United States       R.S. Kerr            Office  of Solid Waste Publication:  9355.4-07FS
                           Environmental       Environmental        and Emergency      January 1992
                           Protection  Agency Research  Laboratory  Response
<&  EPA               Estimating  Potential  for  Occurrence
                           of DNAPL  at Superfund Sites
Office of Emergency and Remedial Response
Hazardous Site Control  Division (OS-220W)                                                 Quick Reference Fact Sheet
GOALS
The presence of Dense Nonaqueous Phase Liquids (DNAPL) in soils and aquifers can control the ultimate success or failure
of remediation at a hazardous waste site. Because of the complex nature of DNAPL transport and fate, however, DNAPL
may often be undetected by direct methods, leading to incomplete site assessments and inadequate remedial designs. Sites
affected by DNAPL may require a different "paradigm," or conceptual framework, to develop effective characterization and
remedial actions  (2).

To help site personnel determine if DNAPL-based characterization strategies should be employed at a particular site, a
guide for estimating the potential for DNAPL occurrence was developed.  The approach, described in this fact sheet,
requires application of two types of existing site information:

                • Historical Site Use Information            • Site Characterization Data

By using available data, site decision makers can enter a system of two flowcharts and a classification matrix for estimating
the potential for DNAPL occurrence at a site.  If the potential for DNAPL occurrence is low, then conventional site
assessment and remedial actions may be sufficient. If the potential for DNAPL is moderate or high, however, a different
conceptual approach may be required to account for problems associated with DNAPL in the subsurface.
BACKGROUND

DNAPLs are separate-phase hydrocarbon liquids that are denser than water, such as chlorinated solvents (either as a single
component or as mixtures of solvents), wood preservative wastes, coal tar wastes, and pesticides. Until recently, standard
operating practice in a variety of industries resulted in the release of large quantities of DNAPL to the subsurface. Most
DNAPLs undergo only limited degradation in the subsurface, and persist for long periods while slowly releasing soluble
organic constituents to ground water through dissolution. Even with a moderate DNAPL release, dissolution may continue
for hundreds of years or longer under natural conditions before all the DNAPL is dissipated and concentrations of soluble
organics in ground water return to background levels.

DNAPL exists in the soil/aquifer matrix as free-phase DNAPL and residual DNAPL. When released at the surface, free-
phase DNAPL moves downward through the soil matrix under the force of gravity or laterally along the surface of sloping
fine-grained stratigraphic units. As the free-phase DNAPL moves, blobs or ganglia are trapped in pores and/or fractures by
capillary forces (7).  The amount of the trapped DNAPL, known as residual  saturation, is a function of the physical
properties of the DNAPL and the hydrogeologic characteristics of the soil/aquifer medium and typically ranges from 5% to
50% of total pore volume.  At many sites, however, DNAPL migrates preferentially through small-scale fractures and
heterogeneities in the soil, permitting the DNAPL to penetrate much deeper than would be predicted from application of
typical residual saturation values (16).

Once in the subsurface, it is difficult or impossible to recover all of the trapped residual DNAPL. The conventional aquifer
remediation approach, ground water pump-and-treat, usually removes only a small fraction of trapped residual DNAPL
(11, 21, 26). Although many DNAPL removal technologies are currently being tested, to date there have been no field
demonstrations where sufficient DNAPL has been successfully recovered from the subsurface to return the aquifer to
drinking water quality. The DNAPL that remains trapped in the soil/aquifer matrix acts as a continuing source of dissolved
contaminants to ground water, preventing the restoration of DNAPL-affected aquifers for many years.
                                                                             Printed on Recycled Paper

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        DNAPL  TRANSPORT  AND  FATE  -  CONCEPTUAL  APPROACHES


The major  factors controlling DNAPL migration in the subsurface include the following (5):

    • the volume of DNAPL  released;
    • the area of infiltration at the DNAPL entry point to the subsurface;
    • the duration of release;
    • properties of the DNAPL, such as density, viscosity, and interracial tension;
    • properties  of the soil/aquifer media,  such as pore size and permeability;
    • general stratigraphy, such as the location and topography of low-permeability units;
    • micro-stratigraphic features, such as root holes, small fractures, and slickensides found in silt/clay layers.

