WATERRESOURCES

RESEARCH,
VOL.30,NO.2,PAGES
355-368,
FEBRUARY
1994

Nonequilibrium
masstransfer
between
thevapor,aqueous,
and
solidphasesin unsaturated
soilsduringvaporextraction
J. E. Armstrong, E. O. Frind, and R. D. McClellan
Waterloo
Centrefor Groundwater
Research,
University
of Waterloo,
Waterloo,
Ontario,
Canada

Abstract.Vaporextraction is a commonlyusedmethod forremovingnonaqueous

phaseliquidvolatileorganiccompounds (VOC)fromthevadose zone.Experience
indicates
thatin theabsence of liquidVOC,theefficiency of vaporextraction
systems
decreasesdramaticallywithtimeaseffluentconcentrations approachzero
asymptotically.
Whensuchsystems arerestarted
aftera temporary shutdown,effluent
concentrations
areoftenfoundto recoverfor a shortperiodbeforedropping backto
preshutdown levels.Thisbehavioris generallyattributed
to kineticprocesses which
limitthetransferof contaminant intothemovingair. A numericalmodelis developed
to simulatethe rate-limitedextractionof volatilecompoundsgoverned by first-order
kineticmasstransferprocesses.A sensitivityanalysisis performed to identifymodel
responsesto variouskinetic and equilibriumpartitioning
processes.
The modelis
calibrated
usingexperimentaldatacollectedfroma pilot-scale experimentinvolving
vaporextractionof trichloroethylene
from finesand.An analysisof therelationships
betweenairflowratesand the kineticmasstransfercoefficientsundervariouspumping
schemesshowsthat for a given condition, increasingthe flow rate has little effect
beyonda certain point. It is also shownthat pulsedpumpingis generallylessefficient
than continuouspumping at a low rate.

Introduction efficiency of SVE in removing VOCs in the subsurface

thereforedependson the extent to which the advecting air
Volatile organic compounds (VOCs) are ubiquitous con- comes into contact with the residual.
taminantsthat have been found in the subsurfaceas pure In the absenceof pure phase, contaminantmass may still
liquidphase, dissolvedin the soil moisture, sorbedto aquifer be presentin the dissolvedand sorbedphases.Controlled-
materials, and volatilized in soil gas. In the cleanup of domainvaporextractionexperimentsundertheseconditions
contaminated sites, because of the high toxicity of VOCs often show very long tailing behavior [McClellan and Gill-
essentiallyall of the contaminant in its various phasesmust ham, 1990; Grathwohl et al., 1990; Gierke et al., 1992;Rauh,
be removed in order to meet drinking water standards. 1992], indicating that SVE by itself may be inefficient in
Experienceshows that this goal can be difficult to meet. achievinga completecleanup. To accountfor the effluent
Soil vapor extraction (SVE), also known as soil venting, tailing, rate-limitedmasstransfer processes,includingparti-
vapor stripping, or in situ volatilization, is an innovative tioningbetweenthe soil gas, the soil moisture,and the soil
technique for the removal of VOCs. SVE procedures are grains, must be considered.
reviewed by Pedersen and Curtis [1991], while screening Phasepartitioningin the absenceof the pure phase in-
toolsfor the evaluation of SVE suitability are describedby volvestwo mainprocesses: vo!atilizationfrom the dissolved
Johnson et al. [1988]. The technique is based on simple phaseand desorption from the soil grainsto the dissolved
physical/chemicalprinciples: By applying a vacuum, con- phase.Direct sorption/desorption from the air phaseto the
taminated air in connected soil pores is extracted and aquifersolidmaterialmay be neglectedin mostsubsurface
replacedby clean atmosphericair; this perturbsthe local environments,exceptundervery arid conditions[Chiouand
chemicalequilibrium, causingthe transferof contaminant Shoup,1985;OngandLion, 1991].Severalauthors[Choand
fromthe residualphase,dissolvedphase,and sorbedphase Jaffe, 1990;LeStrange,1990;Grathwohlet al., 1990;Gierke
into the softgas, where it can be removed.In theory,this et al., 1992] found masstransfer from water to air to be a
shouldeventually lead to a completecleanup. rate-limited processunder advectively dominatedcondi-
Experimentalresultsfor naturalfield-scalesystemsoften tions. Gierke et al. [1992] used a dual-domainmodel which
show effluent concentrations below the theoretical maximum
incorporateddiffusionwithin immobile, spherical,water-
basedon contaminantpartialpressures [Baehret al., 1989; saturatedmicropores,but found that the exact pore geome-
Mackay et al., 1990; Rainwater et al., 1989]. The main try is of little importanceas a simplefirst-orderkinetic
reason for this is the nonuniform distribution of contami-
transfer model can give similar results.
nants [Kueper and Frind, !988] and the loweredlocal The rate-limitingprocesseswhich causethe long tailing
permeabilityof zonescontaining purephaseresidual,which can result in exceedinglylong cleanuptimes [Mackay and
will causesomeof the air to bypassthe residualzone. The
Cherry, 1989],requitingthe pumpingof large volumesof
Copyright1994by the AmericanGeophysical
Union. slightlycontaminated air. This suggests
that by decreasing
Papernumber 93WR02481. the flow rate, the amount of massrecoveredby each pore
0043-1397/94/93WR-02481$05.00 volumeof pumpedair canbe increased
becauseof thelonger
355
356 ARMSTRONG ET AL.: NONEQUILIBRIUM MASS TRANSFER DURING SOIL VAPOR EXTRACTION

