United States
 Environmental Protection
 Agency
Hazardous Waste Engineering
Research Laboratory
Cincinnati OH 45268
 Research and Development
EPA/600/S2-87'110 Feb. 1988
 Project Summary
 Field  Studies  of In Situ Soil
 Washing
 James H. Nash
  The EPA  and U.S.  Air  Force
conducted a  research test program
to demonstrate  the removal of
hydrocarbons  and  chlorinated
hydrocarbons from a sandy soil by in
situ soil washing using surfactants.
  Contaminated  soil from the fire
training area of Volk Air National
Guard  Base,  Wisconsin,  was  first
taken  to   a   laboratory  for
characterization. At the laboratory
the soil was recompacted into glass
columns creating a simulated in situ
environment.  Under  gravity flow, 12
pore volumes of aqueous surfactant
solutions were passed through each
of the columns. Gas chromatograph
(GC) analyses were used  on the
washing  effluent  and  soil to
determine removal efficiency (RE).
The  results  of these  tests  were
highly  encouraging.  RE's of field
tests run at the fire training  area
were evaluated by GC, total organic
carbon (TOC) and oil and grease
data. Ten one foot deep holes were
dug  in the surface  of the fire pit.
Surfactant solutions  were applied to
each hole at a rate of 1.9 gallons per
square foot per day. Soil samples,
taken from  the  undisturbed  layers
beneath each  hole, were analyzed for
residual  contamination.  Samples
experiencing a flow through of  nine
to fourteen  pore  volumes of
surfactant  solution  still  had
contaminant  levels  comparable to
5,000-10,000   ng/g   prewash
conditions.
  The field study  also included the
development of  a  groundwater
treatment process. Measurements of
TOC, VOA and biochemical oxygen
demand (BOD5) were decreased by
50%, 99%,  and 50%,  respectively.
Treated  effluent was  discharged
directly  to  the on-base aerobic
treatment lagoons.
    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 Project Report
ordering information at back).


Introduction
    Surface   and  near-surface
contamination often serve as the source
for groundwater  contamination
Percolation of rainwater through spill sites
quickly carries soluble and  semi-soluble
contaminants away from the point  of
origin  Contaminants  considered
"insoluble"  above parts  per  million
nevertheless migrate more slowly. Gross
contaminant sources supply pure product
that over  many years,  flows  deeply
through unsaturated soils.
    Part of the  EPA's Superfund site
cleanup research has been  directed  at
washing such contaminated soil with the
aid of aqueous surfactant solutions. The
research takes two directions. The first is
to excavate the soil and mix it m a wash
solution. The  second research objective
concentrates on  the application  or
injection  of  a surfactant solution into
undisturbed soil in situ. A segment of this
in situ  research is the  subject of this
project summary.
    This demonstration effort grew out of
mutual need between  the EPA and the
U.S. Air Force. From 1982  to 1985 the
EPA researched  soil washing technology
using surfactants in laboratory studies.
Recompacted soils were used in these
studies to simulate in situ   conditions

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Truly undisturbed contaminated soil was
not tested up to that time. The U.S. Air
Force,  as  part  of  its  Installation
Restoration  Program,  was  seeking
processes to clean  up  128 fire training
pits at Air  Force  installations.  The  Air
Force selected the  Air National  Guard
Base in  Camp Douglas, Wisconsin, as a
candidate site for the EPA to test either
excavated or in situ  soil washing. The
EPA and the Air  Force  representatives
chose  in  situ  washing  after further
consideration.

