24
m-X
35
from spoil
o&p-X
37
m-X* .o&p-X*
<5 <10
<5 <10
<5 <10
<5 <10
<5 <10
EDB*
Pb
<2
<2
<2
<2
<2
* Values given are micrograms per kilogram of soil.
13
-------
SITE F
No groundwater in vicinity. Very confined site and
thick, intractable clay slowed treatment. 1945 cubic
yards of soil treated in ten working days. Some treated
soil was used for on-site grading and some sent to a Class
III landfill.
UNTREATED SOIL
Sample TPH B T m-X o&p-X EB CB Pb
1
W-380 7.6 0.24 0.46 0.53 0.17 0.60 <0.08 <5 0,
W-381 295 0.31 5.49 13.5 2.59 3.21 8.89 <5 £
W-384 675 0.46 23.5 50.4 7.62 18.3 0.16 <5 1
W-385 305 0.22 4.48 15.0 1.17 3.03 1.02 <5 2
W-444 42 0.31 1.56 1.04 0.27 0.57 1.05 NA '•
W-445 16.8 0.17 0.35 0.15 0.31 <0.08 <0.08 NA ''
W-446 236 0.08 10.1 " <0.08 <0.08 2.52 5.53 NA z<
TREATED SOIL '
-------
SITE G
Extensive gasoline and waste oil contamination. Site
excavated to practical limit of 25'. Groundwater
depth: 32*. Significant groundwater contamination being
treated by other means. Moist, sandy clay to 7', followed
by dense, damp, bedded, well-sorted, uncemented sandstone.
Very confined site required some soil to be backfilled
before the job completion in order to have room to treat
remaining soil. Approximately 726 cubic yards of soil
treated in seven working days. Remainder of treated soil
sent to Class III landfill.
UNTREATED SOIL
The laboratory results, in parts per million (ppm),
are as follows:
Tank Cavity Soils Spoils Pile
Sample
1A
IB
2A
2B
3A
3B
4A
4B
Depth (ft) TPH Sample Tank TPH
8-W 5.83> 6,
15-W 3.fc'S 4,
14-G *-*t 1,
14-G V9S- 8,
14-G ?. 2-2. 1,
14-G '
+
G = Gasoline tank area /^ - <
W = Was
TREATED
Sample
W-596
W-597
W-598
W-599
W-600
W-601
W-602
•^v
<
te oil tank area
SOIL
TPH B
6.9 .£<•( 0.22
<2 o.Vxo.08
15.8 \<-L°Q.Q8
15.2 V.lfc 0.09
<2 o,5oo.l9
6.70.W0.32
4.6 QLLQ.n
**-A~ C, 1 (.
3. i> a>. ?7
T
<0.08
<0.08
<0.08
<0.08
<0.08
<0.08
<0.08
«
•
mX o&p-X EB
<0.08 <0.08 <0.08
<0.08 <0.08 <0.08
<0.08 <0.08 <0.08
<0.08 <0.08 <0.08
<0.08 <0.08 <0.08
<0.08 <0.08 <0.08
<0.08 <0.08 <0.08
^ 12.
15
-------
EPA/540/2-89/021
SUPERFUND TREATABILITY
CLEARINGHOUSE
Document Reference:
Summary report "Harbauer Soil Cleaning System." 10 pp. Received at U.S. EPA
Headquarters on November 20,1987.
EPA LIBRARY NUMBER:
Super-fund Treatability Clearinghouse • EVAR
-------
SUPERFUND TRRATABILITY CLEARINGHOUSE ABSTRACT
Treatment Process: Physical/Chemical - Soil Washing
Media: Soil/Sandy
Document Reference: Summary report. "Harbauer Soil Cleaning System."
10 pp. Received at U.S. EPA Headquarters on
November 20, 1987.
Document Type: Contractor/Vendor Treatability Study
Contact: W. Werner, President
Harbauer, Inc.
Berlin, W. Germany
Site Name: Pintsch Oil Site (Non-NPL)
Location of Test: Berlin, West Germany
BACKGROUND; This document reports on the use of a soil cleaning system to
remove contaminants from various types of soils by washing and concurrently
vibrating the soils to force the contaminant into the liquid phase. The
system was developed by Harbauer and is being used in Berlin, Germany at a
site contaminated with waste oils.
OPERATIONAL INFORMATION; The contaminated soil is mixed with the
extractant liquid and introduced into a decontamination chamber. The
chamber contains a device resembling a giant auger to which mechanical
energy is applied axially in the form of vibrations. Separation is
achieved continuously as the contaminated soil is moved through the system.
A vibrating system was utilized as it allows for control of process condi-
tions. The two most important parameters affecting system performance are
residence time and the energy density of the vibrations. Residence time is
varied by controlling the rotation speed of the auger which moves the
material through the chamber. Energy density is controlled by altering the
frequency and amplitude of the vibrations. There are four basic process
parameters that must be optimized or controlled for a successful cleanup.
They are: 1) producing a stable soil/liquid suspension, 2) extraction of
the pollutants through the use of mechanical energy, 3) separation of the
soil/liquid phases after extraction and 4) separation of the pollutant from
the water phase and reuse of the extractant. The system is closed but no
information vas provided on system capacity. No QA/QC plan is contained in
the document. No site specific information on the amount of soils requir-
ing treatment or contaminant levels was provided. Dirty water from the
soil washing operation at the Berlin site is incorporated into the overall
groundwater cleanup process. This water meets effluent standards and may
be released directly into neighboring waterways.
PERFORMANCE; The current state of the art allows for use of this technique
in 0.06 mm to 0.6 mm particle size range. Research is being conducted to
extend the technique down to the 0.006 mm particle size range to clean clay
and other fine materials. Tests were conducted on a variety of different
soils (sandy, silt and clay) contaminated with organic petroleum product,
3/89-26 Document Number: EVAR
NOTE: Quality assurance of data may not be appropriate for all uses.
-------
phenol chloride, PAH, PCB and cyanides. Removal efficiencies ranged from
84X to 100X. Clay soil had the lowest removal efficiency. Table 1 shows
the results of tests on contaminated clay soil. The technique appears to
remove various contaminants from the soil, however, no information is
provided on the amount of contaminant the water extraction process alone
removes versus the amount of contaminant removed by the energy introduced
into the system. No results were provided on the effect of increasing the
energy density on contaminant removal efficiency.
CONTAMINANTS;
Analytical data is provided in the treatability study report. The
breakdown of the contaminants by treatability group is:
Treatability Group CAS Number Contaminants
W02-Dioxins/Furans/PCBs 1336-36-3 Total PCBs
W08-Polynuclear Aromatics TOT-PAH Total Polycyclic
Aromatic Hydrocarbons
W09-0ther Polar Compounds 108-95-2 Phenol
W13-0ther Organics TEH Total Extractable Hydro-
carbons
TOC Total Organic Carbon
TABLE 1
RESULTS OF SOIL WASHING TESTS ON A CLAY SOIL
Input Remaining Washing Success
Pollutants Pollutant Level Pollutant Level X Removed
(mg/kg) (mg/kg)
Total Organics 4440 159 96.4
Petroleum Extract
Total Phenol 165 22.5 86.4
PAH 948 91.4 90.4
BOX (mgCl-/kg) 33.5 ND 100
PCB 11.3 1.3 88.3
ND = None Detected
Note: This is a partial listing of data. Refer to the document for more
information.
3/89-26 Document Number: EVAR
NOTE: Quality assurance of data Bay not be appropriate for all uses.
-------
HARBAUER SOIL CLEANING SYSTEM
The Harbauer soil cleaning system is a wet extraction process
which uses mechanical energy in the form of specially produced
oscillations or vibrations to achieve the initial separation
of soil particles and pollutant.
The sample material, mixed with extractant, is introduced
into the decontamination chamber. This chamber contains a
device resembling a giant auger to which mechanical energy is
applied axially in the form of vibrations. Separation is
achieved on a continuous basis as the sample is moved forward
by rotation of the auger under constant vibration.
Harbauer evaluated all other existing technologies including
the water knife before developing the present system. The
vibrational system was selected because it permits control of
the process conditions. This permits greater efficiency
in the cleanup of the wide range of existing pollutant situations,
e.g. , soil types, pollutant types, and pollutant concentration
levels.
The two most important parameters affecting the success of
clean-up are the residence time of the sample in the decontam-
ination chamber and the energy density of the vibrations in
the chamber. Residence time is controlled by controlling the
rotation speed of the auger which moves the sample material
through the chamber. Energy density is controlled by altering
the frequency, amplitude, and acceleration of the oscillations.
The four basic problem areas for successful clean-up are:
The production of an optimum suspension (minimization of
solids) ,
*
The extraction or. pollutants while minimizing the use
of additional chemicals through substitution of mechanical
energv,
The separation of the solid/liquid phase (extractant from
the sand/pollutant material),
The separation of the pollutant from the water phase and
recirculation of extractant.
The system is a closed system with recirculation of the extractant
It is operating at present in Berlin at the former Pintsch
oil site in conjunction with a groundwater cleanup plant.
Dirty water from the soil washing operation is incorporated
into the overall groundwater cleanup process, and this water
meets all effluent standards and may be released directly into
the neighboring waterway.
-------
HARBAUER SOIL CLEANING PROCESS
STEP 1 PREPARATION
o Sample preparation to 12 mm particle size
o Mixing of Soil and extractant
STEP 2 EXTRACTION
o Sample extractant mixture is introduced into
the chamber.
o Sample is conveyed through the chamber by an
element resembling a large auger screw, which
is turned to move the sample forward through
the chamber.
o Specially produced oscillations or vibrations
(using hydraulic propulsion) at high energy are
applied axially to the screw conveyer to
vibrate soil particles and separate pollutant.
STEP 3 PHASE SEPARATION OF WATER/SAND MIXTURE — WITH REMOVAL
OF CLEANED PARTICLES
STEP 4 EXTRACTANT/POLLUTANT SEPARATED, WITH RECYCLING OF CLEAN
EXTRACTANT
-------
PARTICLE SIZE
Kornverteilung
1
Sand
avg. large
mlttcl I ofoo
20
10 —
0,0010,002
0,006 0.01 0,02
0,06 0,1 0,2
0.06J 0.125 0.25
0,6 1
6 10 20
60 100
Forschungsfeld || Entw/ck/ungll
Horbouer |l Horbouer ||
Stand der Technik
State of the Art
article size in mn
Current Research
Objective
Existing Harbauer Technology
1
-------
RuBschema der Bodenwasche
-Soil
ncroinigtor Doden
LAJ A4 K T
WSsche
Phasentrcnnung
Extrnktlonsmlttel
<• Schndstoff
ExtrakttonsmUtel
Extraktlonsmlltel-
Bufbereitung
hochbel«9l«l* R«it»tolf«
Extraktionsmittelkreislauf
temperatur-
Zersettungssystftm
-------
-------
SANDY EARTH
Sandboden
tollutant
'.chadstoff
Input
belastung
Remaining
Pollutant
Tlesc-
belastung
Cleanup
Results
Wascnerfolg
f°/}
{/OJ
TOTAL ORGAN I CS
PETROLEUM EXTRACT.
rganische Gesamt-
elastung (Petrol-
hter-Extrakt)
i (mg/kg)
3TAL PHENOL (MG/KG)
esamtphenol
i (mg/kg)
UI (MG/KG)
(mg/kg)
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EPA/540/2-89/020
SUPERFUNDTREATABILITY
CLEARINGHOUSE
Document Reference:
Science Applications International Corporation. 'Treatment of Contaminated Soils with
Aqueous Surfactants (Interim Report)." and "Project Summary: Treatment of
Contaminated Soils with Aqueous Surfactants." Prepared for U.S. EPA, HWERL,
ORD. 46pp. December 1985.
