EPA/540/2-89/020
ENVIRONMENTAL
PROTECTION
AGENCY
DALLAS, TEXAS
LIBRARY
SUPERFUND TREATABILITY
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:
Super-fund Ttestability Clearinghouse - EUZU
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SUPERFUND TREATABILIT7 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,
HWERL, 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.
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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.
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Umiea States
Environmental Protection
Agency
Hazardous Waste Engineering
Researcn Laooratory
Cincinnati OH 45268
Researcn and Development
EPA/600/S2 35/129 Dec. 1985
oEPA 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 Suparfund 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/'n 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 Adse«!> 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 leachata were also performed to
investigate separating the surfactant
from the contaminated leachata to allow
reuse of the surfactant. A method for
separating the surfactant plus the con-
taminant from the leachata was devel-
oped; however, all 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 hydrophobia 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 assential 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 Pfoject Summary was developed
by EPA's Hazardous Waste Engineering
Research Laboratory. Cincinnati. OH.
to announce key findings of the research
protect that is fully documented in a
separate report of the same title (set
Project Report ordering information at
back).
Introduction
The Comprehensive Environmental
Response, Compensation, and Lfability
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-
-------
ment and clean up inactive hazardous
ste disposal sites. One key counter-
easure 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.
«Jer the Chemical Countermeasures
gram, the efficacy of in situ treatment
irge 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
body of existing theory and data;
oratory studies on candidate chemicals
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
fueous surfactants for in situ washing
contaminated soils, was the first
:hmque 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 a 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
if 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 hydrophobia 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 m 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 proaucts. or rendered immobile,
using cnemicals 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 in 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 hydrophobia organics from
soils. Texas Research Institute (TRI) used
a combination of equal parts of Witco
Chemical's Richonate-®* YLA, ananionic
surfactant, and Diamond Shamrock's
HyonicS NP-9Q. a nomonic surfactant, in
several laboratory column and two-
dimensional modeling studies for displac-
ing gasoline from sand packs.
•Mention of trade names or commercial product*
does not constitute endorsement or recommendation
(or use
To further verify which organic waste
chemicals should be targeted for counter-
measures development, Field Investiga-
tion Team (FIT) summaries were examined
for the maximum concentrations of
organic contaminants in the soil and
groundwater surrounding 50 Superfund
sites. Results of the survey indicated that
many hydrophobics were detected in the
soils, mainly because hydrophtlics tend to
be washed from soil by infiltrating rain-
water. Hydrophobics had the highest
levels of all the organic contaminants,
with 11 compounds averaging in the 1 to
100 ppm range, and with chlordane
exceeding 1.000 ppm at one site. The soil
concentrations of slightly hydrophilic
compounds were in the range of 0.001 to
10 ppm.
Based on these findings, the following
two hydrophobia and one slightly hydro-
philic pollutant groups were chosen as
model contaminants for testing and de-
velopment of an aqueous surfactant
countermeasure:
• High boiling point Murban crude oil
fraction containing aliphatic and aro-
matic hydrocarbons (1,000 ppm)
• PCS mixture in chlorobenzenes (Aro-
clor® 1260 transformer oil) (100 ppm)
• Oi, tri-, and pentachlorophenols mix-
ture (30 ppm)
Laboratory Studies
The laboratory research was conducted
to determine whether significant improve-
ments to the cleanup of contaminated
soils with just water, the only in situ soil
cleanup method demonstrated to date.
could be obtained using aqueous surfac-
tants. Further laboratory development of
the surfactant countermeasure included
optimizing the concentration of surfactant
used for cleanup, and development of
contaminated leachate treatment meth-
ods.
The aqueous surfactant countermeas-
ure was tested using two basic methods:
shaker table agitation, to quickly deter-
mine the soil/aqueous surfactant parti-
tioning of the model contaminants under
differing conditions; and gravity flow soil
column tests to verify the cleanup be-
havior of the aqueous surfactant under
conditions resembling field use. Besides
the optimum surfactant concentration,
the effects of leachate treatment and
recycling were also studied.
So/7 Characterization
In choosing a soil for the surfactant
washing tests, the applicability of the
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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"*to 10~* 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 (TOC) 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
lb/ft\ 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-S YLA and Hvonic* NP-90
(formerly called HyomcS 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 m the laboratory studies were AdseeS
799 (Witco Chemical) and HyonicS NP-90
(Diamond Shamrock).
Soil 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/cmj (105 to 110 lb/fts), 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.
