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.

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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.

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                                                          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

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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

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   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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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

-------
                                                                        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

-------
                                   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

-------
                                                                   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.

-------
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.

-------
                                                                    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.

-------
                                                                  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.

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   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

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                                                                             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

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                                                                           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

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                                                                     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

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                                                                     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.

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                                                                     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.

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                                                                   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".

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                                   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

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                                                                              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.

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                              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)  
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                                                                   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.

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                                                                   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.

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                                                                   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

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                                                                   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

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                                                                   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.

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                    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

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                                 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

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                                 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

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                                 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-

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 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

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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

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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.
                                    A2-3

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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).
                                    A 2-4

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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
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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).
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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
Handbook  on  Wood Treatment Plant .Sites.    October  1985.    Koppers  and
     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
Ahlborg,  U.  G.,  K.  Larsson,  and   T.   Thunberg.   1978.    Metabolism   of
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Akin, F. J.  et al.  1976.  Identification of polynuclear aromatic hydrocarbons in
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Arrhenius, E., L. Renberg, and L. Johansson.  1977.  Subcellular Distribution, A
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Bauchinger,  M., J. Dresp, E. Schmid, and R. Hauf.  1982.  Chromosome Changes in
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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
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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
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Brown, E. R. et al.  1975.   Tumors in fish caught in polluted waters:  possible
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Gehrs, C. W. 1978.  Environmental Implications of Coal-Conversion Technologies;
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      Systems. Thorp, J. H. and J. W. Gibbons, Editors.  Papers  from a symposium
      held at Augusta, GA   Nov. 2-4, 1977.  Tech. Info.  Center U. S. DOE.  854
      pages.
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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.
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Habs, M. and D. Schmahl 1980.  Local carcinogenicity of environmentally relevant
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     skin.  Arch. Geschwulstforsch. 50(3):  266-274.

Haley, T. J.  1977.  Human Poisoning with Pentachlorophenol and Its Treatment.
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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.
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IARC.    1983.   Polynuclear aromatic  compounds, chemical, environmental  and
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     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.
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Kalman, D. A., and W. S. Horstman. W. S.  1983.  Persistence of Tetrachlorophenol
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Kennaway,  E. L.  1930.  Further  experiments on cancer producing substances.
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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
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Knoblock, K. et al. 1969.  The  investigations of acute and subacute  toxic action of
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Lacassagne, A. et  al.    1963.    Carcinogenic  activity of  polyclic  aromatic
     hydrocarbons with a fluoranthene group.  Unio int contra cancrum  Acta.   19:
     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
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 Lillard,  D. A.,  and J. J. Powers.   1975.  Aqueous odor thresholds of organic
      pollutants in industrial effluents.  US EPA  Rep No. 660/4-75-002.  Natl Envir
      Res Ctr, US Envir Prot Agency, Corvallis, Oregon.


 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
      carcinogenic properties  of 1,12-benzoperylene.  Archives of  Hygiene.   152:
      23-36.

 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
      a Recommended Standard. Occupational Exposure to Phenol.  DHEW (NIOSH)
      Publications No. 76-196.

 NIOSH (National Institute for Occupational Safety and Health). 1978. Criteria for
      a Recommended Standard. Occupational Exposure to Cresol.  DHEW (NIOSH)
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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
      hydrocarbons in shellfish on short, wall-coated glass capillary  columns.  Anal
      Lett 1976.  9:  451.

 Radding, S. B. et al.   1976.   The  Environmental Fate of Selected Polynuclear
     Aromatic Hydrocarbons.  Report of the Office of Toxic Substances. Stanford
      Research Institute.

Salamone, M.  F.  1981.  Toxicity  of 41  carcinogens and noncarcinogenic analogs.
     Progress in Mutation Research. 1:  682-685.
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                            MINOR REFERENCES
Santodonato, J., P. Howard, and D. Basu, "1981.  Health and ecological assessment
     of polynuclear aromatic hydrocarbons. J Environ Pathol Toxicol.  5:  1-364.

Sax, N. I.   1975.   Dangerous properties of industrial materials.   Van Nostrand
     Reinhold Co., New York; 4th ed.

Schwetz, B. A., P. A. Keeler, and 3. P. Gehring.  1974. The Effect of Purified and
     Commercial   Grade  Pentachlorophenol   on  Rat  Embryonal  and  Fetal
     Development.  Toxicol. Appl. Pharmacol.   28:  151-161. (MC 8/4/84).

Snell,  K.  C.,  and  H.  L. Stewart,  1962.   Pulmonary  adenomatosis  induced  in
     dibenz(a,h)anthracene/2     mice     by     oral     administration      of
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Tsapakos, M. J., and E. K. Wetterhahn.  1983.  The Interaction of Chromium with
     Nucleic Acids.  Chem-Biol Inter. 46: 265-277. (MC 5/31/84 CC 1/2/84).

U.S.D.A.  1981.  The Biological and Economic  Assessment of Pentachlorophenol,
     Inorganic Arsenicals, and Creosote.  Vol. I:  Wood Preservatives.  Technical
     Bulletin No. 1658-1 U.S. Dept. of Agriculture.

US  EPA.    1979.   Health and  environmental  effects  profile  for  indeno(l,2,3-
     c,d)pyrene.  Washington, D. C.

US  EPA.   1980.   Ambient water  quality criteria for polynuclear  aromatic
     hydrocarbons.  Report of the Criteria and Standards Division, Office of Water
     Regulations and Standards.  Washington, DC.

US EPA. 1980. Ambient water quality criteria for acenaphthene.  Office of Water
     Regulations and Standards.  Washington, DC.