exposure time of the air to the contaminants. Gierke et al. 1989;Falta et al., 1989],although
of littleimportance
during
[1992], however, point out that a lower limit existswhere the continuousextraction [Rathfelder, 1989], may be apprecia-
diffusive flux becomes of a similar order of magnitude as the ble during nonpumping periods in pulsed pumping;this
advective flux and suggestthat pulsed pumping be consid- mechanism is therefore included.
ered under such circumstances. The vapor transport model developed by Mendoza and
In pulsed pumping [Keely et al., 1987; Crow et al., 1987] Frind [1990a], which uses the above assumptions,is usedas
the strategy is to extract air only until the tailed portion of a basis for the development. The original model has the
the effluent curve is reached, then to turn off the pump and capability to allow a spatially variable temperature distribu-
let the air phase concentrationsrecover. Pulsingis intended tion.
to give lower energy costs and lower effluent treatment
costs. The lengths of the on and off periods depend on the Vapor Transport Equation
physical parameters, the pump capacity, and the rate of
recovery. For an analogoussaturated-zonesituation,extrac- Under the assumptionsof a static moisture distribution
tion of a densenonaqueousphaseliquid(DNAPL) by pulsed and an incompressibleair phase, the advective-dispersive
pumpingwas found not to be significantlymore efficientthan transport equation in Cartesian coordinatesis
continuouspumping[Powerset al., 199!]. In general,little
aI Oavi
OCa 3Ca
L(C)--O 0 \OC
quantitative information is available on the efficiencyof Oa
pulsed vapor extraction. / ot
Mathematical model simulations can be useful in obtaining
insight into the governingmechanisms.Brusseau [1991] OCw OCs
developeda highly generalmodelassumingboth advective + Ow-•-+po Ot i,j=x, z (1)
and nonadvective domains within the soil and allowing both
equilibriumand nonequilibriumphasetransferin each do- where subscriptsa, w, and s designate the gaseous,dis-
main. A drawback of this general approach is the large solved, and sorbedphases(also referred to as the air, water,
number of parametersthat are required to describethe andsoilphases)
ofthecontaminant,
Ca, C•(M/L3),andCs
advective/nonadvective domain fractions and partitioning (dimensionless)are the correspondingconcentrations,0a
parameters.Nevertheless,Brusseausucceeded in matching and Oware the volumetricair and water contents(dimen-
a set of publishedexperimentalresultswithoutresortingto sionless),
andpois thesoildrybulkdensity (M/L3). The
aswellasthose differentialoperatorL(C a) denotesthe dispersiveand ad-
curvefitting.Unfortunately,hissimulations,
of Gierke et al. [1992], extend to air extraction volumes vective terms; we will use this notation in subsequent
rangingfrom 13 to lessthan 100porevolumesonly, whereas developments. The threetermson the right-handsideof (1)