    To  describe the general transport and fate properties of DNAPL in the subsurface, a series of conceptual
    models (24) are presented in the following figures:
 Case 1: DNAPL Release to Vadose Zone Only

 After  release  on the  surface, DNAPL moves
 vertically  downward  under the force of gravity
 and  soil  capillarity. Because only  a  small amount
 of DNAPL was released, all of the  mobile DNAPL
 is eventually trapped in pores  and  fractures in the
 unsaturated  zone.     Infiltration  through  the
 DNAPL zone dissolves  some  of the  soluble
 organic  constituents in  the  DNAPL,  carrying
 organics to the  water table and forming  a
 dissolved organic plume in the aquifer. Migration
 of gaseous vapors can also act  as  a source of
 dissolved organics to ground water (13).
               DNAPL
               Gaseous
               Vapors
           Saturation of
            DNAPL in
           Vadose Zone
                                        Infiltration, Leaching
                                        and Mobile DNAPL
                                             Vapors
Dissolved Contaminant Plume
  From DNAPL Soil Vapor
                      Ground Water
                          Flow

    Dissolved Contaminant
     Plume From DNAPL
     Residual  Saturation

   After, Waterloo Centre for Groundwater Research, 1989.
 Case 2: DNAPL Release to Unsaturated and
         Saturated Zones

 If enough DNAPL is released at the surface, it can
 migrate all the way through the unsaturated zone
 and reach a water-bearing unit.    Because the
 specific gravity of DNAPL is greater than water, it
 continues downward until the  mobile DNAPL  is
 exhausted  and  is   trapped  as  a  residual
 hydrocarbon  in  the porous media. Ground water
 flowing  past the  trapped  residual  DNAPL
 dissolves soluble  components  of  the  DNAPL,
 forming  a dissolved  plume downgradient of the
 DNAPL  zone.  As with  Case  1, water infiltrating
 down from the source zone also carries dissolved
 constituents to the  aquifer and  contributes further
 to the dissolved plume.
                                          Residual
                                         Saturation of
                                       NAPL  in  Soil
                                          From Spill
                                          Infiltration and
                                               Leaching
    Dissolved
Contaminant  Plume
                                             Ground Water
                                          •*—F  1  o  w
        Residual
Saturation in Saturated Zone

   After, Waterloo Centre for Groundwater Research, 1989.

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 CONCEPTUAL  APPROACHES  -  Continued
 Case 3:  DNAPL Pools and Effect of Low-
         Permeability  Units

 Mobile  DNAPL will  continue  vertical migration
 until  it is trapped as a residual  hydrocarbon (Case
 1   and  Case  2)  or until  low-permeability
 stratigraphic units  are  encountered  which create
 DNAPL  "pools"  in  the soil/aquifer matrix.  In this
 figure, a perched DNAPL pool fills up and  then
 spills over the lip  of  the  low-permeability
 stratigraphic  unit. The spill-over point  (or  points)
 can be  some  distance  away from  the original
 source,  greatly  complicating  the process  of
 tracking  the  DNAPL migration.
 Dissolved
Contaminant
   Plume
                                            Low Permeable
                                        ^^Stratigraphic Unit
                                                                               After, Waterloo Centre for Groundwater Research, 1989.
 Case 4: Composite  Site

 In  this case,  mobile DNAPL  migrates vertically
 downward through the unsaturated  zone and the
 first  saturated zone,   producing  a  dissolved
 constituent plume  in the upper aquifer. Although
 a DNAPL pool is formed  on the fractured  clay
 unit,  the fractures  are large  enough to permit
 vertical  migration  downward to  the deeper
 aquifer (see Case 5, below).  DNAPL  pools in a
 topographic low in the  underlying  impermeable
 unit and  a  second dissolved constituent plume  is
 formed.
      Dissolved
    Contaminant
       Plumes
                                                    After, Waterloo Centre for Ground Water Research, 1989.
Case 5: Fractured Rock or Fractured Clay System