*
Soil 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-. tri-,
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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Surfactant Concentration i°'o)
2. Murban Shaker table recoveries vs. surfactant concentration
4
0.75 percent surfactant man with
1.0 percent surfactant, and somewhat
less for the 0.50 percent surfactant
concentration. After three pore volumes.
the PCS concentrations at the bottom of
the column were of 244 j/g/g with the
0.50 percent surfactant, compared with
405 Aig/g 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 m removing PCBs andthe
surfactants from an aqueous solution.
None of the sorbents was very efficient in
removing PCBs from a surfactant solution.
The most efficient sorbent for PCS 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 PCS removal (0.195 g/g).
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Hydrolysis treatment of the surfactant
d contaminant-containing leachate
as also tested. Adsees> 799. a fatty acid
ester, formed a separate organic phase
upon hydrolysis that contained both the
surf actants 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 PCS 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.
iwever. the use of hydrolysis was
cessary 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-
jcted. The results showed that leachate
lyclmg—without some sort of treat-
ent—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
to the treated leachate prior to
cling, 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® 799 (Witco Chemical Corp.)
and Hyonic® NP-90 (Diamond Shamrock)
was chosen because of adequate solubil-
ity m water, minimal mobilization of clay-
sized soil fines (to maintain soil perme-
£ihty), good oil dispersion, and adequate
degradability.
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Figure 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 15 percent total
surfactant. Individual surfactant concen-
trations of 0.25 percent or less were
unacceptable for effective soil washing,
and individual surfactant '•oncentrations
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 m 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
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definitely imponant: however, for this
•chnology to be cost effective, reuse of
e surfactant is equally important.
ccordmgly, 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 mutagemcity
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
game carbon content of the soil. The
TOC (0.1.2 percent) represented little
rganic 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 hydrophobic organics from
a 1 percent TOC soil using the AdseeS
799 - Hyomc£> NP-90 surfactant pair
,/ould require more surfactant solution.
so. the surfactants would become
ecessary 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
results to a broader variety of
matrices.
The hydraulic conductivity of the Free-
hold soil oacked in the soil columns,
which was measured at 1.05 x 10~3
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 hydrophobic 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 recontami-
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 same chemical
and physical properties of the surfactant
mixture that help to extract the pollutants
from the soiI also inhibit separation of the
contaminants from the surfactants. Due
to the high (percentage) level of surfactant
contained in 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"* 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-
phyhc organic contaminants
• Concentrated contamination source
removed or controlled
• Low to moderate natural organic mat-
ter content m 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 m
the laboratory studies but are more
amenable to separation for reuse. Also.
prior to any larger scale/site of opportun-
ity studies, the toxicity of the surfactants
should be ascertained.
-------
TREATMENT OF CONTAMINATED SOILS WITH AQUEOUS SURFACTANTS
(INTERIM REPORT)
by
William 0. Ellis
James R. Payne
G. Daniel McNabb
Science Applications International Corporation
8400 Westpark Drive
McLean, VA 22102
Contract No. 68-03-3113
Project Officer
Anthony N. Tafuri
Hazardous Waste Engineering Research Laboratory
Releases Control Branch
Edison, NJ 08837
HAZARDOUS WASTE ENGINEERING RESEARCH LABORATORY
OFFICE OF RESEARCH AND DEVELOPMENT
U.S. ENVIRONMENTAL PROTECTION AGENCY
CINCINNATI, OHIO 45268
-------
ABSTRACT
This report presents the results, conclusions, and recommendations of a
project performed to develop a technical base for decisions on the use of
chemical countermeasures 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-
tedTo 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 contaminantsTn soil, and should be further
developed on a larger scale at a small contaminated site under carefully
controlled conditions. However, reuse of the surfactant is essential for
cost-effective application of this technology in the field. Accordingly, any
future work should investigate the use of other surfactants/surfactant combi-
nations that may be more amenable to separation.
This report was submitted in partial fulfillment of Contract No. 68-03-
3113 by SAIC/JRB Associates under the sponsorship of the U.S. Environmental
Protection Agency. This report covers the period from May 1982 to August
1985, and work was completed on August 23, 1985.