EPA LIBRARY NUMBER:
Superfund Treatability Clearinghouse - EUZU
-------
SUPERFUND TREATABILITT CLEARINGHOUSE ABSTRACT
Treatment Process:
Media:
Document Reference:
Document Type:
Contact:
Site Name:
Location of Test:
Physical/Chemical - In-situ Soil Washing
Soil/Sandy
Science Applications International Corporation.
"Treatment of Contaminated Soils with Aqueous
Surfactants (Interim Report)." and "Project
Summary: Treatment of Contaminated Soils with
Aqueous Surfactants." Prepared for U.S. EPA,
HVERL, ORD. 46 pp. December 1985.
EPA ORD Report '
Richard Traver
U.S. EPA, ORD
HWERL - Release Control Branch
Woodbridge Avenue
Edison, NJ 08837
201-321-6677
Manufactured Waste (Non-NPL)
HWERL/EPA ORD Cincinnati, OH
BACKGROUND; This treatability study reports on the results, conclusions
and recommendations of a project performed to develop a technical base for
decisions for the use of surfactants in aqueous solutions to wash soils
in-situ. The study reports on the selection of soil and contaminants, the
test equipment and methods, the results of the various surfactant concen-
trations tested and the results of tests to remove the surfactants from the
leachate.
OPERATIONAL INFORMATION: Aqueous monionic surfactants, high boiling point
crude oil, PCBs and chlorophenols were selected for testing. A fine to
coarse loamy soil with 0.12 percent TOC by weight and permeability of
10 cm/s was selected for testing. Shaker table partitioning experiments
were conducted to determine the minimum surfactant concentration required
to accomplish acceptable soil cleanup. This was done for each of the
selected contaminants. The soil was spiked and packed in a 3 inch by 5 ft.
column for washing. Recycling of washing solution was tested and cleaning
of the contaminants from the surfactant solution was tested.
PERFORMANCE; The extent of contaminant removal from the soil was 92 per-
cent for the PCBs, using 0.75 percent each of Adsee 799 (Witco Chemical)
and Hyonic NP-90 (Diamond Shamrock) in water. For the petroleum hydro-
carbons, the removal with a 2 percent aqueous solution of each surfactant
was 93 percent. Water alone removed all but 0.56 percent chlorophenol
after the tenth pore volume of water. Leachate treatment alternatives of
foam fractionations, sorbent adsorption, ultrafiltration and surfactant
hydrolysis were tested in the laboratory. The tests were able to concen-
trate the contaminants in the wastewater to facilitate disposal, and clean
the water enough to allow for reuse or disposal in a publicly owned
3/89-32 Document Number: EUZU
NOTE: Quality assurance of data may not be appropriate for all uses.
-------
treatment works. The study recommends further tests on other surfactants
in particular their amenability to separation and reuse. Report concludes
that the use of aqueous surfactants is a potentially useful technology for
in-situ cleanup of hydrophobic and slightly hydrophilic organic contami-
nants in soil.
CONTAMINANTS;
Analytical data is provided in the treatability study report. The
breakdown of the contaminants by treatability group is:
Treatability Group CAS Number Contaminants
W02-Dioxins, Furans 1336-36-3 Total PCBs
W03-Halogenated Phenols, 87-86-5 Pentachlorophenol (PCP)
Cresols, Thiols
3/89-32 Document Number: EUZU
NOTE: Quality assurance of data may not be appropriate for all uses.
-------
Unuea States
Environmental Protection
Agency
Hazaraous Waste Engineering
Researcn Laooratory
Cincinnati OH 45268
Researcn and Development
EPA/600/S2 q5/129 Dec. 1985
Project Summary
Treatment of Contaminated
Soils with Aqueous Surfactants
William D. Ellis, James R. Payne, and G. Daniel McNabb
The full report presents the results,
conclusions, and recommendations of a
project performed to develop a technical
base for decisions on the use of chemical
countermeasures at releases of hazard-
ous substances. The project included a
brief literature search to determine the
nature and quantities of contaminants
at Superfund sites and the applicability
of existing technology to in situ treat-
ment of contaminated soils. Laboratory
studies were conducted to develop an
improved methodology applicable to
the in situ treatment of organic chemical
contaminated soil.
Current technology for removing
contaminants from large volumes of
soils (too large to excavate economical-
ly) has been limited to in situ "water
washing." Accordingly, the laboratory
studies were designed to determine
whether the efficiency of washing could
be enhanced significantly (compared to
water alone) by adding surfactants to
the recharge water and recycling them
continuously.
The use of an aqueous nonionic
surfactant pair for cleaning soil spiked
with PCBs. petroleum hydrocarbons,
and chlorophenols was developed
through bench scale shaker table tests
and larger scale soil column tests. The
extent of contaminant removal from the
soil was 92 percent for the PCBs. using
0.75 percent each of Adsee& 799
(Witco Chemical) and Hyonic* NP-90
(Diamond Shamrock) in water. For the
petroleum hydrocarbons, the removal
with a 2 percent aqueous solution of
each surfactant was 93 percent. These
removals are orders of magnitude
greater than obtained with just water
washing and represent a significant
improvement over existing in situ
cleanup technology.
Treatability studies of the contami-
nated leachate were also performed to
investigate separating the surfactant
from the contaminated leechata to allow
reuse of the surfactant. A method for
separating the surfactant plus the con-
taminant from the leechate was devel-
oped; however, ail attempts at removing
the surfactant alone proved unsuccess-
ful.
Based upon the results of the labora-
tory work, the aqueous surfactant
countermeasure is potentially useful for
in situ cleanup of hydrophobic and
slightly hydrophilic organic contami-
nants in soil, and should be further
developed on a larger scale at a small
contaminated site under carefully con-
trolled conditions. However, reuse of
the surfactant is essential for cost-
effective application of this technology
in the field. Accordingly, any future
work should investigate the use of other
surfactants/ surfactant combinations
that may be more amenable to separa-
tion.
This Project Summary was developed
by EPA's Hazardous Waste Engineering
Research Laboratory. Cincinnati. OH,
to announce key findings of the research
project that is fully documented in a
separate report of the same title (see
Profect Report ordering information at
back).
Introduction
The Comprehensive Environmental
Response, Compensation, and liability
Act of 1980 (CERCLA or Superfund)
recognizes the need to develop counter-
measures (mechanical devices, and other
physical, chemical, and biological agents)
to mitigate the effects of hazardous sub-
stances that are released into the envi-
-------
nment and clean up inactive hazardous
iste disposal sites. One key counter-
measure is the use of chemicals and
other additives that are intentionally
introduced into the environment for con-
trolling the hazardous substance. The
indiscriminate use of such agents could.
however, worsen the contamination
situation.
The U.S. Environmental Protection
Agency's Hazardous Waste Engineering
Research Laboratory has initiated a
Chemical Countermeasures Program to
define technical criteria for the use of
chemicals and other additives at release
situations of hazardous substances such
that the combination of the released
substance plus the chemical or other
additive, including any resulting reaction
products, results in the least overall harm
to human health and to the environment.
Under the Chemical Countermeasures
Program, the efficacy of in situ treatment
of large volumes of subsurface soils, such
as found around uncontrolled hazardous
waste sites, and treatment of large, rela-
tively quiescent waterbodies contami-
nated with spills of water soluble hazard-
ous substances, will be evaluated. For
each situation, the following activities are
olanned: a literature search to compile
e body of existing theory and data;
boratory studies on candidate chemicals
to assess adherence to theory and define
likely candidates for full-scale testing;
full-scale, controlled-condition, reproduc-
ible tests to assess field operation possi-
bilities; and full-scale tests at a site
requiring cleanup (i.e., a "site of oppor-
tunity").
This project, to develop the use of
aqueous surfactants for in situ washing
of contaminated soils, was the first
technique to be developed under the
Chemical Countermeasures Program.
The results and conclusions from an
information search formed the basis for
the laboratory development work. Simi-
larly, the results and conclusions from
the laboratory work are intended to
provide the basis for another project
involving large-scale testing o' a chemical
countermeasure, either in t. large test
tank or under controlled conditions at a
site of opportunity.
Information Search
The information search was conducted
to determine the nature and quantities of
hazardous soil contaminants at Super-
fund sites, and to assess the applicability
of existing technology for in situ treatment
o< contaminated soils. To determine what
types of soil contaminants requiring
cleanup were likely to be found at hazard-
ous waste sites, a survey was made of the
contaminants at 114 high priority Super-
fund sites. The classes of chemical wastes
found at the greatest number of sites, in
order of decreasing prevalence, were:
slightly water soluble organics (e.g..
aromatic and halogenated hydrocarbon
solvents, chlorophenols), heavy metal
compounds, and hydrophobic organics
(e.g.. PCBs. aliphatic hydrocarbons).
A variety of chemical treatment meth-
ods were considered that might prove
effective in cleaning up soils contami-
nated with these wastes. However.
methods for in situ chemical treatment of
soils will probably be most effective for
certain cleanup situations, such as those
in which:
• The contamination is spread over a
relatively large volume of subsurface
soil, e.g., 100 to 100.000 m3. at a depth
of 1 to 10 m; or
• The contamination is not highly con-
centrated, e.g.. not over 10.000 ppm,
or the highly contaminated portion of
the site has been removed or sealed
off; or
• The contaminants can be dissolved or
suspended in water, degraded to non-
toxic products, or rendered immobile,
using chemicals that can be carried in
water to the zones of contamination.
For contamination less than 1 m deep,
other methods such as landfarming (sur-
face tilling to promote aerobic microbial
degradation of organics) would probably
be more practical. For highly contami-
nated zones of an uncontrolled hazardous
waste landfill or a spill site, methods such
as excavation and removal, or excavation
and onsite treatment would probably be
more practical than m situ cleaning of the
soil.
Findings under the information search
indicated that aqueous surfactant solu-
tions might be applicble for in situ
washing of slightly hydrophilic (water
soluble) and hydrophobic organics from
soils. Texas Research Institute (TRI) used
a combination of equal parts of Witco
Chemical's Richonate
-------
results to actual field situations was a
primary consideration. Selection included
identifying the native soils at the ten
Region II Superfund sites for which data
was available, determining the most
commonly occurring soil type series, and
locating a soil of the same soil taxonomic
classification which could be excavated
and used in the testing experiment. In
addition to taxonomic classification, a
permeability rating of 10~2to 10~4 cm/sec
was desirable since less permeable soils
would take too long to test.
A Freehold soil series typic hapludult
soil was chosen for the study. The total
organic carbon content (TOO of the soil
was 0.12 percent by weight, implying a
relatively low contribution by organic
matter to the adsorption of organic con-
taminants. The cation exchange capacity
(CEC) of the soil was determined to be 8.6
milliequivalents per 100 gms, an extreme-
ly low value, indicating an absence of
mineralogic clay in the soil.
Using a percent moisture content of 11
percent and compacting the soil in the
columns to a density of 1.68 g/cm3(105
Ib/ft3), an optimum percolation rate of 1.5
x 10~3 cm/sec was obtained under a
constant 60 cm head.
Surfactant Selection
The surfactant combination used by
TRI for flushing gasoline from sand,
Richonate-D YLA and Hyonic* NP-90
(formerly called Hyonici) PE-90). was
screened along with several other surfac-
tants and surfactant combinations for the
following critical characteristics: ade-
quate water solubility (deionized water),
low clay particle dispersion, good oil
dispersion, and adequate biodegradabil-
ity. The surfactants selected for ultimate
use in the laboratory studies were AdseeS
799 (Witco Chemical) and HyomcS NP-90
(Diamond Shamrock).
So/7 Contamination Procedures
Soil was contaminated using an aerosol
spray of the contaminant mixture dis-
solved in methylene chloride. The meth-.
ylene chloride was allowed to evaporate.
and the soil was mixed by stirring in pans.