severalauthors[McClellan and Gillham, 1990;Grathwohlet representthe changesin contaminantmassstoredin the
al., 1990;Rauh, !992] showthat effluenttailingcanlastover vapor phase,the dissolvedphase,and the sorbedphase,
thousands of pore volumes. respectively.
The objectiveof this paper is to investigatethe various The linear air velocity, vi(L/T), is determinedfrom the
processes that causetailingoverthe longertimeframe,to solution of the air continuity equation and the subsequent
gain insightinto the influenceof the kinetic masstransfer application
of the Darcyequationto pressure. The disper-
mechanisms,to investigatethe relationshipbetweenextrac- sion tensor, Dij(L2/T),isofthestandard form[Bear,1972]
tion efficiencyand the airflowrate, and to comparepulsed expressed in termsof longitudinal dispersivity
ar (L), trans-
pumping to continuouspumping
schemes.An existingfinite versedispersivity at(L), andthe moleculardiffusioncoef-
elementvaporflow model,modifiedto includerate-limited ficientDa(L 2/T). The tortuositycorrectionof Millington
partitioning,is used. andQuirk[1961]is used.The development of the density-
dependent
airflowequation
is givenby Mendoza
andFrind
[1990a].
Mathematical Model Boundaryconditionsfor (1) canbe of the followingtypes:
We are concerned here with the flow of vapor in the
unsaturated soil zone and the mass transfer of contaminant
Specifiedconcentration(type 1)
betweenthe gas phase,the dissolvedphase,and the ad- Ca= C0 (2a)
sorbedphase.We neglectinfiltration
eventsandassumethe
soil moisture to be immobile and constant in time (a more Specifiedmassflux (type 3)
generalmodelinvolvingmobilevaporandwaterphases was
developedby SleepandSykes[1989]).Theeffectof venting OCa
on soil moisture has been investigatedby Grathwohl et al.
VnCa-- D •On = voCo (2b)
[1990]aswell asby McClellan[1991],whofoundno signif-
icant soil dryingto occur.However,SVE mayleadto soilDuringvaporextraction,
the groundsurface
boundary
dryingunderverywetconditions
[Regalbuto
et al., 1988]. condition
canberepresented
by a zeroconcentration
gradi-
Darcy'slaw canbe usedto describe airflowduringvapor ent if sealed,or by a zero massflux (type 3 boundary
extraction, assumingthat gas slippage(the Klinkenberg condition)if open.Otherinletboundariesfor cleanaircan
effect)is negligible[Massmann,1989;McWhorter,1990], alsobe described by a zeromassfluxboundary condition.
andair compressibility
effectsarealsonegligible
for applied Anextraction
wellisdescribed
usinga vacuum
pressure
and
vacuumpressures prevailing
underSVE conditions [Crois• a zerodispersive
gradientboundary; massis assumedto
et al., 1989; Wilsonet al., 1988].Density-inducedgas leavethesystembyadvection only.Initialconditions
with
advection[Mendozaand Frind, 1990b;Sleepand Sykes, respectto concentrations
in eachphase mustbespecified.
 ARMSTRONG
ET AL.' NONEQUILIBRIUM
MASSTRANSFER
DURINGSOILVAPOREXTRACTION 35-