US EPA. 1980g. Ambient Water Quality Criteria for Phenol. EPA-440/5-80-066.

US  EPA.   1980q.  Ambient Water Quality Criteria for Pentachlorophenol.  EPA
     440/5-80-.

US  EPA.   1984a.   Wood Preservative Pesticides:   Creosote, Pentachlorophenol,
     Inorganic Arsenicals - Position  Document  4.  Office of Pesticides and Toxic
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Uzhdavini,  E.  R., I. K.  Astafeva, and A. A. Mamaeva.  1974.  Acute toxicity of
     lower  phenols.  Gig. Tr. Prof. Zabol.  2:   58-59.   (In Russ.)  Taken  from:
     Abstract, Medlars  II,  National  Library of  Medicine's National  Interactive
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Van Duuren, B. L., A. Sivak, L. Langseth,  B. M. Goldschmidt, and A. Segal.  1968.
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     Monogr.  28: 173-80.
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                            MINOR REFERENCES


Van  Duuren,  B. L., et al.  1970.  Initiating activity  of aromatic hydrocarbons in
      two-stage carcinogenesis.   Journal of  the  National Cancer Institute.   44:
      1167-1173.

Van  Duuren,  B.  L.,  and B. M. Goldschmidt.  1976.   Cocarcinogenic and tumor-
      promoting agents in tobacco carcinogenesis. Journal of the National Cancer
      Institute. 56(6):  1237-1242.

Veldre, I. A., and H. J. Janes.  1979. Toxicological studies of shale  oils, some of
      their components, and commercial products.  Environ.  Health Perspect.  30:
      141-146.                                                             ~

Wilson, D. C., and C. Stevens. 1981. Problems Arising from the Redevelopment of
      Gas Works and Similar Sites. AERE Harwell Report R-10366.  Department of
      Environment, London, England.

Wolfe, R. M., and W. R. Bryan.  1939. Effects induced in pregnant rats by injection
      of chemically  pure carcinogenic agents. American Journal of  Cancer.  36:
      359-368.

Wynder,   E.   L.,   and   D.  Hoffman   1959(a).     The   carcinogenicity   of
      benzofluoranthenes.  Cancer. 12:  1194-1199.

Wynder, E. L., and  D. Hoffman.  1959(b). The study of tobacco carcinogenesis VII.
     The fole of higher polycyclic hydrocarbons.  Cancer. 12: 1079-1086.

Wynder, E. L., and D. Hoffman.   1961.  A study  of tobacco carcinogenesis — The
     role of the acidic fractions as promoters. Cancer.  14: 1306-15.
                                    R-6

-------
        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

-------
                           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


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                                                                                                                                           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
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                                                                                                                                   O
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-------
                                       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.

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            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

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                          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

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                          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

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                          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

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                            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)
 DX  (mg Ci /kg) .

 ^B (mg/kg)
                     (MG/KG)
                        5403,0


                         115,0

                         728,4

                          "90f3
                           v_
                            3,2
201,0
96,3
7,0
97,5
n. n.
0,5
93,9
' 86,6
100,0
84,1

-------
 Merge!
                      TNPiJl
 chadstoff
   Ausgangs-
   betastung
  Rest-       Wascherfolg  (%)
belastung
'OTAL ORGAN ^.S^
  PETROLEUM/l'EXTRACT.
rganische Gesamt-
elastung (Petrol-
ther-Extrakt)
i (mg/kg)

'OTAL PHENOL (MG/KG)
iesamtphenol
-i (mg/kg)

'AH  (MG/KG")
AK  (mg/kg)
     (mg  CL~/kg)
(MG/KG)
   4566.0
     585,0
   1779,4
 83,5



  3,2


 33,2
98,2



99,4


98,1
      50,9   Nachprobe  ist bestellt
>CB (mg/kg)
   0.683
 0,040
> 90

-------
  CLAS




Lehmboden

5chadstoff
To7AL_ 0r^£l\ >£_£,
Pfl.i ro l« D«A O.u \fu e\-> C. ^\<\
jrganische Gesamt-
ielastung (Pet-
Extrakt)
n (mg/kg)
3esamtphenol
n (mg/kg)
3AK (mg/kg; ^
£OX (mg Cf /kg)
3CB (mg/kg)
^ u w r
Ausgangs-
belastung

//da)


4440,5
/
165,0
947,8
33,5
11,3
^ptn;^ lA/AaKiVa
Rest- Wascherfolg (%)
belastung




* 159,0 96,4
22,5 . 86,4
91,4 90,4
n.n. ~100,0
1,3 88,3

-------
                        0 F
        Reinigungserfo/g gemessen  on  der Sum me
        petrolether  —  extrahierbarer  Stoffe
                                             \
  Spitzenwerte
       16tOOO
  A i/g.
Durchschnitts—
        werte
        6}000
                                         o t i
                            Restbelastung
                            50 - 200
              [mg/kg TR]
             95 ^r
Re/nigungserfolg in Z
der Eingangswerte

-------
-o
i-
                                   d  fl
Bei spiel:  Belastung mit Polyaromatischen  KW (PAK's),
          Belastung mit Cyan id
         PAK's
     752
                              99,7
                         UQ £>
                 Relnigun gserfolg
                                    Cn
                                                         0,06
                                                       98,9
                                            Rein fgun gserfolg

-------
                                         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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Figun 3.    PCB soil column cleanup vs. surfactant concentration.
                                                                '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.

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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

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                                 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

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                                  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

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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

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                                  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

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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

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                                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

-------

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

-------
 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

-------
                             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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