The soil was then tested in shaker or
column studies.
Column Packing
The soil columns used in this study
were 7.6 cm (3 in.) inside diameter by 150
cm (5 ft) long glass columns. A plug of
glass wool was placed at the bottom of
the column and successive plugs of
contaminated soil weighing approximate-
ly 775 g were packed to a height of 10 cm
(4 in.) each. To ensure better cohesion
between layers, the upper 1/4 inch of
each plug was scarified. The soil was
packed to a total height of 90 cm (3 ft) and
compacted to a density of 1.68 to 1.76
g/cm3 (105 to 110 Ib/ft3), yielding a
percolation rate which was comparable
to its natural permeability.
Shaker Table Tests
Shaker table partitioning experiments
were conducted to determine the mini-
mum surfactant concentration required
to accomplish acceptable soil cleanup.
After spiking Freehold soil with PCBs and
hydrocarbons, separately, surfactants
were used to wash the soil by shaking in
containers on a constantly vibrating
shaker table.
One hundred grams of contaminated
soil were agitated with 200 ml of the
appropriate surfactant concentration on a
shaker table for one hour, then centri-
fuged. and decanted. Both soil and leach-
ate were analyzed to determine how
much of the contaminant had been
removed.
«
So/V Column Experiments
During the first year of study, the effect
of soil washing with water, followed by
4.0 percent surfactants (2 percent each),
and a final water rinse was investigated
in soil column experiments using Murban
distillate cut. PCBs and di-, tri-, and
pentachlorophenol contaminants. Free-
hold soil was spiked, separately, with
1,000 ppm Murban distillate cut, 100
ppm PCS, and 30 ppm chlorinated
phenols.
Results of these column experiments
showed that the initial water wash had
little effect; however, with surfactant
washing, 74.5 percent of the pollutant
was removed by the leachate after the
third pore volume (i.e., volume of void
space in the soil). Additional surfactant
increased the removal to 85.9 percent
after ten pore volumes. The pollutant
concentration in the soil was reduced to 6
percent of the initial spike value after the
tenth pore volume of surfactant. The final
water rinse also showed only minimal
effects.
Almost identical behavior was observed
for the column experiments using PCB
spiked soil: the initial water wash was
ineffective, but the soil was cleaned
substantially by the 4.0 percent surfactant
solution. After the tenth pore volume. 68
percent of the PCBs were contained in the
leachate. leaving only 2 percent on the
soil.
Similar soil column experiments were
also conducted using a mixture of di-. tn-,
and pentachlorophenols, and. in contrast
to the PCB and Murban distillate cut
results, 64.5 percent of the chlorinated
phenols were removed by the first water
wash, and only 0.56 percent remained on
the soil after the tenth pore volume of
water.
Optimization of Surfactant
Concentration
To make soil washing techniques cost
effective, it was necessary to determine
the minimum concentration of surfactant
that would yield acceptable soil cleanup.
Surfactant concentrations were varied
from 0 to 1.0 percent (2 percent total
surfactant) in shaker table experiments
using both PCB and hydrocarbon con-
taminated soils. Column experiments
were then undertaken to verify shaker
table data and to further optimize surfac-
tant concentrations.
Figure 1 shows the effect of surfactant
concentration on PCB partitioning be-
tween soil and leachate. There was
essentially no cleanup of the soil with
surfactant concentrations of 0.25 percent
(0.50 percent total) or below. Similar PCB
partitioning was observed for 0.75 per-
cent and 1.0 percent individual surfactant
concentrations, and the most effective
cleanup occurred at these levels.
As Figure 2 shows, similar soil/leach-
ate partitioning behavior was also ob-
served for Murban hydrocarbons with
varying surfactant concentrations. Indi-
vidual surfactant concentrations of 0.25
percent and below were ineffective; in-
creased surfactant concentrations caused
increased soil cleanup from 0.50 to 0.75
percent surfactant; above 0.75 percent
surfactant concentration little enhance-
ment of soil cleanup occurred.
Column Verification
To ensure that the optimum surfactant
concentration under gravity flow condi-
tions was not significantly different than
under equilibrated shaker table condi-
tions, columns packed with Freehold soil
spiked with 100 ppm PCBs were also
tested with varying surfactant levels.
The columns were treated with one,
two. or three pore volumes of 0.50, 0.75.
or 1.0 percent surfactant before sacrifice
and soil analysis. The downward migra-
tion of PCBs is apparent in Figure 3,
which presents the PCB concentrations
in the various portions of the columns as
a function of pore volume for each of the
three surfactant concentrations tested
PCB mobilization was not much greater
-------
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4
with 0.75 percent surfactant than with
1.0 percent surfactant, and somewhat
less for the 0.50 percent surfactant
concentration. After three pore volumes.
the PCB concentrations at the bottom of
the column were of 244 A«J/g with the
0.50 percent surfactant, compared with
405 A'Q/Q using 0.75 percent surfactant
and 562 ,ug/g using the 1.0 percent
surfactant.
Results of the column experiments.
coupled with the results of the shaker
table experiments, indicate that the opti- •
mum surfactant concentration for soil
cleanup is about 0.75 percent of each
surfactant or 1.5 percent total surfactant.
Evaluation of Leachate
Treatment Techniques
Large amounts of surfactants and wash
water are required for field application of
this countermeasure technology. Surfac-
tants are expensive, and for this tech-
nology to be cost effective, surfactant
recycling is an important consideration.
Accordingly, various leachate treatment
techniques were evaluated for their ability
to remove and concentrate the contami-
nants, while leaving the surfactants
behind for further use. All treatment
methods evaluated were ineffective in
separating the contaminants from the
surfactant. However, several leachate
treatment techniques were able to (1)
concentrate the contaminants to facilitate
disposal, and (2) clean the water enough
that it could be sent to a publicly owned
treatment works (POTW) or reused.
Four treatment alternatives were
tested, and the conditions for efficient
leachate treatment were optimized in
preparation for large-scale field testing.
Foam fractionation, sorbent adsorption,
ultrafiltration. and surfactant hydrolysis
were subjected to preliminary laboratory
tests using simulated leachate.
The results of the foam fractionation
tests showed that good cleanup of the
leachate was achieved if the concentra-
tion of surfactant was below about 0.1
percent, while no significant reduction in
surfactant occurred at starting concen-
trations above that.
Eleven solid sorbents were tested for
their efficiency in removing PCBs and the
surfactants from an aqueous solution.
None of the sorbents was very efficient in
removing PCBs from a surfactant solution.
The most efficient sorbent for PCB re-
moval was the Filtrol XJ-8401, with an
efficiency of 0.00045 g/g; WV-G 12x40
Activated Carbon, and Celkate magne-
sium silicate were most efficient in overall
surfactant and PCB removal (0.195 g/g).
-------
Hydrolysis treatment of the surfactant
nd contaminant-containing leachate
was also tested. Adse*e> 799. a fatty acid
ester, formed a separate organic phase
upon hydrolysis that contained both the
surfactants and 95 percent of the organic
contaminants.
Further treatment of the aqueous sur-
factant solution with a column of activated
carbon (Westvaco Nuchar WV-B 14x35)
yielded a solution containing only 0.01
ppm of PCBs. Foam fractionation was
also used as a polishing method for
removing traces of surfactants from
aqueous solutions. A four-column series
of foam fractionation columns operating
in a continuous countercurrent flow mode
was used. The test results demonstrated
that the residual PCB level (0.0036 ppm)
should be low enough to allow disposal to
a POTW. and low enough to permit reuse
of the leachate water for soil cleaning.
However, the use of hydrolysis was
necessary for the higher surfactant con-
centrations found in the raw leachate.
Evaluation of Leachate
Recycling
To evaluate the effect of recycling the
untreated aqueous leachate on soil
cleanup, column experiments were con-
icted. The results showed that leachate
^cycling—without some sort of treat-
ment—is not an acceptable method, as
contaminants become redistributed back
onto the soil with each successive pass.
However, a column experiment in which
the recycled leachate was treated be-
tween each pass showed very effective
cleanuo of soil.
Between passes, fresh surfactant was
added to the treated leachate prior to
recycling, and the soil in the column
received four passes of fresh surfactant:
only the water was recycled. After four
passes, less than 1 0 percent of the
original soil contamination remained.
Conclusions and
Recommendations
Effectiveness of the Surfactants
Based on bench-scale tests designed to
screen potential surfactants for use as in
situ soil washing enhancers, a 1:1 blend
of Adsee-S 799 (Witco Chemical Corp.)
and Hyonic® NP-90 (Diamond Shamrock)
was chosen because of adequate solubil-
ity in water, minimal mobilization of clay-
sized soil fines (to maintain soil perme-
bihty). good oil dispersion, and adequate
adegradability.
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'Samples Lost
Shaker table and column experiments
show that 4.0 percent of this blend of
surfactants in water removed 93 percent
of the hydrocarbon and 98 percent of the
PCB pollutants from contaminated soil.
These removals are orders of magnitude
greater than those obtained with just
water washing and represent a significant
improvement to the efficiency of existing
technology. Chlorinated phenols were
readily removed from the test soil by
water washing alone.
Shaker table experiments conducted to
determine the optimum surfactant con-
centration for soil cleanup, with PCB and
petroleum hydrocarbon (Murban) con-
taminated soils, showed the optimum
concentration to be 1.5 percent total
surfactant. Individual surfactant concen-
trations of 0.25 percent or less were
unacceptable for effective soil washing,
and individual surfactant '•uncentrations
above 0.75 percent (1.5 percent total)
were excessive, since no significant
enhancement of cleanup resulted. In
addition, similar partitioning between soil
and surfactant solution by the two pollu-
tant types suggests that the results which
would be obtained in further large-scale
experiments with the low toxicity hydro-
carbons in a fuel oil like Murban might
reliably model the behavior of other more
toxic hydrophobic pollutant groups, such
as PCBs.
The experiment which evaluated the
effect of leachate recycling, with treat-
ment applied to the PCB leachate between
cycles, showed that:
• Soil cleanup with 1 5 percent total
surfactant is good, with less than 1
percent of the PCB remaining on the
soil
• The product of hydrolysis represents a
relatively small volume (about 12
percent of the total mass of leachate)
of highly contaminated material, which
can be further treated by incineration.
or disposed of for a minimal cost
• The use of the same water for repeated
cycles precludes the generation of
large volumes of waste leachate.
• The final treated water after four cycles
contains less than 0.0005 percent of
the initial contamination encountered
in the soil.
Additional surfactant tests are war-
ranted before this technology can be
applied in the field. The surfactant com-
bination used was water soluble, and
effective in soil cleanup, and allowed
good soil percolation rates, as the mixture
did not resuspend a significant amount of
the clay-sized particles in the soil, thereby
inhibiting flow. These characteristics are
-------
'efimtely important; however, for this
chnology to be cost effective, reuse of
.ne surfactant is equally important.
Accordingly, it is recommended that other
surfactants/ surfactant combinations be
evaluated that have the same "flushing"
characteristics but are also more amen-
able to separation for reuse. The surfac-
tant should be screened for solubility,
clay dispersion, and oil dispersion, and
should also be screened by mutagenicity
tests to avoid the distinct possibility that
the release situation could be made worse
by the application of a toxic chemical or
other additive.
Effects of the Test Soil
The efficiency of cleanup of the hydro-
phobic organic contaminated Freehold
soil by the aqueous surfactant solution
was directly affected by the low natural
organic carbon content of the soil. The
low TOC (0.1.2 percent) represented little
organic matter, in the soil to adsorb the
organic pollutants spiked onto the soil, so
the contaminant removal could be ex-
pected to be relatively easy compared to a
soil with, for example, a 1 percent TOC.