iv
-------
CONTENTS
Page
FOREWORD 111
ABSTRACT iv
FIGURES vii
TABLES viii
ABBREVIATIONS AND SYMBOLS ix
ACKNOWLEDGMENTS x
1. INTRODUCTION 1
2. INFORMATION SEARCH 3
2.1 Potential In SItu Counter-measures for Soils . 9
2.1.1 HydTopKoFic 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 Countermeasures 15
2.2.1 Pilot-Scale Testing 15 '
2.2.2 Site of Opportunity Testing 17
3. CONCLUSIONS 19
3.1 Effectiveness of the Surfactants 19
3.2 Effects of the Test Soil 20
3.3 Potential Target Cbntaminants 21
3.4 Effective Treatment Methods 21
4. RECOMMENDATIONS 23
4.1 Selecting Surfactants for In Situ Soil Cleanup 23
4.2 Testing Other Soils 23
4.3 Developing Leachate Treatment Methods 24
4.4 Further Countermeasure Development Before
Field Use 24
5. MATERIALS AND METHODS 25
5.1 Soil Selection and Characterization 25
5.2 Surfactant Screening Tests 29
5.3 Shaker Table Tests 29
5.4 Soil Column Tests 30
5.5 Analytical Procedures 32
5.5.1 Extraction of Organics from Aqueous Media 32
5.5.2 Extraction of Organics from Soil 34
5.5.3 Instrumental Analysis 34
5.5.4 Internal Standards 35
5.6 Leachate Treatment 35
-------
6. RESULTS AND DISCUSSION *-.-»• 36
6.1 Soil Characteristics 36
6,2 Surfactant Selection 41
6.3 Preliminary Soil Column Experiments 42
6.4 Optimization of Surfactant Concentration 47
6.4.1 Shaker Table Tests. 47
6.4.2 Column Tests 50
6.5 Evaluation of Leachate Treatment Techniques 50
6.5.1 Laboratory Tests of the Most Feasible
Treatment Alternatives 52
6.5.1.1 Foam Fractionation 53
6.5.1.2 Sorbent Adsorption 56
6.5.1.3 Surfactant Hydrolysis and Phase
Separation 56
6.5.1.4 Ultrafiltration 59
6.5.2 Less Feasible Treatment Alternatives 62
6.5.2.1 Flocculation/Coagulation/Sedimentation. . 62
6.5.2.2 Centrifugation 63
6.5.2.3 Solvent Extraction 63
6.6 Evaluation of Leachate Recycling 63
6.6.1 Column Tests With Untreated Leachate 63
6.6.2 Column Tests With Treated Leachate 64
REFERENCES 72
APPENDICES
A. Shaker Table Extraction Procedure 77
B. Gas Chromatography Run Conditions and Run Programs 78
C. High Performance Liquid Chromatography Run Conditions
and Run Programs 80
D. Calculations and Quality Control for Instrumental
Analysis 82
E. Metric Conversion Table 84
vi
-------
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 countermeasure 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 Counter-measures 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 envi ronment.
i
The Chemical Countermeasure Program has been designed to evaluate the
efficacy of ni 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) organics and
slightly hydrophilic (slightly water soluble) organics, was the first tech-
nique to be developed under the Chemical Countermeasures Program. Another
countermeasure for soils, the use of acids and chelating agents for washing
heavy metals from soils, is also being developed under the Program.
The Aqueous Surfactant Countermeasures Project included an Information
search and laboratory development of the Countermeasures. The results and
conclusions from the information search formed the basis for the laboratory
1
-------
development work. Similarly, the results andvconclusions 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 counter-measure
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 jm
situ chemical countermeasure will be developeji^ 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 afcer 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 chose 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
• £ 10,000 ppm
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
^-—r
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-Dichlorobenzene
PCB's
Dioxin
Naphthalene
Oil
Grease
1 ,2,4-Trichlorobenzene
Hexachloro butadiene
T rich lor ophenol
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
i
)
1
0.3
0.003
0.003
0.003
0.003
-
-
-
-
-
-
••
NUMBER OF
SITES WHERE
DETECTED
1
1
1
1
1
1
1
2
3
1
2
7
1
1
1
1
1
-
-
-
-
.-— -y»
"•
GROUNDWATER
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
1
4
1
1
1
1
NOTE: "Hydrophobic" 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
Mechylene Chloride
Perch loroe thy lene
Toluene
T rich loroe thy lene
Dichlorophenol
Methyl Chloroform
Vinylidene Chloride
Chloroform
Ethyl Chloride
Fluorot rich lorome thane
Ethylene Dichloride
Methyl Isobutyl Ketone
Vinyl Chloride
Benzene
1 , 2-Dich loroe thy lene
1 ,2-Diphenylhydrazine
Tetrahydropyran
1 , l-Dichloroethane
Chlorobenzene
2-Ethyl-4-methyl-l,3-dioxolane
Isopropyl Ether
1 §6tL NEAft 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
0.5
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).
-------
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-------
TABLE 4. CONCENTRATIONS OF INORGANIC CONTAMINANTS AT 50 SUPERFUND SITES
HEAVY/TOXIC METALS
Cadmium
Zinc
Lead
Nickel
Chromium
Copper
Aluminum
Silver
Arsenic
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
j
.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
I
^
I
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 hydrophiiic 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 hydrophili.es, 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 splyjtion is expressed as follows:
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
17. organic carbon)
L >°° J
(Koc>
ug adsorbed/g soil
K. _ "—™^^
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.