Adv• Air

dissolvedcontaminant
OaD
(i• • Oxj i •=
/ 0av ROa
at
(6)

where R is the retardation factor:

partitioning
0w P bKd
R = I +•+ {7)
OaH O.H
The equilibrium form is valid for diffusion-dominated or
Soil Grain
weakly advective conditions such as those described by
Mendoza and Frind [1990b]. Under strongl.xadvective con-
.

ß ditions such as occur with SVE schemes,the equilibrium

Water/Solid
modelis not suitableas it is unable to reproducethe typically
partitioning
long tailing of the effluent curve observed in experimental
(d½sorption) data [Johnson et al., 1987' Mackay et al., 1990' Grathwohl et
al., 1990].
Figure 1. Schematicrepresentationof masstransferpro-
cesses in the vadose zone. NonequilibriumMass Transfer Relationships
Several authors have shown that long effluent tailing can
be reproduced by models based on first-order kinetic mass
transfer relationships [e.g., Sleep and Sykes, 1989; Rath-
Equilibrium Mass Transfer Relationships felder, 1989]. Various conceptual models based on either
physical or chemical nonequilibrium processes (or both) of
In the absence of pure phase, contaminant will be storedin vaporization and sorption have been proposed [van Genu-
the dissolvedand the sorbed phases, in addition to the gas chten, 1981' Brusseau and Rao, 1989; Cho and Ja•', 1990;
phase.We assumethat a continuousfilm of water, beingthe Brusseau, 1991; Gierke et al., 1992]. The behavior of the
wettingfluid, coats the soil grains so that gas-to-solidmass different models and their success in representing experi-
transfer is possible only via the water phase. The relevant mental observations are often very similar.
masstransfer processes(Figure 1) are therefore between the As a conceptual basis we will here assume that diffusive
soil gas and the dissolved phase, and the sorbed phase and mass transfer between the air phase and the water phase
the dissolvedphase. We assumethat each processis revers- takes place through a boundary layer which is part of the
ible and either instantaneous (equilibrium) or rate limited. water phase. The driving force is the concentration gradient
Equilibrium partitioning between the gas and the water between the average concentration in the aqueous phase and
phasescan be expressed by Henry's law: the equilibrium concentration at the water/air interface. This
idealized diffusive masstransfer process is approximated by
Ca = HC,,. (3)
a first-order kinetic relationship and representsthe aggregate
where H is Henry's constant (dimensionless). of all physical nonequilibrium processesaffecting the migra-
Likewise, equilibrium partitioning between the dissolved tion of contaminant mass between the water and air phases,
andthe solid phases(sorption) can be expressedin the form including diffusion within the soil moisture and dead-end
of a linear Freundlich isotherm: pore effects. A similar first-order mass transfer process is
envisaged to represent partitioning between the water and
C s = KdC w {4) the solid phases. This second process can account for
kinetically limited desorption from soil grains and/or intra-
whereKa is thedistribution coefficient
(L3/M). Thedistri- particle diffusion within saturated soil grains.
bution coefficient is commonly expressedin empirical form A mass balance equation for the stationary water phase•
[Lyman et al., 1982]: with mass transfer across the air-x•ater and the water-solid
interfaces, can be written as
K d =focroc (5)
wherefoc is the massfractionof organiccarbon(dimension-
0 •= O,Aa,,.(C,,-HC,,.)- 0 A,,,s C - (8)
less)and K oc is the organiccarbonpartitioningcoefficient
(L•/M). Theaboverelationship
isgenerally
considered
tobe
where the first term on the right-hand side expresses air-
valid for soils with high organic carbon content (foc >
water transfer while the second term describes water-solid
0.1%). For soils with lower o•anic carboncontent(foc<
0.1%), sorptionto mineralgrainsmay be dominant[Piwoni transfer, with Aa,. and A,,.sbeing the correspondingmass
and Bannerjee, 1989;Brusseauet al., 1991]. The former transfercoefficient.,,
{T-l). C,•,represents
the averagecon-
authorsrecommendusinga minimumvalueoffoc = 0.1% to centrationin the water, while Ca/H and C.•/K d representthe
equilibriumconcentrationsat the air-water interface and the
calculateK a in suchcases.Under certainconditions,an
water-solid interface, according to {3) and {4). respectively.
organiccarbon-based distribution coefficientmay be mis-
A mass influx is taken to be positive.
leading[Boettcher et al. , 1991].
The correspondingmas• balance equation for the soil
Theaboveequilibriumrelationships
canberearranged
and
phase is
usedto expressthe dissolvedand sorbedphase concentra-
tions,C,, andCs, on thefight-handsideof (1), in theform
of equivalentair phaseconcentrations,Ca. Equation(1) {9)
then becomes
358 ARMSTRONG ET AL.: NONEQUILIBRIUM MASS TRANSFER DURING SOIL VAPOR EXTRACTION