The removal of hydrophobia organics from
a 1 percent TOC soil using the AdseeD
"'SS - HyonicK NP-90 surfactant pair
ould require more surfactant solution
^Iso, the surfactants would become
necessary for removing chlorophenols
from a 1 percent TOC soil; water alone
would not be very effective.
If additional laboratory or pilot-scale
testing were undertaken, a second soil
type with greater percentages of organic
carbon should be considered for testing to
expand the overall applicability of the
program results to a broader variety of
soil matrices.
The hydraulic conductivity of the Free-
hold soil packed in the soil columns.
which was measured at 1.05 x 1CT3
cm/sec, would be practical for field
implementation of the countermeasure.
However, the time required for surfactant
solution to flow through the soil should be
considered. With this hydraulic conduc-
tivity, if surface flooding were used to
obtain saturated conditions from the
surface to a groundwater depth of 10 m
(33 ft), and assuming a porosity of 50
percent, it would take 5.5 days for one
pore volume of solution to flow through
the soil from surface to groundwater. A
flow rate under similar conditions, with a
soil permeability of 1 x 10~4 cm/sec.
would yield flow rates of about 1.2 m/wk,
which is probably a practical lower limit
or the method.
Potential Target Contaminants
The types of hazaraous chemicals for
which the surfactant countermeasure
was more effective than water without
surfactant, included hydrophobia organics
(PCBs and aliphatic hydrocarbons in the
Murban fraction) and certain slightly
hydrophilic organics (aromatic hydrocar-
bons in Murban). The chemicals for which
the method is probably not applicable are
heavy metal salts and oxides, and cya-
nides. For soils with low TOC values.
chlorophenols and certain other slightly
hydrophilic organics can be removed with
water alone. However, for soils with high
TOC values, the use of aqueous surfac-
tants would significantly improve the
removal efficiency of slightly hydrophilic
organics.
Effective Treatment Methods
A need to conserve both water and
surfactant prompted the investigation of
leachate reuse or recycling. Recycling of
the untreated leachate is unacceptable
because portions of the soil that have
been previously cleaned are recontarm-
nated rapidly by the introduction of spent
leachate. The ideal treatment method
removes and concentrates contaminants
while leaving the surfactants behind for
further use. However, the samechemical
and physical properties of the surfactant
mixture that help to extractthe pollutants
from the soil also inhibit separation of the
contaminants from the surfactants. Due
to the high (percentage) level of surfactant
contained m the leachate. most of the
treatment methods evaluated were inef-
fective The best treatment that could be
obtained removed both surfactants and
pollutants, leaving clean water for pos-
sible reuse or easy disposal.
Additional efforts should be directed
toward optimizing feasible and cost-
effective methods of leachate treatment
and in particular separation of the sur-
factant for reuse. Ultrafiltration appears
promising and warrants further investi-
gation along with foam fractionation. The
use of already existing equipment and
technologies should be examined m
greater detail to minimize scale-up costs.
Further Countermeasure
Development Before Field Use
The testing of a new technique, in
which hazardous contaminants are rend-
ered more mobile, presents a potentially
greater environmental threat unless the
tests can be readily stopped at any point
as required to permit the immediate
remedy of any failure by established
techniques. Because the aqueous sur-
factant countermeasure is still develop-
mental, the field tests should be conducted
on a reduced scale until the procedures
are proven workable and the important
parameters are understood and control-
led.
The laboratory tests have established
that the technique of in situ washing with
aqueous surfactants is sufficiently effec-
tive for soil cleanup to justify tests on a
larger scale. Pilot-scale testing requires
the use of disturbed soil, and will probably
not further the development of the method
as much as controlled-condition .field
testing at a site of opportunity. An appro-
priate site for field testing should have the
following characteristics:
• Moderate to high permeability (coef-
ficient of permeability of 10~4 cm/sec
or better)
• Small size (e.g., 30 m x 30 m x 10 m
deep)
• Minimal immediate threat to drinking
water supplies
• Hydrophobic and/or slightly hydro-
phylic organic contaminants
• Concentrated contamination source
removed or controlled
• Low to moderate natural organic mat-
ter content in soil (TOC 0.5 to 2
percent).
If either small sites, or physically sepa-
rated sections of a large site (e.g., with a
slurry or grout wall) were selected, the
aqueous surfactant countermeasure
described in this report could be applied,
tested further, and improved to a point of
full field countermeasure applicability.
However, future work should evaluate
other surfactants that have the same
cleanup characteristics as those used in
the laboratory studies but are more
amenable to separation for reuse. Also.
prior to any larger scale/site of opportun-
ity studies, the toxicity of the surfactants
should be ascertained.
-------
TREATMENT OF CONTAMINATED SOILS UITH AQUEOUS SURFACTANTS
(INTERIM REPORT)
by
William D. Ellis
James R. Payne
G. Daniel McNabb
Science Applications International Corporation
8400 Westpark Drive
McLean, VA 22102
Contract No. 68-03-3113
Project Officer
Anthony N. Tafuri
Hazardous Waste Engineering Research Laboratory
Releases Control Branch
Edison, NJ 08837
HAZARDOUS WASTE ENGINEERING RESEARCH LABORATORY
OFFICE OF RESEARCH AND DEVELOPMENT
U.S. ENVIRONMENTAL PROTECTION AGENCY
CINCINNATI, OHIO 45268
-------
ABSTRACT
This report presents the results, conclusions, and recommendations of a
project performed to develop a technical base for decisions on the use of
chemical counter-measures at releases of hazardous substances. The project
included a brief literature search to determine the nature and quantities of
contaminants at Superfund sites and the applicability of existing technology
to in situ treatment of contaminated soils. Laboratory studies were conduc-
ted~~Fo develop an improved methodology applicable to the in situ treatment of
organic chemical contaminated soil.
Current technology for removing contaminants from large volumes of soils
(too large to excavate economically) has been limited to in situ "water wash-
ing." Accordingly, the laboratory studies were designed to determine whether
the efficiency of washing could be enhanced significantly (compared to water
alone) by adding aqueous surfactants to the recharge water and recycling them
continuously.
The use of an aqueous nonionic surfactant pair for cleaning soil spiked
with PCBs, petroleum hydrocarbons, and chlorophenols was developed through ,
bench scale shaker table tests and larger scale soil column tests. The extent
of contaminant removal from the soil was 92 percent for the PCBs, using 0.75
percent each of Adsee 799« (Witco Chemical) and Hyonic NP-90* (Diamond Sham-
rock) in water. For the petroleum hydrocarbons, the removal with a 2 percent
aqueous solution of each surfactant was 93 percent. These removals are
orders of magnitude greater than obtained with just water washing and repre-
sent a significant improvement: over existing in situ cleanup technology.
Treatability studies of the contaminated leachate were also performed to
investigate separating the surfactant from the contaminated leachate to allow
reuse of the surfactant. A method for separating the surfactant plus the con-
taminant from the leachate was developed; however, all attempts at removing
the surfactant alone proved unsuccessful.
Based upon the results of the laboratory work, the aqueous surfactant
countermeasure is potentially useful for in situ cleanup of hydrophobic and
slightly hydrophilic organic contaminants~Tn soil, and should be further
developed on a larger scale at a small contaminated site under carefully
controlled conditions. However, reuse of the surfactant is essential for
cost-effective application of this technology in the field. Accordingly, any
future work should investigate the use of other surfactants/surfactant combi-
nations that may be more amenable to separation.
This report was submitted in partial fulfillment of Contract No. 68-03-
3113 by SAIC/JRB Associates under the sponsorship of the U.S. Environmental
Protection Agency. This report covers the period from May 1982 to August
1985, and work was completed on August 23, 1985.
iv
-------
CONTENTS
FOREWORD iii
ABSTRACT 1v
FIGURES vii
TABLES viii
ABBREVIATIONS AND SYMBOLS 1x
ACKNOWLEDGMENTS x
1. INTRODUCTION 1
2. INFORMATION SEARCH 3
2.1 Potential In Situ Counter-measures for Soils 9
2.1.1 HyJFopTuJFic Organics 9
2.1.2 Slightly Hydrophilic Organics 13
2.1.3 Hydrophilic Organics 14
2.1.4 Heavy Metals 14
2.2 Potential Pilot-Scale, and Full-Scale Tests
of Soil Counter-measures 15
2.2.1 Pilot-Scale Testing 15 '
2.2.2 Site of Opportunity Testing 17
3. CONCLUSIONS 19
3.1 Effectiveness of the Surfactants 19
3.2 Effects of the Test Soil 20
3.3 Potential Target Cbntaminants 21
3.4 Effective Treatment Methods 21
4. RECOMMENDATIONS 23
4.1 Selecting Surfactants for In Situ Soil Cleanup 23
4.2 Testing Other Soils 23
4.3 Developing Leachate Treatment Methods 24
4.4 Further Countermeasure Development Before
Field Use 24
5. MATERIALS AND METHODS 25
5.1 Soil Selection and Characterization 25
5.2 Surfactant Screening Tests 29
5.3 Shaker Table Tests 29
5.4 Soil Column Tests 30
5.5 Analytical Procedures 32
5.5.1 Extraction of Organics from Aqueous Media 32
5.5.2 Extraction of Organics from Soil 34
5.5.3 Instrumental Analysis 34
5.5.4 Internal Standards 35
5.6 Leachate Treatment 35
-------
6. RESULTS AND DISCUSSION ^-.-»- 36
6.1 Soil Characteristics 36
6.2 Surfactant Selection 41
6.3 Preliminary Soil Column Experiments 42
6.4 Optimization of Surfactant Concentration 47
6.4.1 Shaker Table Tests 47
6.4.2 Column Tests 50
6.5 Evaluation of Leachate Treatment Techniques 50
6.5.1 Laboratory Tests of the Most Feasible
Treatment Alternatives 52
6.5.1.1 Foam Fractionation 53
6.5.1.2 Sorbent Adsorption 56
6.5.1.3 Surfactant Hydrolysis and Phase
Separation 56
6.5.1.4 Ultrafiltration . . . . , 59
6.5.2 Less Feasible Treatment Alternatives 62
6.5.2.1 Flocculation/Coagulation/Sedimentation. . 62
6.5.2.2 Centrifugation 63
6.5.2.3 Solvent Extraction 63
6.6 Evaluation of Leachate Recycling 63
6.6.1 Column Tests With Untreated Leachate 63
6.6.2 Column Tests With Treated Leachate 64
REFERENCES 72
APPENDICES
A. Shaker Table Extraction Procedure 77
B. Gas Chromatography Run Conditions and Run Programs 78
C. High Performance Liquid Chromatography Run Conditions
and Run Programs 80
D. Calculations and Quality Control for Instrumental
Analysis 82
E. Metric Conversion Table 84
-------
SECTION 1
INTRODUCTION
The "Comprehensive Environmental Response, Compensation, and Liability
Act of 1980" (CERCLA or Superfund) recognizes the need to develop counter-
measures (mechanical devices, and other physical, chemical, and biological
agents) to mitigate the effects of hazardous substances that are released
into the environment and are needed to clean up inactive hazardous waste
disposal sites. One key counter-measure is the use of chemicals and other
additives that are intentionally introduced into the environment for the
purpose of controlling the hazardous substance. The indiscriminate use of
such agents, however, poses a distinct possibility that the release situation
could be made worse by the application of an additional chemical or other
additive.
The U.S. Environmental Protection Agency's Hazardous Waste Engineering
Research Laboratory has initiated a Chemical Countermeasures Program to >.
define technical criteria for the use of chemicals and other additives at
release situations of hazardous substances such that the combination of the
released substance plus the chemical or other additive, including any result-
ing reaction or change, results in the least overall harm to human health and
to the environment.
