\ I /
                   United States
                   Environmental Protection
                   Agency	
Risk Reduction Engineering
Laboratory
Cincinnati OH 45268
                   Research and Development
 EPA/600/S2-89/066 Apr. 1990
&ERA         Project  Summary
                   Technologies  of  Delivery  or
                   Recovery for  the Remediation of
                   Hazardous Waste  Sites

                   L. Murdoch, B. Patterson, G. Losonsky, and W. Harrar
                    Remediating techniques that
                  involve recovering  contaminants or
                  delivering  treating material are
                  particularly  attractive because they
                  can  be less expensive and  more
                  permanent than either  containment
                  or excavation.   A few delivery or
                  recovery techniques are In use today,
                  but  on  the  horizon  are  new
                  technologies that offer improvements
                  in both the rate and  the ultimate
                  effectiveness of remediation.
                    A review was conducted of In-situ
                  delivery or recovery techniques that
                  show promise for the remediation of
                  contaminated ground or groundwater.
                  Of the  techniques reviewed, some
                  are currently being Investigated for
                  remedial actions:  others  show
                  promise but have yet to be investi-
                  gated for remedial purposes. Current
                  Investigations are funded  chiefly by
                  the U.S. Environmental Protection
                  Agency (EPA) or other government
                  agencies.     The   promising
                  technologies have  been drawn from
                  methods developed by the petroleum
                  or solution mining industries.
                    The   review   examined   17
                  technologies.  Twelve are  currently
                  being investigated  in some way as
                  remedial techniques;  four  are from
                  the enhanced oil recovery industry,
                  and one from the  solution mining
                  industry.
                    This  Project  Summary  was
                  developed by EPA's Risk Reduction
                  Engineering 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 the back).

Introduction

Definitions
  Delivery and recovery technologies are
processes that facilitate the  transport of
materials  either  into  or  out  of  the
subsurface.   Delivery  technologies, in
general, involve transporting materials
into the subsurface. Liquids are  the
principal  phase  in  most delivery
operations, although some of the new
techniques allow either vapor or solid
phases to be delivered as well.
  Recovery technologies,  in general,
include any process to remove material
from the subsurface.  Existing recovery
technologies used for  remediation  are
associated with fluid flows  driven by
hydraulic gradients.   Some  innovative
technologies are driven by other types of
processes,  such as thermal methods, as
well as processes to expedite recovery
by employing  chemical reactions that
alter the behavior of contaminants.
  An  innovative delivery  or recovery
technology is a process that offers some
improvement  when compared  with
existing methods.  For  hazardous waste
remediation, improvements either in the
rate of recovery or in the  amount of
contaminants remaining in the subsurface
are considered valuable. Improvements
in delivery would occur with development
of  a method  to deliver an  increased
volume of a liquid phase, or a method to
deliver vapor or solid phases.

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Limitations of Current
Technologies
  Delivery and recovery techniques have
been used for many years to remediate
contaminated sites.  Most currently used
techniques  rely principally on pumping
from wells  to recover  contaminated
groundwater followed  by treatment  and
injection at delivery wells.  These pump
and  treat  techniques   reduce
concentrations to  acceptable  levels for
some  contaminants  under  certain
saturated  site  conditions.    But  these
technologies are generally not applied to
tight  formations  where   hydraulic
conductivities are less than 10-4 cm/sec.
  Currently the delivery of remediating
materials is  limited to injecting  liquids
through  wells.  Methods of  delivering
solid or vapor phases are for the  most
part unavailable, although such methods
would facilitate some remedial  actions.
  Existing  technologies are usually not
effective at sites with contaminants of low
water solubilities or those that  are readily
adsorbed to  soil.    Current delivery or
recovery  methods  are  also  usually
ineffective  for contaminated unsaturated
soils.   Low  hydraulic  conductivities  and
local stagnant zones in unsaturated
media  inhibit the  rates  and ultimate
effectiveness  of  most  delivery  or
recovery technologies.   Furthermore,
some  current recovery methods applied
to the unsaturated zone  require an
underlying  impermeable barrier that
precludes their use at some sites.
  Another problem not addressed by
current  delivery  and   recovery
technologies  is the presence in  some
natural soils  of preferred pathways of
high conductivity separated by blocks of
low conductivity.   Delivery or recovery
from such  soils is  limited by rates of
diffusion through the soil matrix blocks to
the preferred pathways.