DNAPL  introduced  into  a fractured  rock  or
fractured  clay system  follows a  complex  pathway
based  on the distribution  of fractures  in  the
original  matrix.  The number,  density, size,  and
direction  of the  fractures  usually  cannot  be
determined due to  the extreme heterogeneity  of a
fractured  system  and the  lack  of economical
aquifer characterization technologies.  Relatively
small  volumes of  DNAPL  can  penetrate  deeply
into  fractured systems due  to  the  low  retention
capacity  of the fractures  and the  ability of some
DNAPLs to migrate  through very  small (<  20
microns)  fractures.    Many clay  units, once
considered  to  be  relatively  impermeable  to
DNAPL  migration,  often act as  fractured media
with preferential  pathways for  vertical  and
horizontal  DNAPL  migration.
                                                 Fractured
                                                  Rock or
                                                 Fractured
                                                   Clay  .
                          After, Waterloo Centre for Ground Water Research, 1989

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           f  Does Historical Site Use Information Indicate Presence of DNAPL?
  5-H
  tC
  X
  u
  c
  o
   U
   QJ
  Q
                                                       YES
  Q
   0)
   u
   C
   0)
   JH
   in
   3
   U
   u
  o
        Does the
industry type suggest a high
  probability of historical
     DNAPL release?
       (see Table 1)
               Does a
          process or waste
     practice employed at the site
     suggest a high probability of
      historical DNAPL release?
             (see Table 2)
              Were any
       DNAPL-related chemicals
used in appreciable quantities at the site?
         (> 10-50 drums/year)
             (see Table 3)
                                                                                 Go To Next Page
      INSTRUCTIONS

  Answer questions in Flowchart 1
   (historical site use info. - page 4).

2. Answer questions in Flowchart 2
  (site characterization data - page 5).

3. Use "Yes," "No,"and "Maybe"
  answers from both flowcharts and enter
  Occurrence of DNAPL matrix
  (page 6).
            TABLE 1
Industries with  high probability
of historical DNAPL release:

•  Wood preservation (creosote)
•  Old coal  gas  plants
   (mid-1800s to mid-1900s)
•  Electronics manufacturing
•  Solvent production
•  Pesticide  manufacturing
•  Herbicide manufacturing
•  Airplane maintenance
•  Commercial  dry  cleaning
•  Instrument  manufacturing
•  Transformer oil production
•  Transformer reprocessing
•   Steel industry coking
     operations (coal tar)
•  Pipeline  compressor stations
                            TABLE 2
                   Industrial processes or waste
                   disposal  practices with high
                   probability of historical DNAPL
                   release:

                   • Metal cleaning/decreasing
                   • Metal  machining
                   • Tool-and-die  operations
                   • Paint  removing/stripping
                   •Storage of solvents  in
                     underground  storage  tanks
                   • Storage of drummed solvents
                     in  uncontained  storage  areas
                   • Solvent loading  and unloading
                   •Disposal  of mixed chemical
                     wastes in landfills
                   •Treatment of  mixed chemical
                     wastes in lagoons  or ponds
                                                   TABLE 3 DNAPL-Related Chemicals (20):
           Note:
           The potential for DNAPL release increases with the  size
           and active period of operation for  a facility,  industrial
           process, or waste disposal practice.
                                                   Halogenated Volatiles

                                                   Chlorobenzene
                                                   1,2-Dichloropropane
                                                   1,1-Dichloroethane
                                                   1,1 -Dichloroethy lene
                                                   1,2-Dichloroethane
                                                   Trans-1,2-Dichloroethylene
                                                   Cis-l,2-Dichloroethylene
                                                   1,1,1- Trichloroethane
                                                   Methylene Chloride
                                                   1,1,2-Trichloroethane
                                                   Trichloroethylene
                                                   Chloroform
                                                   Carbon Tetrachloride
                                                   1,1,2,2-Tetrachloroethane
                                                   Tetrachloroethylene
                                                   Ethylene  Dibromide

                                                   Halogenated
                                                    Semi-Volatiles

                                                    1,4-Dichlorobenzene
                                                    1,2-Dichlorobenzene
                                                   Aroclor 1242, 1254, 1260
                                                   Chlordane
                                                   Dieldrin
                                                   2,3,4,6-Tetrachlorophenol
                                                   Pentachlorophenol
            Non-Halogenated
            Semi-Volatiles