The Chemical Countermeasure Program has been designed to evaluate the
efficacy of in situ treatment of large volumes of subsurface soils, such as
found around uncontrolled hazardous waste sites, and treatment of large,
relatively quiescent waterbodies contaminated with spills of water-soluble
hazardous substances. For each situation, the following activities are
planned: a literature search to develop the body of existing theory and data;
laboratory studies on candidate chemicals to assess adherence to theory and
define likely candidates for full-scale testing; full-scale, controlled-
condition, reproducible tests to assess field operation possibilities; and
full-scale tests at a site requiring cleanup (i.e., a "site of opportunity").
This project, to develop the use of aqueous surfactants for in situ
washing of soils contaminated with hydrophobic (water insoluble) organic* and
slightly hydrophilic (slightly water soluble) organics, was the first tech-
nique to be developed under the Chemical Countermeasures Program. Another
countermeasure for soils, the use of acids and chelating agents for washing
heavy metals from soils, is also being developed under the Program.
The Aqueous Surfactant Countermeasures Project included an information
search and laboratory development of the Countermeasures. The results and
conclusions from the information search formed the basis for the laboratory
1
-------
development work. Similarly, the results and>-conclusions from the laboratory
work are intended to provide the basis for another project involving large-
scale testing of a chemical countermeasure, either in a large test tank (e.g.,
15 m x 15 m x 7.5 m deep), or under controlled conditions at a similarly
sized contaminated site or portion of a site of opportunity.
-------
RATIONALE FOR CHOOSING COUNTERMEASURE TEST COMPOUNDS
1.0 INTRODUCTION
The compounds which are used for testing of a chemical countermeasure
in the laboratory and in the CAT tank should meet the following criteria:
• occur frequently in high concentrations in the soil surrounding
Superfund sites
• present a significant hazard to human health and the environment
• have low to moderate mobility and high persistence in soil
• be treatable by an existing chemical method
• have an appropriate chemical analogue, if too hazardous or expensive
for experimentation
Data was gathered on the concentrations, frequency of occurrence,
soil adsorption, and toxicity of waste chemicals found at Superfund sites.
Sections 2 through 5 present the data and discuss the implications for
choosing a test mixture for future countermeasures testing.
i
In .general, it is assumed in the following discussions that an _in_
situ chemical countermeasure will be developjj^ for treating a large volume
of soil with relatively low levels of contamination. The purpose of the
countermeasure is for treating the soil surrounding an uncontrolled hazard-
ous waste sice after the main contamination source has been removed or
sealed off from the surrounding soil.
-------
2.0 HIGH CONCENTRATION, FREQUENTLY OCCURRING SOIL CONTAMINANTS
Chemical countermeasures are most needed for those chemicals which
are found most often and in the greatest concentration in the soils surround-
ing Superfund sites. To determine which waste chemicals should be targeted
for countermeasures development, the Field Investigation Team (FIT) Summaries
were examined for 50 Superfund sites on EPA's list of the 115 most hazardous
waste sites. The maximum concentrations of-contaminants in the soil sur-
rounding the sites and in the groundwater near sites were summarized using
the following set of concentration categories:
• detectable to * 10 ppb
• 10 ppb to •*- 100 ppb
• 100 ppb to^-1 ppm
• 1 ppm to ^-10 ppm
• 10 ppm to .£100 ppm
• 100 ppm to ^1,000 ppm
• 1,000 ppm to ^-10,000 ppm
• i. 10,000 ppm
I
Although the soil concentrations are most important, the groundwater concen-
trations can be used to roughly estimate soil concentrations using the
soil absorption constant. The soil and groundwater concentration data
thus gathered and summarized were used to calculate the average peak concen-
tration for each organic compound, metal, or inorganic ion. The results
-—>•
are presented in Tables 1-4. (Note that since the concentrations were
summarized by concentration categories covering one order of magnitude
each, the average volues were often calculated to be multiples of 3, which
is the logarithmic mean of one order of magnitude.)
The FIT Summaries provided data on the concentrations of the following
numbers of soil contaminants:
• 17 hydrophobic organics
• 7 slightly hydrophilic organics
• 12 heavy/toxic metals
• 1 toxic inorganic anion
-------
TABLE 1. CONCENTRATIONS OF HYDROPHOBIC CONTAMINANTS AT 50 SUPERFUND SITES
Chlordane
Dieldrin
Anthracene
Benzo(a)anthracene
Benzo(a)pyrene
Fluoranthene
Pyrene
DDT
Bis(2-ethylhexyl) Phthalate
Di-n-butyl Phthalate
o-Dich lor obenzene
PCB's
Dioxin
Naphthalene
Oil
Grease
1 ,2 ,4-T rich lor obenzene
Hexachlorobutadiene
Trichlorophenol
Ethyl Benzene
Bis(2-ethylhexyl) Adipate
Cyclohexane
Benzo(b)pyrene
1, 1,2-Trichlorotrifluoroethane
SOIL NEAR SITES
AVERAGE PEAK
CONCENTRATION
(ppm)
3000
30
30
30
30
30
30
20
10
3
2
1
1
0.3
0.003
0.003
0.003
0.003
-
-
-
-
-
-
~
NUMBER OF
SITES WHERE
DETECTED
I
1
1
1
1
1
1
2
3
1
2
7
1
1
1
1
1
-
-
-
-
-
-
"
GROQNDWATER
AVERAGE PEAK
CONCENTRATION
(ppm)
^
-
-
0.003
0.003
-
-
-
2
-
0.003
20
-
100
1
-
-
30
30
8
3
0.003
0.003
0.003
NUMBER OF
SITES WHERE
DETECTED
—
-
-
1
1
-
-
-
2
-
1
2
-
3
4
-
-
1
I
4
1
1
1
1
NOTE: "Hydrophobia" means log P > 3.00 (P = octanol/water partition coefficient).
-------
xBLE 2. CONCENTRATIONS OF SLIGHTLY HYDROPHILIC ORGANICS AT 50 SUPERFUND SITES
Xylene
Phenol
Carbon Tetrachloride
Methylene Chloride
Perch loroechylene
Toluene
T rich lor oethylene
Dichlorophenol
Methyl Chloroform
Vinylidene Chloride
Chloroform
Ethyl Chloride
Fluorotrichlorome thane
Ethylene Dichloride
Methyl Isobutyl Ketone
Vinyl Chloride
Benzene
1 , 2-Dichloroethylene
1 ,2-Diphenylhydrazine
Tetrahydropyran
1 , 1-Dichloroethane
Chlorobenzene
2-Ethyl-4-methy 1-1, 3-dioxo lane
Isopropyl Ether
SOIL NEAR SITES
AVERAGE PEAK
CONCENTRATION
(ppm)
3
1
.003
.003
.003
.003
.003
-
-
-
-
i
-
-
-
-
-
-
-
-
-
-
™ •
NUMBER OF
SITES WHERE
DETECTED
1
4
1
1
1
3
2
-
-
-
-
—
-
-
-
-
-
-*""">* *"•
-
-
-
-
—
GROUNDWATER
AVERAGE PEAK
CONCENTRATION
(ppm)
8
.02
0.3
30
10
7
3
30
8
8
4
3
3
2
2
1
0.7
o.s
0.3
0.3
0.1
.02
.003
.003
! NUMBER OF
SITES WHERE
DETECTED
4
3
1
6
5
9
10
1
4 '
4
8
1
1
4
2
4
9
6
1
1
4
3
1
1
NOTE: "Slightly hydrophilic" means log P > 1.00, £ 3.00 (P » octanol/water
partition coefficient).
-------
TABLE 3. CONCENTRATIONS OF HYDROPHILIC CONTAMINANTS AT 50 SUPERFUND SITES
\
J
Acetone
Methyl Ethyl Ketone
Acrolein
Tetrahydrofuran
1 ,4-Dioxane x
\
Ac ryloni trite
Isobutanol
2-Propanol
SOIL NEAR SITES
AVERAGE PEAK
CONCENTRATION
(ppm)
-
-
-
_
-
—
NUMBER OF
SITES WHERE
DETECTED
-
-
-
__
-
—
GROUNDWATER
AVERAGE PEAK
CONCENTRATION
(ppm)
800
2
0.3
0.2
0.03
0.003
0.003
0.003
NUMBER OF
SITES WHERE
DETECTED
4
3
I
2
1
1
1
1
NOTE: "Hydrophilic" means log P < 1.00 (P = octanol/water partition coefficient).
-------
TABLE 4. CONCENTRATIONS OF INORGANIC CONTAMINANTS AT 50 SUPERFUND SITES
HEAVY /TOXIC METALS
Cadmium
Zinc
Lead
Nickel
Chromium
Copper
Aluminum
Silver
\rsenic
Jarium
Beryllium
Manganese
Iron
Strontium
Titanium
Boron
Cobalt
Mercury
Selenium
OTHER TOXIC IONS
Cyanide
Thiocyanate
Perchlorate
Ammonium/Ammonia
SOIL NEAR SITES
AVERAGE PEAK
CONCENTRATION
(ppm)
30,000
20,000
10,000
10,000
2,000
1,000
300
30
20
.003
.003
i
.003
-
-
-
-
-
-
-
.003
-
-
~
NUMBER OF
SITES WHERE
DETECTED
4
5
7
3
5
3
1
1
2
1
1
1
-
-
— .. V-
' — >•
-
-
-
2
,
_
•-
GROUNDWATER
AVERAGE PEAK
CONCENTRATION
(ppm)
0.01
0.1
0.2
0.3
0.02
80
20
-
0.9
2
1
10
3
3
0.3
0.3
0.003
0.003
^
300
30
.20
NUMBER OF
SITES WHERE
DETECTED
3
4
3
1
4
4
2
"-
7
2
5
6
1
1
1
1
2
1
.
1
1
2
-------
No concentration data for hydrophilic organics was found. The categories
of organic compounds were based on the logarithm of the octanol/water parti-
tion coefficients (log P) of the compounds, as follows:
o Hydrophobic organics: log P> 3.00
o Slightly hydrophilic organics: log P>1.00, £3.00
o Hydrophilic organics: log P £1.00
The log P is a measure of the tendency of a compound to dissolve in hydro-
carbons, fats, or the organic component of soil rather than in water.
For instance, many hydrophobics, some slightly hydrophilics, and no hydro-
philics were detected in soil, which contains organic components that tend
to adsorb other organics; only groundwater samples contained any hydrophilics
(see Table 3). This does not mean that only hydrophobics and slightly
hydrophilics are found in soil, but they are normally found more than hydro-
philics are.
Not only is the log P a measure of the tendency of a compound to dissolve
in octanol, fat, or soils, it can also be used to estimate the tendency
of an organic compound to become (or remain) adsorbed in soil. Several
researchers have published regression equations relating log P to the soil
adsorption constant (K or K). The partitioning of a compound between
the organic components of soil and a water salvation is expressed as follows:
K _ ug adsorbed/g organic carbon
oc ~ ug/mL solution
The adsorption tendency is mainly dependent on the weight of organic carbon
(oc) in the soil. If the organic carbon content of a soil is known, then
the soil adsorptions constant (K) can be derived from K :
oc
„ j% organic carbon!
L 100 J
(Koc)
v ug adsorbed/g soil
K. — —•••—^——^— u.«—^^
ug/mL solution
Thus, K can be used to estimate what fraction of a compound will be adsorbed
-------
co soil and what fraction will remain dissolved in water when the soil
and water are in equilibrium with each other.
The K values for the waste compounds found in soil and groundwater
at Superfund sites are presented in Table 5-7 for hydrophobic organics,
slightly hydrophilic organics, and hydrophilic organics, respectively.
They were obtained from published data or calculated from log P values.