Procedures
  The  innovative  technologies reviewed
were identified during  a literature survey
of topics related  to the remediation of
contaminated ground  and groundwater,
enhanced  petroleum recovery,  and
solution  mining.   When   published
descriptions  were  insufficient  to
adequately  describe a  technology,
interviews  were conducted  with
researchers or developers.
  Some of the technologies are currently
being  investigated  as   possible
remediation  methods,  whereas  others,
principally the ones from the petroleum
and mining  industries, have  yet  to  be
investigated.  They  may, however, offer
potential as remediation methods.

Results and Discussions
  The 17 innovative methods of delivery
or recovery  identified  during the review
are listed  in Table  1  and  summarized
below.
  Colloidal  gas  aphrons  (CGA)  are
microdispersions  of gas in  water.
Typically, a  CGA  dispersion is 60 to 70
volume percent gas occurring in the form
of minute bubbles or aphrons.  The use
of gas aphrons has been suggested as a
technique to enhance  the in-situ aerobic
biodegradation  of  dissolved  and
dispersed  organic contaminants.   This
suggestion  is  based  on laboratory
experiments showing that aphrons deliver
a  much greater  concentration of  gas
when compared with other methods that
deliver gases dissolved in water.
  Hydraulic  fracturing  is a process of
cracking rock in  the neighborhood of a
borehole.   The cracks are formed  by
injecting  a fluid,  usually water,  at
pressures exceeding the confining  stress
at the  bottom of  the  borehole.   Sand
pumped into the fracture at the time of its
creation holds the fracture open forming
a  high-permeability  channelway.
Hydraulic fracturing could  be used to
increase the rates of  either delivery or
recovery  to contaminated  soil  or rock
from a well.
  Radial well drilling is a technique used
to place horizontal wells radially outward
from a central borehole (4.5  inches in
diameter or larger).  The horizontal radial
is cut by high velocity  water pumped out
of a conical jet nozzle. The  nozzle is fed
from the surface through steel tubing and
cuts a  borehole with a diameter several
times larger than the tubing. Completed
radials  can be used to enhance access,
for either delivery  or recovery,  to  a
contaminated formation or aquifer for
groundwater control and in-situ treatment.
  Ultrasonic vibration is used extensively
by soil scientists to disperse clay and silt
particles  in the laboratory.   Most
commercial  ultrasonic  probes contain  a
transducer that converts electrical energy
to mechanical energy and  results in  a
mechanical  disturbance  of  the  sample.
Possible  applications of ultrasonic
vibration to remedial actions include: (1)
dispersing  clay particles clogging  soil
pores adjacent to  wells,  (2)  reducing
adsorption of contaminants  onto the
surfaces  of  clays,  and (3) eliminating
microorganisms  clogging soil  pores
adjacent to wells.
  Kerfing  (or  borehole notching) is  a
technique  to cut  a slot either normal or
parallel to the axis of a borehole.  Kerfi
uses a high pressure jet  of water, wa
with entrained air, water and bentonite,
water and an abrasive material to cut I
slot.   Although recent interest in kerfi
has been as a technique to help stop I
migration of pollutants from uncontroll
waste sites, it may also have  applicati
as a recovery technique.
  Electro-kinetics (electro-osmos
occurs when a liquid migrates througr
charged porous medium under the acti
of an  electric field.  The  electric field
applied  through  the  anodes  that cau
the cations to  migrate through  t
saturated medium towards the negativi
charged cathodes.   Viscous drag of I
water  molecules  by the cations causes
net flow of water towards the cathodi
Basically, this  is how the flow of wa
can be induced from the application of
electric  field.  Electro-kinetics has  t
potential  for  delivering remediati
materials and recovering  spent solutic
or contaminants,  principally  metals, frc
contaminated soil.
  The jet-induced  slurry method is
technique used to excavate an ore bo
at  depth   without removing  t
overburden.  A  borehole-mining tool
lowered down a predrilled borehole.  T
borehole-mining  tool generates a hi<:
velocity hydraulic jet that erod
subsurface  material and then  pumps 1
slurry through  a well to the  surface
processing.  This technology  could of
the unique capability   of  recoveri
contaminated  material  from  t
subsurface  without  removing  t
overburden.
  Carbon dioxide flooding is an enhanc
oil recovery technique. Carbon dioxide
injected into oil-bearing formations
maintain pressure  and displace   c
Carbon dioxide injection  mobilizes oil
reducing oil viscosity and increasing 1
pressure in  the reservoir.  Carbon dioxi
flooding   to  recover  groundwat
contaminants would likely be  limited
applications where carbon   dioxide
either dissolved  in  water or contained
aphrons. In either case,  carbon dioxi
flooding could be used to decrease I
viscosity and increase the  recovery
hydrocarbons.
  Water-soluble polymers  added
waterfloods are used to enhance
recovery.   Water-soluble polymers  c
used  to decrease  the viscosity contr
between the oil and fluids in waterfloc
or to  homogenize reservoir  permeabili
The  homogenezation  of  permeability
one possible application of  polymers
the   recovery  of  contaminanl
Temporarily filling high-permeabil