            2-Methyl Napthalene
            o-Cresol
            p-Cresol
            2,4-Dimethylphenol
            m-Cresol
            Phenol
            Naphthalene
            Benzo(a)Anthracene
            Fluorene
            Acenaphthene
            Anthracene
            Dibenzo(a,h)Anthracene
            Fluoranthene
            Pyrene
            Chrysene
            2,4-Dinitrophenol

            Miscellaneous

            Coal Tar
            Creosote
                                                                                 Note: Many of these
                                                                                  chemicals are found
                                                                                  mixed with other chemicals
                                                                                  or carrier oils.

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   1% of pure
                        phase volubility or effective volubility,
                        (defined in Worksheet 1, pg. 7) (25).

                        Condition 2:
                        Concentrations of DNAPL-related chemicals
                        on soils are >10,000 mg/kg (equal to 1 % of
                        soil mass) (6).

                        Condition 3:
                        Concentrations of DNAPL-related chemicals
                        in ground water calculated from water/soil
                        partitioning relationships and soil samples
                        are > pure phase volubility or effective
                        solubility(see Worksheet 2, pg. 7).

                        Condition 4
                        Concentrations of DNAPL-related chemicals
                        in ground water increase with depth or
                        appear in anomalous up gradient / across
                        gradient locations (25).
Note: This procedure is designed primarily for hydrogeologic settings comprised of gravel, sand, silt, or
      clay and may not be be applicable to karst or fractured rock settings.

                                                              5
                                                                            TABLE  6

                                                                 Characteristics of extensive field
                                                                 programs that can help indicate the
                                                                 presence or absence of DNAPL (if
                                                                 several are present, select "NO"):

                                                                • Numerous monitoring wells, with
                                                                  wells screened in topographic  lows
                                                                  on the surface of fine-grained,
                                                                  relatively impermeable units.

                                                                • Multi-level sampling capability.

                                                                • Numerous organic chemical analyses
                                                                  of soil samples at different depths
                                                                  using GC or GC/MS methods.

                                                                • Well-defined site stratigraphy, using
                                                                  numerous soil borings, a cone
                                                                  penetrometer survey, or geophysics.

                                                                • Data from pilot tests or "early action"
                                                                  projects that indicate the site
                                                                  responds as predicted by
                                                                  conventional solute transport
                                                                  relationships, rather than responding
                                                                  as if additional sources of dissolved
                                                                  contaminants are present in the
                                                                  aquifer (11, 25).

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               Potential for Occurrence of DNAPL at Superfund Sites    J
                                                                DNAPL Category
[^^^^^^^^^^^^^^ Do Characterization Data Indicate
"*\^5^MBfc*- Presence of DNAPL? (Chart 2)
\
^H
g s
| y Yes
Ol r^.
« , 1
!-• L
"73 ^>
•| o Maybe
*TH QJ
s s
£ No
Yes
I

I

I
Maybe
I -II

II

II
No
II

II - III

III
     Category
    high potential
    for DNAPL
    at site.
                            Implications for Site  Assessment

• The risk of spreading contaminants increases with the proximity to a potential DNAPL zone. Special
  precautions should be taken to ensure that drilling does not create pathways for continued vertical
  migration  of  free-phase DNAPLs. In DNAPL  zones, drilling should be suspended  when a low-
  permeability unit or DNAPL is first encountered. Wells should be installed with short screens (< 10
  feet). If required,  deeper drilling through known DNAPL  zones should be conducted only by using
  double or triple-cased  wells to prevent downward  migration of DNAPL. As  some  DNAPLs can
  penetrate  fractures as  narrow as 10 microns, special  care must  be  taken during all grouting,
  cementing, and well sealing activities conducted in DNAPL zones.

• In some hydrogeologic settings, such as fractured crystalline  rock, it is  impossible to drill through
  DNAPL with existing  technology without causing  vertical  migration  of the  DNAPL down the
  borehole, even when double or triple casing is  employed (2).

