IntroductiontoNAPLs

Reviewofgeneralconcepts
LNAPLandDNAPLmigrationpatterns
Behaviorinthesubsurface
Measurementinwells
Emergingremediationmethods
DetailedcasestudyHillAirForceBase

WhatareNAPLs?
Immisciblehydrocarbonsinthesubsurfacewhich
canpartiallydissolveintowateratveryslowrates
Canbeeitherlighterthanwater(LNAPL)or
denserthanwater(DNAPL)
Formavisible,separateoilyphaseinthe
subsurface
Complexmigrationgovernedbygravity,
buoyancy,andcapillaryforces,andsoiltexture

PhaseDistribution
Freephase,aqueous,gaseous,andsolid
Distributiondictatedbyfourprocesses:

Volatilization(HenrysLaw)
Dissolution(solubility)
Sorption(tailingeffectsinpump/treatsystems)
Biodegradation(aqueousphasemostly)

LNAPLTransportProperties

Density(LNAPLvsDNAPL)
Viscosity(governsmobilityinsubsurface)
Interfacialtension(porescaleeffect)
Wettability(affinityofsoilforfluids)
Capillarypressure(pressureacrossaninterface)
Saturation(fractionofporespacecontainingfluid)
Relativepermeability(functionofsaturation)

Mobilevs.ResidualNAPL
Trappe d
Water

Continuous
"Slug" of NAPL

Solid (such
as sand
grain)

MobilePhaseNAPLor
(FreePhaseNAPL)isa
continuousmassofNAPL
thatcanflowundera
hydraulicgradient

Individual
NAPL "Blobs"

Wate r
Solid (such
as sand
grain)

ResidualPhaseNAPLis
trappedintheporespaces
betweenthesoilparticles,
andcannotbeeasilymoved
hydraulically

LongTermSources
TotalmassofNAPLatasiteisoftenmanytimes
thetotaldissolvedmassatthesamesite
TheEPAin1989and1992concludedthatpoor
performanceofpumpandtreatsystemswasdue
toNAPLsactingasacontinuingsource
OnekgofNAPLcancontaminate:
100,000Lofgroundwaterat10mg/L,or
100,000,000Lofgroundwaterat10g/L

ItcantakemanyyearstodissolvealargeNAPL
source

SmearingofLNAPL
Seasonalfluctuationofwatertable
Pumpandtreatsystemwithlarge
drawdownscausesseriousproblemif
wellsfailandwaterlevelincreases
TrappingofLNAPLbelowthewatertable
TrappingofLNAPLonclaylensaswater
tabledeclines

LNAPLReleasetoVadoseZone
Residual
Saturation of
NAPL in
Vadose Zone
Vadose
Zone

Infiltration, Leaching

Ground Water
Flow
Dissolved Contaminant
Plume From NAPL Residual
Saturation

LNAPLattheWaterTable
Residual
Saturation
of LNAPL
in soil

Infiltration and
Leaching

Vadose
Zone

Groundwater
Flow

Dissolved
Contaminant Plume

Free-Phase Product Layer

in Saturated Zone

DNAPLbelowtheWaterTable
Dissolved
Contaminant
Plume

Residual
DNAPL
Low Permeable
Stratigraphic Unit

DNAPL Pools

Sand
Groundwater Flow

Clay
After Waterloo Centre for Groundwater Research, 1989.

Wettability
Capillarypressureproportionaltointerfacial
tensionandinversetoradiusofcurvature
Fluiddrawnintoporeisthewettingfluid
Fluidrepelledbycapillaryforcesisthenon
wettingfluid
Waterisalmostalwayswettingwhenmixedwith
airorNAPLsinthesubsurface
NAPLisgenerallythewettingfluidinairbutnon
wettingfluidinwater

WettingRelationships

Testing fluid: water

Background fluid: NAPL
< 70

Testing fluid: NAPL

Background fluid: air
> 110

NAPLisNonwettingfluid
Conclusion:
NAPL is
the wetting fluid

Conclusion: Water is
the wetting fluid

AIR

NAPL
NAPL

Water
SOLID

SOLID

= Contact Angle
General Wetting Relationships for Air, Water, NAPL:
System

Wetting Fluid

Non-Wetting Fluid

air:water
air: NAPL
water:NAPL
air:NAPL:water

water
NAPL
water
water>organic>air

air
air
NAPL
air

NAPLmigrationinprimaryvs.
secondaryporosity.
(A)NAPLmigrationthroughprimaryporosity.
(B)NAPLmigrationthroughsecondaryporosityfeatures
(fractures,rootholes,etc.).
Source

Source

B
DNAPL

DNAPL

LNAPLMovingUpgradient
Source
Zone Forcing
LNAPL into
Confined Aquifer

Confining
Layer

Dissolved
Contaminant Plume

LNAPL Plume Moving

"Upgradient" to
Stratigraphic Trap

Groundwater
Flow

FracturedRockSystem
Vadose
Zone

Residual
DNAPL

Sand

Fractured
Rock or
Fractured
Clay

After Waterloo Centre for Ground Water Research, 1989.