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                           Table 1.  Summary of the Development Status of Innovative Delivery or Recovery
                                   Technologies
                                                          Delivery               Recovery
                                  Technology
           General   Remedial    General    Remedial
1.

2.
3.
4.
5.
6.
7.
8.
9.
10.
11.
12.
13.
14.

15.
16.
17.
Colloidal gas
aphrons
Hydraulic fracturing
Radial drilling
Ultrasonic methods
Kerfing
Electro-kinetics
Jet slurrying
Co2 injection
Polymer injection
Vapor extraction
Steam stripping
Hot-brine injection
In-situ combustion
Radio frequency
heating
Cyclic pumping
Soil flushing
Ground freezing
E"

E
E
NA
E
D
NA
NA
NA
NA
NA
NA
NA
NA

C
NA
NA
E

E
E
NA
E
D
NA
NA
NA
NA
NA
NA
NA
NA

C
NA
NA
A

A
D
A
A
A
A
A
A
A
A
C
A
D

A
A
A
NA

E
D
C
E
D
C
C
C
D
D
C
C
D

C
D
D
                           "Level of development
                             A  - available fully proven and in routine use;
                             D  -  developed, passed bench- and pilot-scale testing;
                             E  -  emerging, research in progress;
                             C  -  conceptual, applicable but unevaluated;
                             NA - not applicable.
channelways with polymer gels could be
used to  induce  flow and  transport
contaminants out of local zones  of low
permeability.
  Vapor extraction involves the recovery
of vapor-ladened air  from  unsaturated
soils by applying a  vacuum  at extraction
wells.  The  pore space of unsaturated
soils is composed  of  liquid and vapor
phases. Compounds with  moderate to
high vapor pressures  will  be partitioned
more strongly into the  vapor phase than
will compounds of lesser vapor pressure.
Vapor extraction techniques make use of
the strong partitioning  by removing the
vapor phase from the soil  through the
application of a vacuum at well  points.
Pressure gradients are  established within
the soil to  induce  convective air flow
through the  porous  media.  The process
appears  to  be  limited to   those
contaminants that exhibit significant
volatility at ambient temperatures.
  In-situ  steam  stripping  is a method
intended  to  recover highly  volatile  and
also moderately low  vapor  pressure
organic compounds from  contaminated
soil.  The steam is  injected  into the
contaminated soil through  wells where it
releases  heat  to  the  soil  when  it
condenses.   The steam has  two main
functions:  it  vaporizes  the  contaminants
 tat would  be  immobile  at ambient
iemperatures  and it becomes  the
transport  medium  for  the  vaporous
materials. The  rate  of vaporization and
transport of these compounds increases
with increasing  soil temperature following
contact with the steam.
  Hot-brine  injection is being  developed
to recover natural gas  from  solid and
liquid gas-hydrate deposits.   Hot-brine
injection  increases both the temperature
and salinity of  a  reservoir  thereby
promoting dissociation  reactions  that
drive solid or liquid  gas-hydrates into a
vapor phase  and  water  for easier
recovery.    Hot-brine injection could be
used at  uncontrolled hazardous waste
sites to  recover certain contaminants
whose dissociation  temperatures
decrease  with  an increasing salinity  of
pore fluid.  The  applicability  of  this
method will require a salinity dependence
on  the dissociation  temperature of the
contaminant species to be recovered.
  In-situ combustion methods are used to
recover crude  oil from  tar sands  and
other deposits of  viscous hydrocarbons.
In-situ combustion uses  an injection and
production well system  to  create  and
migrate a thermal front through an oil-
bearing formation.  As the front advances
and  the formation  temperature  increases,
lighter oil fractions are mobilized through
volatilization and  reduced  viscosity.
Similar  techniques  could  possibly  be
used to  recover hydrocarbons  from
uncontrolled hazardous waste sites.
  Radio-frequency  (RF) heating  was
developed in the 1970's  for the thermal
recovery  of  hydrocarbons.   Electro-
magnetic energy  is  applied  to the
contaminated soil  through  bound-wave
exciter electrodes.  In this way molecular
agitation rather than  thermal conduction
is used to heat the soil.   RF  heating
techniques   may have  two  general
applications as a remedial technique: (1)
thermal vaporization and recovery  of
contaminants with low boiling points and
(2)  the  improvement of  reaction  rates
between contaminants  with  high boiling
temperatures and applied  reagents.
  Cyclic  pumping  is  a  delivery or
recovery technique that  systematically
varies  rates of  either injection or
extraction. Pumps  are  turned on during
an active  cycle and  turned  off  during a
rest cycle. The rest cycle allows time for
diffusion between high-permeability path-
ways and the low-permeability blocks
between them. Treating solutions diffuse
from the  pathways into  the blocks, or
contaminants diffuse  from the blocks  to
the  pathways.  The active  cycle  is
designed to deliver the minimum volume
of nutrients or reactants or to remove the
maximum possible concentration of
reaction products.  The optimization of
pumping practices has the  potential to