• The  subsurface DNAPL  distribution is difficult  to delineate accurately  at some sites.  DNAPL
  migrates preferentially  through selected pathways (fractures,  sand  layers, etc.)  and is  affected by
  small-scale changes in the stratigraphy of an aquifer. Therefore, the ultimate path taken by DNAPL
  can be very difficult to  characterize and predict.

• In most cases,  fine-grained aquitards  (such  as clay  or  silt units) should be  assumed to  permit
  downward migration of DNAPL  through  fractures unless proven otherwise  in  the field. At  some
  sites it can be exceptionally difficult to prove otherwise even with  intensive site investigations (2).

• Drilling in areas known to be DNAPL-free should be performed before drilling in DNAPL  zones in
  order to form a reliable conceptual model  of  site hydrogeology,  stratigraphy, and potential DNAPL
  pathways.  In  areas where it is difficult  to form  a reliable  conceptual model, an "outside-in" strategy
  may be appropriate: drilling in DNAPL zones is avoided or  minimized  in favor of delineating the
  outside  dissolved-phase plume  (2). Many fractured rock  settings  may  require this approach to
  avoid opening further pathways for DNAPL migration during site-assessment.
[i Moderate        1  Due  to  the  potential  risk for exacerbating  ground-water contamination  problems during drilling
    potential  for      through  DNAPL zones, the precautions described for Category I should be considered during  site
    DNAPL at site.    assessment. Further work should focus on determining if the site is a "DNAPL site."
Ill Low potential
    for DNAPL
    at site.
1 DNAPL is not likely to be a problem during site characterization,  and special DNAPL precautions
  are  probably  not  needed.  Floating  free-phase organics (LNAPLs), sorption, and other factors can
  complicate site assessment and remediation activities, however.
                                      6

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Worksheet 1:  Calculation of Effective Volubility (from Shiu,  1988; Feenstra, Mackay, & Cherry, 1991)

For a single-component DNAPL, the pure-phase volubility  of the organic constituent can be used to estimate the theoretical
upper-level concentration  of organics in aquifers or for performing dissolution calculations. For  DNAPLs comprised  of  a
mixture of chemicals, however, the effective volubility concept should be employed:
                      Where
                                S J    = the effective volubility (the theoretical upper-level  dissolved-phase concentration
                                        of a constituent in ground water in equilibrium with a mixed DNAPL; in mg/1)

                                Xj  = the mole fraction of component i in the DNAPL mixture (obtained from a lab
                                        analysis  of a DNAPL  sample or estimated from waste characterization data)

                                Sj =  the pure-phase  volubility of compound i in mg/1  (usually obtained from
                                        literature sources)
For example, if a laboratory analysis indicates that the mole fraction of trichloroethylene (TCE) in DNAPL is 0.10, then the
effective solubility would be 110  mg/1  [pure phase solubility of TCE times mole fraction TCE: (1100 mg/1) * (0.10) =110
mg/1]. Effective solubilities can be calculated for  all components in a DNAPL mixture.  Insoluble  organics in the mixture
(such as long-chained alkanes) will reduce the mole fraction and effective  volubility of more soluble organics but will not
contribute dissolved-phase  organics to  ground  water.  Please note that this relationship is approximate and does not account for
non-ideal behavior of mixtures, such  as co-solvency, etc.


Worksheet 2: Method for  Assessing Residual  NAPL  Based  on  Organic Chemical
                    Concentrations  in  Soil  Samples  (From Feenstra,  Mackay,  and  Cherry,  1991)