The Laboratory  Study
    Previous laboratory work identified a
50/50  blend  of two  commercially
available surfactants  that work well  in
removing contaminants  from soil.  They
are Adsee 799 and  Hyonic PE-90,  sold
by  Witco   Chemical  and Diamond
Shamrock, respectively  To  determine if
this same blend would work at the Volk
Field fire training  pit, contaminated soil
samples were collected
    Five physical tests characterized the
soil. They were: grain size,  TOC, cation
exchange capacity (CEC), mineralogy by
x-ray  diffraction,  and permeability  The
grain size of the contaminated soil was
98% sand.  By  x-ray diffraction,  alpha-
quartz comprises the major portion of the
soil with a  minor amount  of  feldspar
being present.  TOC was  as  high as
14,900  ng/g.  The  cation  exchange
capacity of 5 milliequivalents.100 g was
not significant  to  the  contamination
levels, however, it did support  the x-ray
diffraction  mineralogic  findings.  The
permeability of the  fire pit  soil, at  10-3
and 10'4 cm/sec, was one to two orders
of  magnitude  less than adjacent
uncontaminated soil
    Chlorinated  hydrocarbons were part
of  the  volatile   contamination.
Dichloromethane,  chloroform,  1,1,1-
trichloroethane    (TCA),   and
trichloroethylene (TCE) at concentrations
up  to  3 ppm  and total  chlorinated
solvents up to 3.5 ppm were determined
by the  VOA  procedure.  Other
hydrocarbons are aliphatic, aromatic and
polar  constituents.  The  level  of
hydrocarbon contamination is in  the
hundreds of ng/g based on the laboratory
analysis.
    Contaminated  groundwater, a
significant  problem, from  the aquifer
below  the  fire training  pit,  was  also
characterized in  the  lab study.  VOA,
TOC,  and ultraviolet spectroscopy  (UV)
was used. The investigations determined
that the  groundwater contains chlorinated
and  non-chlorinated hydrocarbons  in
excess of 300 ppm
    The soil adsorption constant (K) is a
measure  of  a pollutant's  tendency to
adsorb and stay on soil. A value of 2,000
for  PCB's indicates a two-hundred-fold
greater adsorption  (holding power)  than
benzene  at  K=10.  Benzo(a)pyrene, a
toxic substance, and  oil  have similar
values - K  = 30,000 - 40,000. Grouping
contaminants according to a K value and
evaluating  removal efficiencies  (RE)
gives  order to  an  otherwise  complex
collection of chemical  classes. This is a
report of the EPA's and  the  U.S.  Air
Force's  field  evaluation of in situ   soil
washing of compounds having  K values
between 101 and 106

The Field Study
    The field study was  conducted by
laying out ten 2' x  2' x 1'  pits, dug into
the contaminated  surface of the  fire
training area,  which served as reservoirs
that held  various surfactant  solutions.
Field technicians applied wash solutions
into the holes at the maximum rate of 1 9
gallons per  square  foot per  day  The
daily  dosage  was applied  m  four
increments Since each hole percolated
the solutions  at different rates, the  time
interval between doses varied from  hole
to hole.  Testing in  three of the  pits
stopped when the time intervals for the
next application  approached  ten hours
indicating  unacceptable permeabilities
being  created. Following seven days of
washing,  the pits received rinses  with
local, potable well water
    A  combination  of  infrared
spectroscopy  (IR)  and  gravimetric
determinations of soil extracts was used
to  evaluate  "before   and  after"
contaminant  concentrations.   To
determine  contaminant concentration,
soil samples  were  taken after the rinse
process,  extracted  with  carbon
tetrachlonde,  and  analyzed by IR
spectrophotometer for   spectral
absorbance by  the carbon  hydrogen
bond  The  extracts  were  then air dried
and weighed to determine gravimetrically
the contaminant concentration (non-
volatile).
    The  contaminant  concentration
before soil washing was  based on  the
extracts of soil samples taken adjacent to
the test holes  No samples  were  taken
directly  from  the  test  holes before
washing in order not to bias  permeation
rates
    Based on both the gravimetric  and
IR  determinations  of  contaminant
concentrations, there was no  measurable
decrease  in  contaminants following as
many as 14 pore volumes of soil washing
in the field tests.
    In addition to the soil washing,
field crew  conducted a  bench-s>
groundwater treatment study.  From
study a treatment system was asseml
and operated which successfully redi
TOC, VOA  and BOD5, by  50, 99,
50%, respectively.  At  these effh
levels,  discharge  to the local  aen
sewage lagoon was below the  Wisco
Department of  Natural Resources' pe
limits  A total  of  320,000  L of  c
tammated  groundwater was treatec
rates of 15,000 to 45,000 Lday.
    The bench-scale study investig,
the use  of  lime,  alum,  ferric  sulf
hydrogen peroxide,  polymeric  elec
lytes and mineral  acids. The apphce
of these  chemicals was guided
conventions  appropriate to wastew
treatment plants.  The resulting  w
treatment process  (shown in  Figure
was  based  on  the  addition  of lime ;
g;L.  The  lime  created  a flocculatior
iron  oxides  and  organics.   "
contaminant plume  contained up  to
mg/L iron. Particulate sedimentation
clanfier, followed by additional reside
time in a holding  lagoon,  reduced
TOC, BOD5,  and  VOA  to  accept;
discharge levels. A final polishing  of
volatiles m  an  air stripper was the I
step  in  the process  Table  1   i:
summary of the analytical data