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reduce remediation  costs at hazardous
waste sites by minimizing pumping costs.
  In-situ soil flushing is  a technology
designed to accelerate the movement of
a  contaminant  through  unsaturated
materials.  The efficacy of soil flushing is
related to two processes: (1) the increase
in  hydraulic  conductivity  that
accompanies  an  increase  in  water
content of unsaturated  soil  and (2)  the
engineering of treatment solutions to the
composition of the contaminants and the
contaminated  medium.  A treatment
solution is applied to the soil and allowed
to percolate  downward and  interact with
contaminating chemicals.  Contaminants
are mobilized and transported downward
to a  saturated zone where  they  are
pumped to the surface.
           Ground freezing is a technique with the
         potential  to  migrate  and  concentrate
         solutes. When pore water freezes slowly,
         crystals of nearly pure ice form, and any
         dissolved  species  are concentrated  in
         pockets or thin films of liquid around solid
         particles.  The  film around the particles
         can  be  very  mobile  allowing  ion
         movement to occur through  diffusion.
         Artificial ground freezing potentially can
         concentrate contaminants  ahead  of
         freezing  fronts  reducing the  volume  of
         contaminated soil at a site and thereby
         facilitate remediation.

         Conclusions
           Innovative technologies of delivery and
         recovery  offer  a  range of  potentially
valuable  new  methods  of  remediati
contaminated   sites.     Furth
investigations  that  would develop t
appropriate technologies to a  level
routine field application  should  certaii
enhance  the  remediation  of  sor
problematic  uncontrolled hazardo
waste sites.
  The full report  was  submitted
fulfillment of  Work  Assignment 1-11
Contract  No.  68-03-3379  by  t
University of  Cincinnati  under  t
sponsorship of the U.S.  Environmen
Protection Agency.
    L Murdoch, B. Patterson, G. Losonsky, and W. Harrar are with the University of
          Cincinnati, Cincinnati, OH 45221.
    Kenneth Dotson was the Work Assignment Manager.
    The complete report, entitled  "Technologies oj Delivery or Recovery for the
          Remediation of Hazardous Waste  Sites,"nprder No. PB90-156 2251 AS;
          Cost: $23.00 subject to change) will be avvfable only from:
              National Technical Information Service
              5285 Port Royal Road
              Springfield, VA 22161
              Telephone: 703-487-4650
    For further information, Michael Roulier can be contacted at:
              Risk Reduction Engineering Laboratory
              U.S. Environmental Protection Agency
              Cincinnati, OH 45268
 United States
 Environmental Protection
 Agency
Center for Environmental Research
Information
Cincinnati OH 45268
  Official Business
  Penalty for Private Use $300

  EPA/600/S2-89/066

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