To estimate  if NAPLs  are present, a partitioning calculation based on chemical and physical  analyses of soil samples from
the saturated zone (from cores, excavations, etc.)  can be applied.  This method tests the assumption that all of the organics
in the subsurface  are either dissolved  in ground  water or adsorbed to  soil  (assuming  dissolved-phase sorption, not  the
presence of  NAPL). By using the concentration of organics on the soil and the partitioning calculation, a theoretical pore-
water concentration of organics in ground water  is determined.  If the theoretical pore-water  concentration is greater than
the estimated  volubility of the organic constituent of interest, then NAPL may be present  at the site. A worksheet  for
performing this calculation  is presented  below; see Feenstra, Mackay, and Cherry (1991) for the complete methodology.
Step 1: Calculate Sj , the effective volubility of organic constituent of interest.    |See Worksheet 1, above. |
Step
       Determine Koc, the organic carbon-water partition coefficient from one of the following:
       A) Literature sources (such as 22) or
       B) From empirical relationships based on Kow, the octanol-water partition coefficient, which is also found in the
          literature (22). For example, Koc can  be estimated from Kow using the following expression developed for
          polyaromatic hydrocarbons (8):   i - L
                                           Log Koc = 10* Loe Kow - 0 21 I  Other empirical relationships between Koc
                                                                            and Kow are presented in refs. 4 and 15.
Step 3: Determine foe, the fraction of organic carbon on the soil, from a laboratory analysis of clean soils from the site.
       Values for foe typically range from 0.03 to 0.00017 mg/mg (4). Convert values reported in percent to mg/mg.

Step 4: Determine or estimate pfo, the dry bulk density of the soil, from a soils analysis. Typical values range from 1.8 to 2.1
       g/ml  (kg/1). Determine or estimate  (pw, the water-filled porosity.
Step 5: Determine Kd, the partition (or distribution) coefficient between
       the pore water (ground water) and the soil solids:
                                                                                   Kd = Koc * foe
Step 6 Using Ct, the measured cone, of the organic compound in saturated soil in mg/kg,
       calculate the theoretical pore water cone, assuming no DNAPL (i.e., Cw in mg/1):
                                                                                          Cw =
                           e
Step 7  Compare  Cw and Sj (from Step 1):
                                                       Q
                                                Cw > S | suggests possible presence of DNAPL
                                                       a
                                                         suggests possible absence of DNAPL
                                                Cw< S:
  (Ct * pb)

(Kd*pb + (pw)

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                                  GLOSSARY (adapted from Cherry, 1991):
DNAPL: A Dense Nonaqueous Phase Liquid. A DNAPL can be either a single-component DNAPL  (comprised of only
one chemical) or a mixed DNAPL (comprised of several chemicals). DNAPL  exists in the subsurface as free-phase DNAPL
or as residual DNAPL (see following definitions). DNAPL does not refer to chemicals that are dissolved in groundwater.

DNAPL ENTRY LOCATION: The area where DNAPL  has entered the subsurface, such as a spill location or waste pond.

DNAPL SITE:  A site where DNAPL has been released and is now present in the subsurface as an immiscible phase.

DNAPL ZONE: The portion of a site affected by free-phase or residual DNAPL  in the subsurface (either the unsaturated
zone  or saturated zone).  The DNAPL  zone has organics in  the  vapor phase (unsaturated zone), dissolved  phase (both
unsaturated and saturated zone), and DNAPL phase (both unsaturated  and  saturated zone).

DISSOLUTION:  The process by which soluble organic components from DNAPL dissolve in ground  water or dissolve in
infiltration water and form a  ground-water contaminant plume.  The duration of remediation measures (either clean-up or
long-term containment) is determined by  1) the rate of dissolution that can be achieved in the field,  and 2)  the mass of
soluble components in the residual DNAPL  trapped in the aquifer.

EFFECTIVE  SOLUBILITY:  The theoretical  aqueous  volubility of  an  organic constituent  in  ground water that  is in
chemical equilibrium with a mixed DNAPL  (a DNAPL containing several organic chemicals).  The effective volubility of a
particular organic  chemical can  be estimated  by multiplying its mole fraction in the DNAPL mixture by its pure phase
volubility (see Worksheet 1, page 7).

FREE-PHASE  DNAPL: Immiscible liquid existing in the subsurface with a positive pressure such that it can flow into a
well.  If not trapped  in  a pool, free-phase DNAPL will flow vertically  through an aquifer or  laterally down sloping  fine-
grained stratigraphic  units.  Also called mobile  DNAPL or continuous-phase DNAPL.

PLUME: The zone  of contamination containing organics  in the dissolved phase.   The plume  usually will originate  from
the DNAPL  zone  and extend downgradient for  some  distance  depending on site  hydrogeologic and chemical  conditions.
To avoid confusion, the term  "DNAPL plume" should not  be used to describe a DNAPL pool; "plume"  should be used only
to refer to dissolved-phase organics.