Besides the 17 hydrophobic compounds found in soil, another 7 hydro-
phobic compounds were found in groundwater near the Superfund sites. These
compounds may have been found in the soil if^nalyses were made, but ground-
water samples are analyzed more often than soil samples in FIT investiga-
tions. The same is true for the 17 slightly hydrophilic organics and the
10 inorganic contaminants measured in groundwater but not in soil.
-------
.C .S, HAZARD PARAMETERS OF HYDROPHOB1C ORGAN 1CS
Sobstance
Soil Adsorption . EPA Water Rat Oral LD,
Constant K *•* Quality Criteria (mg/kg)
(ppm)
Carcinogenic Dose (mg/kg)
Chlurdane
Die Idrin
Anthracene
Benzo(a)anthracene
Benzo(a)pyrene
FIuoranthene
Pyrene
DDT
*]s(2-ethy)hexyl)phthalate
Di-n-butyl phthalate
o-Dich1orobenzene
PCBs
Dioxin
"Naphthalene
Crease v
1,2,4-Trichlorobenzene
Nexachlorubuladiene
Trichlorophenol
"Ethyl benzene
Bis(2-ethylhexyl)Adipate
CycIohexane
Benzo(b)pyrene
I, 1,2-Trichlorut rifluuruethane
200
200
700
60.OOO
40,000
8.OOO
2,000
10,000
20.OOO
1OO
70
2.OOO
2.000.OOO
600
(30,000)**
(5,OOO.OOO)***
200
200
2.OOO
50
90.OOO
70
4O.OOO
60
4.6xlO~?*
2.8x10"**
2.8x10" *
0.042
2.8x10 *
2.4xJo"8*
15
34
7.9x10" *
283
46
TDLo: 4 (mouse, ural)
1.4
2.8xlO~6-
- TDLo: 18 (mouse, skin; neoplasm)
50(scu) TDLo: .002 (mouse, skin)
2,000
TDLo: 10,000 (mouse, skin, 3 wks.
iniermit tent)
113 TDLo: 73 (mouse, ural 26 weeks continuous)
3J.OOO
3,050 (ipr)
500
TDLu: 1,220 (rat, oral, el weeks; neoplasm)
TDLo: .00114 (rat, ural, 65 weeks cunl.)
1,780
756
90
820
3.500
9,110
29,820
\
J.
TDLo: 15.0OO (rat, oral, 2 years continuous)
-corresponds tu an incremental increase in cancer risk of 10
**estimated based on n-C.,
***estimated based on n-C?_
-6
-------
TABLE 6. HAZARD PARAMETERS OF SLIGHTLY HYDROPH1L1C ORGAN1CS
Xylene
Phenol
Carbon Tetrachloride
Methylene Chloride
Perchloroethylene
Toluene
Trichloroethylene
Dichlorophenol
Methyl Chloroform
Vinylidene Chloride
Chloroform
Ethyl chloride
Fluorotrichloromethane
Ethylene Dichloride
Methyl Isobutyl Ketone
Vinyl Chloride
Benzene
1,2-Dichloroethylene
1,2-Diphenylhydrazine
Tetrahydropyran
],1-Dichloroethane
Chlorobenzene
2-Ethyl-4-methyl-l,3-dioxolane
Isopropyl Ether
Soil Adsorption
Constant (K)1'*"
Water Quality
Criteria (ppm)
Oral Rat LD
(mg/kg)
50
Carcinogenic Dose (mg/kg)
30
20
20
5
20
30
20
50
20
10
10
6
20
6
_
3.5
0.004
—
0.008
14.3
0.0027
1.4
-
-
Ir9xl0~ *
_
_
9.4xlO~ *
4300
414
2800
167
—
5000
4920
580
14,300
200
800
_
_
0.012
J6
10
10
20
4
6
20
10
9
0.002
6.6x10 *
4.2x10
-5,
0.49
TDLo: 18,000 (mouse, oral,
days intermittent)
2080
500
3800
770
725
2910
8470
120
TDLo: 81,000 (mouse, oral,
78 weeks intermittent)
TCLo: 2,lOOmg/m (human,
inhalation, 4 years
intermittent)
-corresponds to an incremental increase in cancer risk of 10
-6
-------
TABLE 7. HAZARD PARAMETERS OF HYDROPHILIC ORGAN1CS
3 3
Soil Adsorption EPA Water Quality Oral Rat LD^n Carcinogenic Dose
Acetone
Methyl Ethyl Ketone
Acrolein
Tetrahydrofuran
1,4-Dioxane
Acrylonitrile
Isobutanol
2-Propanol
reme
\
r
• m
Constant (K) • Criteria (ppm)
0.7
1
0.8 0.32
2
0.4 5.8xlO~5*
2 - *~
1
ntal increase in cancer risk of 10
JU
9750
3400
46
—
4200
82
2460
5840
\
J
TDLo: 1.7 ug/]cg (rat, oral,
37 weeks continuous)
-------
TABLE 1. Candidate Organic and Inorganic Test Mixtures for Initial
Insitu Soil Treatment Evaluation >
Waste Type
Processes
Waste Amount (1b./yr.)*
1) Organics -
Fuel Oils;
PCB;
Organophosphate
Pesticides;
Chlorinated Hydrocarbon
Pesticides;
Methanol;
Reclaimers residues wastes
Nonutilitv polvchlorinated biohenvl wastes
Pesticide wastes
Production wastes
Production wastes
Cosvnthesis Methanol production wastes
2) Chlorinated Hydrocarbons -
Carbon Tetrachloride;
Perch!oro & Trichloro-
ethylene;
Pentachlorophenol;
Dichlorobenzene;
3) Amines -
Ethylenediamine;
Ethanolamine;
, Acids and Bases -
Hydrochloric Acid;
Fire extinguisher; solvent
Chlorinated Hydrocarbon
pesticide production
Wood preservatives waste
Spent wood preserving liquors
Residue from Manufacture of ethylene
dichloride/vinyl chloride
Sulfuric Acid;
Potassium Dichromate;
Sodium Hydroxide;
Ammonium Hydroxide;
Solvent and emulsifier uses, textile lubricant
Gas purification, emulsifier and'
tanning agent
Petroleum Refining-WoStes
Chloride production
Chemical Industry wastes
Metals Production wastes
Chemical Industry wastes
Petroleum Refining wastes
Primary Metal production
Manufacturing wastes
Leather production""*'
Pigments and dyes production
Petroleum Refining wastes
Paper products
Chemical Industry wastes
Textile Manufacturing
Polymer Production wastes
3 x 10?
8 x 10°
1 x 10§
6 x
2 x
10
108
1 x 10e
Not Available
2 x 108
2 x 10
2 x 10
2 x 10'
11
12
Various
Various
Various
Various
Various
Various
Various
Various
Various
Various
Various
Various
Various
Various
Various
Various
Various
Cheremisinoff, N.P., P.N. Cheremisinoff, F. Ellerbusch and A.J. Perna (1979),
Industrial and Hazardous Wastes Impoundment. Ann Arbor Science pp 16-23
-------
TABLE 2. Candidate Metals, Salts, and Halldes for Initial Insitu Soil Treatment Evaluation
Anion Or Cation
Chromates
Copper
Nickel
Iron (Ferric)
Cadmium
Arsenic (As3+)
Uses
Electroplating Metal
Finishing Leather
Chemical Industry
Electroplating Metal
Finishing, Metal Refining
Circuit Boards
Electroplating, NiCd Batteries
Electronics. Chemical Industry
Chemical Industry
Manufacturing
NICd Batteries
Electronics
\
,|
Gas Purification
Specialty Glass
Discharge Type and Volume (lb./yr.)*
Pigments and Dyes 1 x ..„
Sodium Dlchromale Production 3 x 10°
Military Sodium Chromate Not Available
Potassium Chromate Production 1 x 10°
Textile Dyeing 2 x 10'
Chrome Tanning 2 x 10'
Chrome Plating Not Available
Metal Finishing 4.4 x 10'
Cooling Tower 2 x 10'
Electronic Circuitry Manufacture 5 x 10*
Cyanide 2 x 106
Brass Mill Wastes 5 x 107
Brass Plating Not Available
Rotogravure printing plate 1 X 10*'
Nickel Carbonyl Production Negligible
Consolidated Steel PI ant Hastes
Stainless Steel Pickling Liquor
Iron Manufacturing Waste Sludge
Cadmium Plating Wastes
Cadmium Ore Extraction Hastes
Cadmium/Selenium Pigment
Military Cadmium Wastes
Aresenic Haste from Transportation Not Available
Industry
Arsine Production Wastes 1 10*
Organic Arsenate Contaminated 5 10*
Containers
Arsenic from Refinery Flues 4 10(
Manufacture of Pesticide/Herbicide 2 10{*
Pesticide Arsenate Hastes 2 10**
Pesticide Arsenic Hastes 2 x 101Z
Purification of Phosphoric Acid Negligible
Previously Attempted Treatment
Hater Rinse
\
J.
5x 10°
5 x 107
6 x 10*
1 x 10*
2 x 10s
Not Available
Not Available
Hater Rinse then Na2S. Dilute
Hater Rinse
Hater,' Ca(OH)2 Dilution
Hater (Partial Removal)
Not Treatable
-------
TABLE 2.(cont.)
Anlon Or Cation
Arsenic (As3*)
Lead
Cobalt
Antimony
Selenium
Phosphate
Sulfate. Sulfite
Sulfides
Mercury
Uses
Gas Purification
Specialty Glass
Discharge Type and Volume (Ib./yr.)
NiCd Battery
Chemical Industry
Electronics
Dye Stuffs. Petrochemical
Metallurgical Industry
Gas Purification
Metallurgical Industry
Chemical Industry
Power Generation
Leather Production
Dyes Manufacturing
Gas Purification
Metal Refining
Arsenic Trichloride Recovery
From Coal
Agricultural Pesticides
Pharmaceutical Wastes
Arsenic Trioxide Smelting Industry
Calcium Arsenate Contaminated
Containers
Lead Arsenate Contaminated Con-
tainers
Battery Manufacturing Waste Sludge
Battery Manufacturing Wastes
Production of T.E.L., T.M.L.
Lead Arsenate Containers
Copper and Lead Bearing Petroleum
v_ and Refining Wastes
Contaminated Antimony Pentafluorlde
Contaiminated Antimony Trlfluorlde
Selenium Production Wastes
Cadmium/Selenium Pigment Wastes
Organophosphate Pesticide Wastes
Phosphoric Acid Purification Wastes
Production Works from Ammonium
Sulfate
Dimethyl Sulfate Production Wastes
Old or Contaminated Thallium and
Thallium Sulfate Rodentidde
Mercury Fungicide Contaminated
Containers
Stored Military Mercury Compounds
6 x 106
2 x
Negligible
2 x 10'
6 x 103
1 x 10*
7
12
1.1 x 10
3 x 10J
1 x 10J
8 x 108
Negligible
Negligible
2 x 104
Not Available
1 x 105
Negligible
1 x 103
Z x 105
Not Available
1 x 104
2 x 102
Previously Attempted Treatment
Not Treatable
Water Rinse, then Na2S. Dilute
Water Rinse (Partial Removal)
Not Treatable
Water Rinse (Partial Removal)
Water Rinse
Water Rinse
Water Rinse (If Soluble)
-------
TABLE 2.(cont.)