Conclusions
 1. In situ soil washing of the Volk Fi
   fire training  pit  with  aquec
   surfactant  solutions  was  r
   measurably  effective  It is  likely t
   this same ineffectiveness would  oc
   at other  chronic spill  sites  that h;
   contaminants with high  soil-sorpt
   values (K >1Q3).
 2. In situ soil washing requires groui
   water  treatment.  Groundwa
   treatment at this  site  was  ve
   successful with the simple addition
   lime Air stripping effectively remov
   the volatile  organics. Advantages
   this site  were  its remoteness
   workable air  emission  limits  tl
   facilitated  groundwater treatrm
   operations and  a  local  sewa
   treatment  system  owned by t
   responsible  party  TOC levels of
   recovered groundwater were reduc
   to one  half the  initial values
   precipitation with lime which  allow
   for direct discharge  to  the  aerol
   treatment lagoons. Obviously,  not
   waste  sites have these  favorai
   conditions   Other  fire  pit sites w
   lower  effluent  limits would  requ
   systems with greater retention time:

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                                                                                               Volatiles
                                    Lime


2
I
t
*
—
Flash
Mix <




JB1 	 ~~ta
Clarifier
^
                                                                                  Lagoon
                                                                                                         Air
                                                                      To Aerobic
                                                                        Lagoon
                             Well
Figure 1.     Volk Field pilot treatment for water.
              Table 1
                Pt No.
Analytical Tests and Sampling Points for the Water Treatment Process
    Description
Tests Performed
Approximate Values, Average or
            Range
                   1      Individual we/I head
                   2     Well field effluent
                   3     Flash mixer effluent
                   4     Clarifier effluent
                   5     Air stripper feed
                   6     Air stripper effluent
                   7     Clarifier
                   8     Clarifier bottom
                   9     Soil
                     volatile organic
                     total organic
                     chemical oxygen demand
                     oil and grease
                     pH
                     volatile organic
                     total organic
                     iron
                     pH
                     chemical oxygen demand
                     flow rate
                     total organic (dissolved)
                     suspended solids
                     pH
                     flow rate
                     total organic
                     suspended solids
                     pH
                     flow rate
                     volatile organic
                     total organic
                     temperature
                     flow rate (water)
                     oil and grease
                     volatile organic
                     total organic
                     flow rate (air)
                     oil and grease
                     biochemical oxygen demand
                     chemical oxygen demand
                     suspended solids
                     suspended solids
                     oil and grease	
                           70-20 mgiliter
                           60-760 mgiliter
                           6-500 mgiliter
                           0 2-46 mgiliter
                           5.7-62
                           70-20 mgiliter
                           250 ± 14% mgiliter
                           32 mglliter
                           6.0 ± 0.2
                           41 mgiliter
                           .25 -  2 Mer.sec
                           7 60 mg 'liter
                           350 mgtliter
                           68-9.7
                           .5 - 2 liter'sec
                           205 ± 7% mgiliter
                           13 6-W4 mgiliter
                           76
                           .5 - 2 liter,'sec
                           3.5 -  7.0 mgiliter
                           151  ± 73% mgiliter
                           6-I5"C
                           95 -  7 26 /ifer/sec
                           3.6 mgiliter
                           0.3-05 pgMer
                           146 mgiliter
                           101 //sec
                           3.6 mgiliter
                           2.5 mgiliter
                           180 mgfliter
                           4.4 mgiliter
                           2331  mgiliter
                           800-16000 mgikg

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  James H. Nash is with Mason and Hanger-Silas Mason Co., Inc., Leonardo,
     New Jersey 07737
  Richard P. Traver is the EPA Project Officer (see below).
  The complete report, entitled "Field Studies of InSitu So/7 Washing" (Order No. PB
  88-1468081 AS; Cost: $14.95, subject to change) will be available only from:
           National Technical Information Service
           5285 Port Royal Road
           Springfield, VA22161
           Telephone:  703-487-4650
  The EPA Project Officer can be contacted at:
           Releases Control Branch
           Hazardous  Waste Engineering Research Laboratory-Cincinnati
           U.S. Environmental Protection Agency
           Edison, NJ 08837
United States
Environmental Protection
Agency
Center for Environmental Research
Information
Cincinnati OH 45268
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