POOL and LENS: A pool is a zone  of free-phase DNAPL at the bottom of an aquifer.  A lens is a pool that rests on a fine-
grained stratigraphic unit  of  limited areal extent.  DNAPL  can be recovered from a pool or lens if a well is placed in the
right  location.

RESIDUAL DNAPL:  DNAPL held in  soil pore spaces  or fractures by capillary forces (negative pressure on DNAPL).
Residual will remain trapped  within the pores  of the porous media unless the viscous forces (caused by the dynamic force
of water against the DNAPL) are greater than  the  capillary forces holding the  DNAPL in the pore. At most sites the
hydraulic  gradient required to mobilize all of the residual  trapped in an aquifer is usually many times  greater than the
gradient that can be produced by wells or trenches (26).

RESIDUAL SATURATION:  The saturation  (the fraction of total pore  space containing DNAPL) at  which DNAPL
becomes discontinuous  and is immobilized by  capillary  forces (14).  In  unsaturated  soils, residual  saturation typically
ranges from  5% to 20% of total pore volume, while  in the saturated zone the  residual saturation is higher, with  typical
values ranging from  15% to  50%  of total pore  volume (14,17). At many  sites, however, DNAPL migrates preferentially
through small-scale fractures  and heterogeneities in the soil, permitting  the DNAPL  to penetrate much deeper than would
be predicted from  application of typical  residual saturation values (16).


                                                               DNAPL ZONE              Dissolved-Phase PLUME
Defined Areas at a DNAPL Site          (contains free-phase DNAPL in pools or
                                                         lenses and/or residual DNAPL)
                                                          z.
         DNAPL ENTRY LOCATION
         (such as a former waste pond)
                                                                                            Ground Water Flow Direction

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                                                     References
1. Anderson, M. R., R.L. Johnson, and J.F. Pankow, The Dissolution of Residual Dense Non-Aqueous Phase Liquid (DNAPL) from a
        Saturated Porous Medium, Proc.:  Petrol. Hcarb. and Org.  Chemicals in Ground  Water NWWA. Houston, TX, Nov., 1987.
2. Cherry, J. A., written communication to EPA DNAPL Workshop, Dallas, TX, R. S. Kerr Environmental  Research Laboratory, U.S.
        EPA, Ada, OK., Apr. 1991.

3. Connor, J. A., C.J. Newell, and D.K. Wilson, Assessment, Field Testing, and Conceptual Design for Managing Dense Nonaqueous
        Phase Liquids (DNAPL) at a Superfund Site, Proc.: Petrol. Hcarb. Org. Chemicals in Ground Water. NWWA, Houston, TX, 1989.
4. Domenico, PA. and F.W. Schwartz, Physical and Chemical  Hydrogeology, Wiley, New York, NY, 1990.

5. Feenstra, S. and JA. Cherry, Subsurface Contamination by Dense Non-Aqueous Phase Liquids (DNAPL)  Chemicals. International
        Groundwater Symposium. International Assoc. of Hydrogeologists, Halifax, N. S., May 1-4,1988.
6. Feenstra, S., D. M. MacKay, and JA. Cherry, A Method for Assessing Residual NAPL Based on Organic Chemical Concentrations in
        Soil Samples, Groundwater Monitoring Review, Vol. 11, No. 2, 1991.

7. Hunt, J. R., N. Sitar, and K.D. Udell, Nonaqueous Phase Liquid  Transport and Cleanup, Water Res. Research. Vol. 24 No. 8,1991.
8. Karickhoff, S. W., D.S. Brown, and TA. Scott, Sorption of Hydrophobic Pollutants on Natural Sediments, Water Res. R.. Vol. 3,1979.

9.   Keller, C. K., G. van der Kamp, and J.A. Cherry, Hydrogeology of Two Saskatchewan Tills, J. of Hydrology, pp. 97-121,1988.
10.  Kueper, B.H. and E. O. Frind, An Overview of Immiscible Fingering in Porous Media. J. of Cont. Hydrology. Vol. 2,1988.