AnIon Or Cation
Mercury
Fluoride
Uses
Metal Refining
Glass, Chemical Industry
Discharge Type and Volume (Ib./yr.)*
Mercury Ore Extraction Wastes Not Available
Mercury Bearing Textile Wastes Not Available
Wastes from Manufacture of Mercuric Negligible
Cyanide
Pharmaceutical Mercurial Wastes Negligible
Mercuric Fungicide Production Wastes 2 x 10*2
Mercury Cell Battery Wastes 1.1 x 1012
Waste Bromine Pentafluorlde Negligible
Waste Chlorine Pentafluorlde Negligible
Waste Chlorine Tnfluorlde Negligible
Contaminated Fluorine Negligible
Contaminated Antimony Pentafluorlde Negligible
Contaminated Antimony Trlfluorlde Negligible
Production Wastes and Contaminated Negligible
_ Lots
Previously Attempted Treatment
Water Rinse (If Soluble)
Water Rinse. Ca(OH)2> Dilution
Cheremislnoff, N.P., P.N. Cheremlslnoff. Fred Ellerbush, A. J. Perna (1979) Industrial and Hazardous Wastes Impoundment .
Ann Arbor Science, Ann Arbor, N.J. pp 16-24
Huibregtse. K.R., K.H. Kastman, "Development of a System to Protect Groundwater Threatened by Hazardous Spills On Land",
Report to U.S. EPA, Contract No. 68^03-2508 \
v 4
-------
3.0 SIGNIFICANT HUMAN HEALTH HAZARD
The substances for which councermeasures are most needed are those
likely to cause significant adverse health effects in the exposed population.
Several measures of the human health risk are available, and the EPA Water
Quality Criteria are most appropriate. A large proportaion of the chemicals
reported at Superfund sites are carcinogenic or at least highly acutely
toxic. The EPA Water Quality Criteria for carcinogens are expressed as
levels presenting a known increase in risk, rather than as safe levels.
These are presented in Tables 5-8, along wich median acuce lethal dose
date (LD, 's) for rats, and whenever available, lowest carcinogenic dose
data (TDLo's) for all listed carcinogens. Clearly, although both are carcino-
genic, the carcinogenic potency of PCB's (TDLo: 1220 mg/kg) is much less
than that of dioxin (TDLo: 0.00114 mg/kg), and the TDLo values allow one
to assess relative carcinogenic hazard.
-------
TABLE 8. HAZARD PARAMETERS OF INORGANIC CONTAMINANTS
Heavy Toxic Metals
EPA
Water Quality
Criteria (ppm)
Rat Oral LD50 (mg/kg)'
Carcinogenic Dose*
Cadmium
Zinc
Lead
Nickel
Chromium
Copper
Aluminum
SiIver
Arsenic
Barium
Beryl 1ium
Manganese
Iron J
Stront ium
Titanium
Boron
Cobalt
Mercury
Selenium
Other Toxic Ions
0.01
0.05
0.01
170 (Crlll)
0.05 (CrVl)
88 (CdCl )
350 '" '
2.2x10
3.7x10 *
1.44x10 A*
0.01
105 (NiCl )
1,870 (CrCl^)
265 (CuCl)
140 (CuCl )
3,700 '
8(As 0 )
20 (As.O,)
118
86 (BeClJ)
319 (FeSO )
2,250 (SrClp
80 (CoCI9)
210 (HgCl,
37 (HgCl0)
TCLo: 0.700 mg/m (human, inhalation, 1 year
intermittent)
TDLo: 17 mg/kg (rat, inlratracheal, 3 weeks
intermittent)
\
J-
Cyanide
Throcyanate
Perchlorat e
Ammon i um/Ammon i a
0.2
10 (KCN)
854 (KCNS)
1,650 (NH Cl)
'•'•"corresponds to an incremental increase in cancer risk of 10
-6
-------
4.0 EFFECTIVE COUNTERMEASURES AVAILABLE
The Information Search Report submitted to OHMSB in September, 1982,
discussed a wide variety of chemical countermeasures with potential for
in situ soil treatment. The method*we consider to have the greatest poten-
tial for success in treating a wide variety of waste chemicals is the aqueous
surfactant wash method. Table 9 contains our best scientific prediction
of the potential effectiveness of several countermeasures. for in situ treat-
ment of soil contaminated with hydrophobics, slighly hydrophilics, or heavy
.-—»•
metals.
-------
Idble 9. SUHMAKY OF CANDIDATE TEST COMPOUNDS
Maximum
in Sol Is
(ppm)
IIYUKOPIIOU1CS
Chlordane 3000
Uleldrin 3O
PNA's {j)enzo(a)jiuhraceiie 3()
Pyreiie, benzo(a )|>yrene ,
Bt-nzo(b) pyremj
Anthracene, Fluoianlhene .003-30
N<«ulit ha 1 enc1
DDT 2O
PCU's 1
Trichlorophenol (CUOO)*
\
Slightly liydroph) 1 ics
Xylene, Toluene -OO3-3
Phenol, Dichlorophenol l;CW-3l>
Carbon lei rac hloride , . O03
Perehloroc-l liylene ,
1 r ichliiroel hylene ,
Chlurobenzene
Number ol Potential
Sites Where Toxiciiy Persistence- Effectiveness of Other
round Hazard in Soil (K) Count errneasures Adv.intdKc-s
1 carcinogenic 2OO aqueous surf art ant -good
1 moderate acute 2OO aqueous surl ac tant -good non-carcinogenic
model lor chlordanc
1-2 t arc inugenit 2.0OO-60.0OO aqueous sur 1 ac t ant -good
1-4 high acute dOO-8,OOO aqueous sur 1 act ant -good nun-carcinogenic
model* for PNA's
2 carcinogenic 1O.OOO aqueous sur I aclanl -good
7 carcinogenic 20,000 aqueous surf act ant -good
1 moderate acute 2,OOO aqueous base-good
5-12 mode-rale acute 3O aqueous surfactant-good cheap chemicals
|_4 mode-rale acute- 2O-iO aqueous base-very good
2-!2 nioderal e-high acute 2O aqueous surf act an I -good cheap chemicals
Other
Disadvantages
expensive to prole
pruje-cl personnel
expensive to prole
project personnel
i 1
it
expensive io protect
project personnel
expensive to prole
project personnel
•ct
volatile: hard to con
i onl aiuinani level
volatile: hard to con
contaminant level
Ca dm i um
Nickel
Ch romium
3O.OOO
1O.OOO
2.OOO
2()
H) In t,'1 Jl ul l'
t i i 1 low ,lc ul e
Cr .6 h I gh 4ic ul e
C.ll « Illllgfllll
(varies) aqueous acid-1 air
prec ipitani -lair
(varies) aqueous acid-fair
prec IL>I t ant -lai i
(varies) aqueous acid-lair
prec i pi i am-(air
(v.tries) aqueous ai id-fair
aqueous acid-fair 10 good
(v.nics) jquecius acid-fair
i vc- to iirolftt
-------
REFERENCES
(1) Lyman, W.D., W.F. Reehl, and D.H. Rosenblatt. 1982. Handbook of
Chemical Property Estimation Methods, pp. 4-1 to 4-33. McGraw-Hill
Book Company, New York.
(2) Hansch, C. and A.J. Leo. 1979. Substituent Constants for Correlation
Analysis in Chemistry and Biology. John Wiley and Sons, New
New York.
(3) Registry of Toxic Effects of Chemical Substances. 1978. National
Institute for Occupational Safety and Health, U.S. Department
of Health and Human Services.
-------
SECTION 5
MATERIALS AND METHODS
5.1 SOIL SELECTION AND CHARACTERIZATION
In choosing a soil to be used in the surfactant washing tests, the
applicability of the results to actual field situations was a primary con-
sideration. The selection process included identifying the native soils at
each of the Region II Superfund sites for which data was available, deter-
mining the most commonly occurring soil type series, and locating a soi.l of
the same soil taxonomic classification which could be excavated and used in
the testing experiment. The limited availablity of published soil surveys
and the fact that some of the sites were mapped only as "urban land," which
indicated that the original soil had been altered or removed, reduced the
number of Superfund sites for which information could be gathered to 10 sites.
Supplementary data for the D'Imperio, Price, and Lipari Landfill sites were
obtained from the Region II Superfund site investigation files located in the
New York City Regional office.
Each site's exact location was ascertained using topographic maps and
information supplied in the Field Investigation Team (FIT) report summaries.
Next the site was located on soils maps contained within Soil Survey Reports
compiled by the U.S. Department of Agriculture (USDA) Soil Conservation
Service (SCS). The soils indicated within a radius of two times the square
root of the total area of each* site were identified. If more than five
different soil series were present, the five major soils in terms of area
were chosen. Table 7 lists the soils series as well as the taxonomic classi-
fication to the subgroup level according to Soil Taxonomy (Soil Survey Staff,
1975) for the soils encountered at the Region II Superfund sites. Also
outlined within Table 7 are the textural classes and permeability ranges
for each soil series. The most commonly occurring classification was Typic
Hapludults, fine- to coarse-loamy. An explanation of the nomenclature is as
follows:
Typic Representative of the great group
Hapl Great group element meaning "simple or minimum horizons"
ud Suborder element meaning "of humid climate"
ults Of the order Ultisols: the soils have an argillic horizon,
i.e., a zone of clay accumulation, and have low base saturation.
The coarse-loamy textural class indicates a soil with a low content of clay
(less than 18 percent) and a high content (more than 15 percent) of fine,
25
-------
TABLE 7. SOILS OF TEN REGION II SUPERFUND SITES
Site
Soil Series
Taxonomlc Classification
Texture
Permeability*
Llparl Landfill
Aura
Sassafras
Typlc Hapludulte
Typlc Hapludults
f ine-loamy
f Ine-loany
moderately alow to moderate
moderate to moderately rapid
D1Imperlo
rv>
cr>
Price
Facet Enterprises
Love Canal
Mat awan
KleJ
Woodstown
Pocomoke
Sassafras
Downer
KleJ
Sassafras
Howard
Canandalgua
Madalla
Bridgeport Brothers Sassafras
Downer
Dragston
KleJ
Woodstown
Holra
Nlagj-a Co. Refuse
Coveytown
Scarboro
Wai pole
Empeyvllle
Fahey
Canandalgua
Raynhacn
Aqulc Hapludults
Aqulc Quartzlpsanments
Aqulc Hapludults
Typlc Umbraquulta
Typlc Hapludults
Typic Hapludulta
Aqulc Quartzlpsaranents
Typlc Hapludulta
Clossoborlc Hapludalfa
Molllc Haplaquepta
Mollic Ochraqualfa
Typlc Hapludulta
Typlc Hapludulta
Aquic Hapludulta
Aquic Quartcipaammenta
Aquic Hapludulta
Aerie Haplaquenta
Hiatic Humaquepta
Aerlc Haplaquepta
Aquic Fraglorthode
Aquentic Haplorthoda
Mollic Haplaquepta
Aerlc Haplaquepta
fine-loamy
sandy
fine-loamy
coarse-loamy
fine-loamy
coarse-loamy
aandy
fine-loamy
loamy-skeletal
flne-sllty
fine (30-60Z clay)
fine-loamy
coarae-loamy
coarse-loamy
aandy
fine-loamy
aandy/loam
aandy
aandy
loam
aandy-akeletal
flne-sllty
coarse-sllty
moderately slow to moderate
rapid to very rapid
moderate to very rapid
moderate to moderately rapid
moderate to moderately rapid
moderate to moderately rapid
moderate
moderate to moderately rapid
moderate
moderate
moderate
moderate to moderately rapid
moderate to moderately rapid
moderate
moderate
moderate
moderately rapid to rapid
rapid to very rapid
moderately rapid
alow
rapid
moderate
moderate to moderately rapid
(continued)
-------
TABLE 7. (continued)
Site
Pollution Abatement
Services
Soil Series
Sc r 1 ba
Ira
Sodus
Taxonomlc Classification
Aerlc Fraglaquepts
Typlc Fraglochrepts
Typlc Fragiochrepta
Texture
coarse-loamy
coarse-loamy
coarse-loamy
Permeability*
slow
slow
slow
Helen Kramer
Landfill
Freehold
Typlc Hapludults
fine-loamy
moderate
rs>
* Terms used to describe permeability are as follows:
Very slow <4.2 x 10~5 cm/sec
Slow 4.2 x 10-5 to 1.4 x 1(H cm/sec
Moderately Slow 1.4 x 10~4 to 4.2 x 1(H cm/sec
Moderate 4.2 x 10-4 to 1.4 x 10~3 cm/sec
Moderately Rapid 1.4 x 10~3 to 4.2 x 10~3 cm/sec
Rapid 4.2 x 10~3 to 1.4 x 10'2 cm/sec
Very rapid >1.4 x 10-2 cm/sec
\
-------
medium, and coarse sands plus coarse fragments up to three inches. Fine-loamy
is the same as above except that clay content is 18 to 35 percent. Table 8
outlines the frequency of occurrence of the various soil subgroups and
permeability ranges for each.