CompositeDNAPLSite
Residual
DNAPL
Dissolved
Contaminant
Plumes

Sand
Fractured
Clay

Residual DNAPL
DNAPL Pool

Sand

Impermeable Boundary
After Waterloo Centre for Ground Water Research, 1989.

DissolvingNAPL
Fresh Wate r

Residual NAPL Containing

Soluble Hydrocarbons

Contaminated
Groundwater
Forming
Dissolved
Hydrocarbon
Plume

RelativePermeability
100%

80%

Relative
Permeability

NAPL

Water

60%

40%

Residual
Saturation
of NAPL

Irreversible
Saturation 20%
of Water
0
0
100%

Water Saturation

100%

NAPL Saturation
Sor

FlowRegimes
1.00

1.00

0.80

0.80

0.60

0.60

0.40
0.20

Kr = relative
0.10
permeability 0.08

0.40

I
DNAPL
Flow

0.20

III
Water
Flow

0.06
0.04
0.02
0.01

II
Mixed
Flow
Increasing DNAPL Saturation
Increasing Water Saturation

K r = relative
0.10
0.08 permeability
0.06
0.04
0.02
0.01

HydraulicMobilizationofNAPL
SLOPE OF
WATER TABLE

100

Easiestto-Move
Blobs
Are

10

Required
Hydraulic
Gradient
(ft/ft)

100

All Blobs
Mobilized

10

Mobilized
1

No Blobs Mobilized - NAPL

Trapped by Capillary Forces
10-3

10-2
CLEAN SAND
SILTY SAND

10:1

Z
X

0.1

100 :1

10-1

1
GRAVEL

HYDRAULIC CONDUCTIVITY
(cm/sec)

0.1

1:1
X

1:10

Z
X

CalculatingSaturation
Continuous Individual
Slug of
NAPL
NAPL
"Blobs"
Wate r
Solid
Volume of NAPL
VNAPL

Volume of Open
Pore Space
(Effective Porosity)
VPore

S NAPL

VNAPL

VPore

Canbeestimatedin
thelabviathe
following:

b TPH
So
n n 106

Where:
b=soilbulkdensity[g/cm3]
n=NAPLbulkdensity[g/cm3]
n=porosity
TPH=TotalPetroleum
Hydrocarbons
[mgNAPL/kgdrysoil]

PartitioningTracerTestforSN
Chemicalsareintroducedconsistingofconservative
andpartitioningtracers(PTT)
NAPLWaterPartitionCoefficientKN.
KN=CN/CwwhereCNistheconc.inNAPLandCwis
waterconc.
Atsteadystate,theeffectistodelayorretardthePT
transportrateaccordingtoaretardationfactor
R=1+(KNSN)/(1SN)=tp/tn

PartitioningTracerTestforSN
TpistraveltimeforthePartitioningtracer
Tnisthetraveltimefortheconservativetracer(Br)
Sorptionisassumedinsignificant
PTcompoundsoftenusedincludealcoholssuchas

ethanol (0.1)KNvaluesinparentheses
npentanol(1.4)
nhexanol(4.6)
2,2dimethyl3pentanol(12.9)
nheptanol(20.0)

TypicalValuesofSN
EW1fromUFtestcell
EW2fromUFtestcell
EW3fromUFtestcell

0.031
0.049
0.088

TotalorAvgforUFcell

0.054orabout5.4%
NAPLSaturation

PartitioningTracerTestforSN
MeasuredBTCforPTTwithbromide
Timedifferencebetweendifferentchemicalsallows
calculationofSN
Bromide
npentanol
2,2DMP

C/C0

500

1000

1500

2000

EffluentVolume(L)

ApparentLNAPLThickness
Monitoring Well
True
LNAPL
Thickness

Apparent
LNAPL
Thickness

Vadose Zone
Capillary Fringe
Saturated
Zone

w LNAPL
h f hw
LNAPL

ApparentLNAPLThickness
Thicknessinscreenedwellcasingonlyindicator
ofactualthicknessintheunit
Thicknessinthewellmaybe2to10timeslarger
thanactualthicknessofmobileLNAPLinthe
surroundingaquifer
Nomethodsexisttoimprovetheseestimates

DNAPLDetectionProblems
Vadose
Zone
Saturated
Zone

DNAPL

DNAPL

Saturated
Zone
DNAPL

DNAPL
Clay
Screen Too High
Above Confining Unit
No Accumulation

Clay

Clay
Screen Too Deep
Into Confining Unit
Too Much Accumulation

Clay
Screen Penetrates Clay Lens
Accumulation in Wrong
Place

RemediationofLNAPL

Excavation
Trenches,drains,andwells
Soilvaporextraction(SVE)
Airsparging
Enhancedoilrecovery(water,steam,cosolvents,
surfactants,etc)
Bioremediation
Physicalbarriers

HillAFBinUtah

LargestRemediationProjectfor
NAPLinaSourceZone
Jointprojectwithseveral
universities,U.S.EPA,U.S.Air
Force,andprivateindustry
19941998