11. Mackay, D.M. and J.A. Cherry, Ground-Water  Contamination:  Pump and Treat Remediation, ES&T Vol. 23, No. 6,1989.
12. Mackay, D. M., P.V. Roberts, and J.A. Cherry, Transport of Organic Contaminants  in Ground Water, =  Vol. 19, No. 5,1985.

13. Mendoza, C.A. and T.  A. McAlary, Modeling of Ground-Water Contamination Caused by Organic Solvent Vapors, Ground
        Water.  Vol. 28, No. 2, 1990.
14. Mercer, J.W. and R.M. Cohen, A Review of Immiscible Fluids in the Subsurface: Properties, Models, Characterization and
        Remediation, J. of Cont. Hydrology. Vol. 6, 1990.

15. Olsen, R.L. and A. Davis, Predicting the Fate and Transport  of Organic Compounds in Groundwater, HMC. May/June  1990.
16. Poulson, M. and B.H. Kueper, A Field Experiment to Study  the Behavior of Perchloroethylene in Unsaturated Porous Medium.
        Submitted to = ,   1991.

17. Schwille,  F.. Dense Chlorinated Solvents in Porous and Fractured Media: Model Experiments (English Translation), Lewis
        Publishers, Ann Arbor, MI, 1988.
18. Shiu, W.Y., A. Maijanen, A.L.Y. Ng, and D. Mackay, Preparation of Aqueous Solutions of Sparingly Soluble Organic Substances:
        11. Multicomponent System - Hydrocarbon Mixtures and Petroleum Products, Environ. Toxicology & Chemistry. Vol.  7,1988.

19. Sitar, N., J. I<. Hunt, and J.T. Geller, Practical Aspects of Multiphase Equilibria in Evaluating the Degree of Contamination, Proc. of
        the Int. Asso. of Hydrog. Conf. on Subsurface Cont.  by  Immiscible Fluids. April 18-20, Calgary, Alb., 1990.
20. U.S. EPA. Dense Nonaqueous Phase Liquids. EPA Ground Water Issue Paper,  EPA/540/4-91-002, 1991.

21. US. EPA. Evaluation of Ground-Water Extraction Remedies. Volume  1  (Summary Report). EPA/540/2-89/054, 1989.
22. Verschueren, K., Handbook of Environmental Data on Organic Chemicals. Van Nostrand Reinhold, New York, NY, 1983.

23. Villaume, J. F.,  Investigations at Sites  Contaminated with Dense Non-Aqueous  Phase Liquids (~NAPLsl Ground Water  Monitoring
        Review. Vol. 5, No. 2, 1985.
24. Waterloo  Centre for Ground Water Research, University  of Waterloo Short  Course, Dense Immiscible Phase Liquid Contaminants
        in Porous and Fractured Media, Kitchener,  Ont, Oct., 1991.

25. Waterloo  Centre for Ground Water Research, University of Waterloo  Short Course, Identification of DNAPL Sites: An  Eleven
        Point Approach. Kitchener. Ont., Oct., 1991.
26.  Wilson, J.L. and S.H. Conrad, Is Physical  Displacement of Residual Hydrocarbons a Realistic Possibility in Aquifer Restoration?,
        Proc.: Petrol. Hcarb. and Org. Chemicals in Ground Water. NWWA. Houston, TX, NWWA, Nov. 5-7,1984.
 NOTICE:  The policies and procedures set out in this document are intended solely as guidance.  They are not intended, nor can they
 be relied upon,  to create any rights enforceable by any party in litigation with the United States. EPA officials may decide to follow
 the guidance provided in this  memorandum,  or to act at variance with  the guidance,  based on an analysis  of specific  site
 circumstances. The Agency also reserves the right to change  this guidance at any time without public  notice.
    For more information, contact:     Randall  R.  Ross
                                       R.  S.  Kerr Environmental Research Laboratory
                                       Office  of Research  and Development
                                       U.S.  Environmental Protection Agency
                                       Ada, Oklahoma 74820

                          Authors:     Charles  J. Newell, Groundwater Services,  Inc., Houston,  Texas
                                       Randall  R.  Ross,  R.  S. Kerr  Environmental  Research Laboratory

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