TABLE 8. MOST COMMON SOIL SUBGROUPS AT REGION II SUPERFUND SITES
Soil Subgroup
Range of Permeabi1ity
Frequency of
Occurrence *
Typic Hapludults
Aquic Hapludults
Aquic Quartzipsamments
Mollic Haplaquepts
Aerie Haplaquepts
Typic Fragiochrepts
Typic Umbraquults
Aerie Haplaquents
Aquentic Haplorthods
Mollic Ochraqualfs
Aerie Fragiaquepts
Typic Rhodudults
Histic Humaquepts
Glossoboric Hapludalfs
moderately slow to moderately rapid
moderately slow to very rapid
moderate
moderate
moderate to moderately rapid
slow
moderate to moderately rapid
moderately rapid to rapid
rapid
moderate
slow
moderate
rapid to very rapid
moderate
10
4
3
2
2
2
1
1
1
1
1
1
1
1
*of 10 sites studied
In addition to taxonomic classification, other factors were considered in
choosing the soil for surfactant tests. A permeability rating of 10'2 to
10'4 cm/sec was considered an acceptable range; less permeable soils would
take too long to test. Also, the soil could not contain significant amounts
of the clay of marine origin called glauconite. The glauconitic soils found
in the Coastal Plain of Region II are known to lose their permeability upon
wetting.
28
-------
The soil selected for use in the study was a Freehold series typic
hapludult from Clarksburg, New Jersey. Initial characterization of the soil,
consisting of grain size analyses, determination of natural moisture content,
compaction tests, and permeability vs density tests, was conducted by Raamot
Associates, Parlin, NJ. Mineralogy by X-ray diffraction was undertaken by
Technology and Materials Company, Santa Barbara, CA, on a Phillips Electronics
X-ray diffractometer; the X-ray diffraction charts were interpreted by compari-
son with standard diffraction file data. The total organic carbon content
(TOC) was measured by Laucks Testing Laboratories, Inc., Seattle, WA, according
to EPA Method 415.1. Laucks Testing Laboratories, Inc., also determined the
cation exchange capacity of the soil using the method of Jackson (1960).
5.2 SURFACTANT SCREENING TESTS
The surfactant combination used by Texas Research Institute for flushing
gasoline from sand (TRI, 1979), Richonate«-YLA and Hyonic* NP-90 (formerly
called Hyonic* PE-90), was screened along with several other surfactants and
surfactant combinations for three critical characteristics:
o Water solubility (deionized water)
o Clay particle dispersion
o Oil dispersion.
Any candidate surfactant must dissolve in water to form an effective solution
for in situ cleanup. Deionized water was used to test the solubility because
it was available in quantity and had constant physical and chemical charac-
teristics. The laboratory tap water varied greatly in salts content from'week
to week.
Preliminary soil column tests with the Richonate*-YLA and Hyonic* NP-90
surfactant combination showed constantly decreasing flow rates; this was
attributed to clay-sized particle mobilization and redeposition by one or both
surfactants. To minimize this effect, and to assist in selection of another
surfactant combination other than the one used by TRI, screening tests for
clay dispersion were run. A 250 mg sample of the Freehold soil was shaken on
a wrist action shaker with 10 ml of the surfactant solution for 5 minutes in a
15 ml screwcap vial, then allowed to settle overnight. The cloudiness of the
solution was noted as an indication that the clay was still suspended.
The ability of the chosen surfactant(s) to disperse a hydrophobic organic
like an oil (Prudhoe Bay crude was used for the test) was considered an
accurate model for the ability to clean organics from soil. A 50 ml aliquot
of the surfactant solution was swirled in a 100 ml beaker with two drops of
oil, and the extent of oil dispersion was determined by the cloudiness and
darkness of the solution.
5.3 SHAKER TABLE TESTS
To represent the approximate levels found at waste sites (Section 2,
Information Search), soils were spiked with 100 ppm PCS, 1000 ppm Murban
29
-------
•^^^^^^^^j |^^u^^^^uv^^M
ENVIROSCIENCE
January 26, 1983
Mr. Anthony N. Tafuri
Oil & Hazardous Materials Spill Branch
U.S. Environmental Protection Agency
Edison, Mew Jersey 08837
Dear Tony:
Subject: Chemical Countermeasures Control Program Meeting of January 25
I consider yesterday's meeting to have been constructive. I believe the
choice of chemicals for initial testing, PCS, high boiling oil fractions,
and di- tri- and pentachlorophenols are a suitable starting point for
laboratory testing in this program.
The discussions during the day also alleviated my concerns expressed to •
you in my letter of January 24. Specifically, the choice of carrying out
single component laboratory studies is a good pne. Second, the comments
that a large number of surfactants have been tested by TRI alleviated my
concern about a reasonable selection of surfactants for this work. I
would appreciate greatly if you could provide me with a copy of this TRI
report. Third, I believe th^e concern expressed about the variability of
desorption behavior as a function of soil parameters is warranted and will
be pursued at the proper stage of testing._.V.I believe we had general
agreement that adsorption and desorption of the organic chemicals considered
in this work would be affected primarily by the organic content of the soil.
I look forward to my continued involvement in this very interesting project
and believe that I can continue to provide valuable insights because of my
several activities in areas related to this work. I look forward to getting
Initial results from this laboratory study. Also, can you provide me with
some of the documents regarding the proposed pilot plant study at the OHNSETT
facility?
Please don't hesitate to contact me if I can be of any assistance to you.
Best regards,
H.[Exner
bro
.'.12 O.rec'Ofi Drive • Knoxviitf • ennessea 37923 • (615; 690-3211
1 o!' ' ''o'porauon
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ENV1ROSCIENCC
January 24, 1983
Mr. Anthony N. Tafuri
Oil & Hazardous Materials Spill Branch
U.S. Environmental Protection Agency
Edison, New Jersey 08837
Dear Tony:
Subject: Initial Comments on Chemical Countermeasures Program
You requested my initial comments on the program to carry out laboratory
and pilot plant studies on removing chemicals from soils by in situ
treatment. X have some specific comments to make about your request on
what type of chemicals to study in the laboratory and in the pilot plant
work. In addition I have some more general comments regarding the whole
program which I will try to elaborate later. .
In my opinion, chemicals for this program should be chosen on the basis
of their frequency of occurrence at abandoned sites and on the basis of
the presence in concentrations high enough to be of concern. Secondly,
these compounds must pose a health risk so that concern is sufficiently
warranted. Third, the chemicals chosen should represent different chemical
classes so that extrapolations and judgments about other chemicals may
be made. Finally, the chemicals chosen should cover a range of soil
adsorption constants that are representative of the types of problems
that occur at landfills. For that reason I suggest the following
chemicals with their^approximate soil adsorption constants in paren-
theses: PCS (2 x.lOH , dioxin (2 x 10^), trichlorophenol (2 x 10 ),
napthalene 6 x 10 ), phthalate (2 x 10 ), xylene (3 x 10), and two or
three appropriate metals. For pilot plant studies I would suggest PCS,
xylene, trichlorophenol, napthalene, and two metals. I believe this list
and the list presented by JRB can be the basis for useful discussions at
our meeting tomorrow. We should also discuss appropriate concentrations.
I believe that selection of a multicoraponent>mixture and one soil for
laboratory -testing and for pilot plant evaluation of engineering problems
can be useful if there are economic and time constraints on the program.
However, I am concerned about whether we have sufficient fundamental
data or. adsorbability and rates of desorption of pollutants of concern
from soil. Specifically, I want to point out that experimentation on
pilot scale can be very expensive, and that experimentation in field
application can be very expensive and be politically dangerous for the
treatment technology that is to be demonstrated in the field. I am
concerned about the variability that can occur with different multicomponent
mixtures in the field application because of chromatographic and chemical
interaction effects that occur in adsorption processes. I would suggest
312 Directors Drive • Knuxville. Toniu-swe VM^ • (6l5) 690
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2
Mr. Anthony N. Tafuri
January 24, 1983
that, as the program develops, research for opportunities to fill in
these fundamental data gaps be carried out, perhaps by funding research
studies at an appropriate university. Without economic and tine constraints,
I would normally begin work in this kind of processing application by
carrying out single compound isotherms on four or five specific compounds,
using three soils of widely different composition, particularly a wide
range of organic concentration, and several different types of water
surfactant or water-solvent mixtures. I would then follow up with some
multicomponent isotherm data similar to the shake tests that we are
talking about, and then determine the rates of desorption by column
tests as are proposed.
I have a comment about the use of surrogate chemicals. Surrogate chemicals
can be very useful and economical to use if there exists good data that
correlates behavior of surrogates with compounds of concern. Surrogates
dc not address the problem that we are trying to solve. Rather surrogates
make it easier for the experimenter to carry out the proposed work. The
idea is to solve the problem and not to accommodate technical personnel.
*
I have some concerns about whether we have thought through the whole
concept of in situ cleanup of soils by chemical treatment. I am concerned
about the quantity of water arid surfactant that is required, the concen-
tration of pollutant in that water, and the removal of that pollutant
from the aqueous system. I suspect however that you have considered
this area and I just have not seen the appropriate backup documents.
)
Finally, let me reiterate comments that I have made to you before. We
are facing the problem of developing a new jnetpiodology for solving an
important pollutant problem. It is important to develop the process
rapidly and within considerable economic constraints. However, we must
remember chat problems occurring in startup situations, or in this case
in field demonstration of the technology, can be solved either by extensive
trial and error approaches or by rational judgment based on a reasonable
data base. Although we need to balance field demonstration and laboratory
studies to solve the problem, I have not seen sufficient knowledge about
che fundamentals of this proposed- chemical countermeasures process to
maXe me comfortable.
Plaase remember that these are my initial comments. I will try to think
through the problem some more in the next few days and hope to be able
to contribute to your meeting tomorrow.
regards,
er
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List of Attendees
CHEMICAL COUNTERMEASURES PROGRAM MEETING
Edison, NJ
January 25, 1983
Name
Jeffrey Bloom
Jurgen Exner
Kenneth E. Honeycutt
Bill Ellis
James R. Payne
Hank N. Lichte
Jim Nash
John E. Brugger
Uwe Frank
Frank J. Freestone
Rich Griffiths
Anthony N. Tafuri
Ric Traver
Affiliation
EarthTech
IT Corporation
IT Corporation
JRB Associates, Inc.
SAI/JRB Associates, Inc.
Mason & Hanger
Mason & Hanger
EPA, OHMSB, Eciison
EPA, OHMSB, Edison
EPA, OHMSB, Edison
EPA, OHMSB, Edison
EPA, OHMSB, Edison
EPA, OHMSB, Edison
Phone
(301) 796-5200
(615) 690-3211
(201) 548-9660
(703) 734-2529
(619) 456-6635
(201) 291-0680
(201) 291-0680
(201) 321-6634
(201) 321-6626
(201) 321-6632
(201) 321-6629
(201) 321-6604
(201) 321-6677
4980A
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