1 2
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^analyses 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.
-------
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TABLE 1. Candidate Organic and Inorganic Test Mixtures for Initial
Insitu Soil Treatment Evaluation >
Waste Type
Processes
Waste Amount (Ib./yr.)*
1) Organics -
Fuel Oils;
PCB;
Organophosphate
Pesticides;
Chlorinated Hydrocarbon
Pesticides;
Methanol;
3)
Reclaimers residues wastes
Nonutilitv oolvchlorinated biphenvl wastes
Pesticide wastes
Production wastes
Production wastes
Cosvnthesis Methanol production wastes
2) Chlorinated Hydrocarbons -
Carbon Tetrachloride;
Perchloro & Trichloro-
ethylene;
Pentachlorophenol;
Dichlorobenzene;
Fire extinguisher; solvent
Chlorinated Hydrocarbon
pesticide production
Wood preservatives waste
Spent wood preserving liquors
Residue from Manufacture of ethylene
dichloride/vinyl chloride
Amines -
Ethylenediamine;
Ethanolamine;
Acids and Bases -
Hydrochloric Acid;
Sulfuric Acid;
Potassium Dichromate;
Sodium Hydroxide;
Ammonium Hydroxide;
Solvent and emulsifier uses, textile lubricant
Gas purification, emulsifier and'
tanning agent
Petroleum Refining-wastes
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
8 x
1 x
6 x
2 x
10
10
10;
108
1 x 106
Not Available
2 x 108
10
10
11
12
2 x 10y
Various
Various
Various
Various
Various
Various
Various
Various
Various
Various
Various
Various
Various
Various
Various
Various
Various
* Cheremisinoff, N.P., P.M. Cheremisinoff, F. Ellerbusch and A.J. Perna (1979),
Industrial and Hazardous Wastes Impoundment. Ann Arbor Science pp 16-23
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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 with median acute 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.
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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
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-------
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.
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- 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
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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 Permeability
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
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*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'* 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 Electrorrics
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), R1chonate»-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 PCB, 1000 ppm Murban
29
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|^^——^j fe^^^^^MW^^g
ENVIROSC1ENCE
January 26, 1983
Mr. Anthony N. Tafuri
Oil £ Hazardous Materials Spill Branch
U.S. Environmental Protection Agency
Edison, New 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, PCB, 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 the 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.,^.! 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,
^
4me*v
THH. ytxnei
bm
.'.12 Oirec'orb Drive •
e 'ennessee 37923 • (6^5; 690-3211
1 ol ' ' ''oiporauon
-------
ENVIROSCIENCE
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 Countenneasures 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. I 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
she 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 thei^approximate soil adsorption constants in paren-
theses: PCB (2 x210*), 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 PCB,
xylene, trichlorophenol, napthalene, and two metals. I believe this list
and the list presented by JRB can be the basis for useful discussions at
^r meeting tomorrow. We should also discuss appropriate concentrations.
I believe that selection of a multicomponent>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
froai 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 • Kno*viHe. T«.r»ni-swe 1/4^3 • (6l5) 690
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2
Mr. Anthony N. Tafuri
January 24, 1983
that, as the program develops, research for opportunities to fill in
these fundamental data gaps be carried out, perhaps by funding research
studies at an appropriate university. Without economic and time 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 and 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 jne^hodology for solving an
important pollutant problem. It is important to develop the process
rapidly and within considerable economic constraints. However, we must
remember that 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
the fundamentals of this proposed- chemical counterraeasures process to
make me comfortable.
Please 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.
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
JR8 Associates, Inc.
SAI/JRB Associates, Inc.
Mason & Hanger
Mason & Hanger
EPA, OHMSB, Edison
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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JRB Associates. Inc. 8400 Westpark Drive, McLean. Virginia 22102 (703) 821-4600
A Subsidiary of Science Applications, Inc.
December 21, 1982
•Ir. Anthony Tafuri
Oil and Hazardous Materials Spills Branch
USEPA/MERL
Woodbridge Avenue
Edison, New Jersey 08837 .*--v
Reference: EPA Contract No. 68-03-3113, Task 29-1
JRB Project No. 2-817-03-956-29
FDear Mr. Tafuri:
Enclosed is a report on the Rationale for Choosing Countermeasure
Test Compounds, as we discussed. We have made several recommendations,
but the final decision, which is quite complex, must be made by you. I
would suggest a meeting, at your convenience, as soon as possible to discuss
the options. Call me at (703)734-2529 if you have any questions or comment.
Sincerely,
William D. Ellis, Ph.D.
Task Manager
WDE/tab
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