In the boundary layer model the masstransfer coefficient study, only the seasonalthermal gradientwith depthis
dependson the diffusioncoefficientand, conceptually,the considered.
thicknessof the respectiveboundary layer. The thickness,
however, is not a measurable quantity since the process
representsa variety of diffusionpathwaysthroughthe het- Numerical Model
erogeneousmedium. The kinetic masstransfercoefficients The partial differential equations describing flow and
thus have meaningonly as lumped parametersrepresenting transport are solved using the Galerkin finite element
the integralof a multitudeof pore-scaleprocesses.Correla- method with triangular elements and linear basis functions.
tion relationships for thesecoefficientshavebeenproposed A centereddifferenceapproximationis used to represent
by Brusseau[1991];however,we feel that thesecan at best time, and masslumpingis usedto dampenoscillationsdueto
give an order-of-magnitudeestimate. More accurate case- parameterswhich may vary widely over relatively short
specificvalueswill haveto be determinedfromlaboratoryor distances. Details of the finite element method are found in
field tests by model calibration. textbooks [e.g., Huyakorn and Pinder, 1983].
Incorporationof two nonequilibrium partitioning
reactions By assuminga stationary water phase, the only spatial
in the model implies that there are three possiblecasesto linkage in the numerical equationsis due to the air phase.
consider:The extractionrate may be controlledprimarily by The water and solid phasesare linked in the systemvia the
(1) soil moisture/gaspartitioning(air/water, or AW), (2)spatiallyindependentequilibriumand kinetic masstransfer
desorptionfrom the soil matrix into the moisture(water/ relationships.The masstransfer relationshipscan be incor-
solid, or WS), or (3) somecombinationof the two processes porateddirectly into the numericalair phasetransportequa.
(air/water/solid,or AWS). The threecaseswill be referredto tions by using a technique developed by Leismann et al.
using these acronyms.In the AW model, sorptionis an [1988]. The development of the correspondingmatrix terms
equilibriumprocess,while in the WS modelthe air-water for the different model versions are given in the appendix.
partitioningis an equilibriumprocess. With this approach, only the air phase transport equations
The partitioningprocesses are incorporatedinto the air (in matrix form) need to be solved simultaneously,whilethe
phasetransportequationby replacingthe equilibriumphase dissolvedphaseand sorbedphaseequationscan be solved
mass changeterms on the fight-hand side of (1) by the explicitly.
corresponding kineticmasstransferterms.In the caseof the Spatialand temporalgrid discretizationsare controlledby
partially kinetic versions(AW and WS), one of the terms the standard Peclet and Courant criteria [Daus et al., 1985].
remainsin the equilibriumform while the otherassumesthe The matrix equationsfor flow and transportare solvedusing
kinetic form. The governingequationsfor the three model the conjugategradientandORTHOMIN iterativetechniques
types are as follows: implementedin the ORTHOFEM solversubroutines [Men-
AWS model. The equation for the air phase is doza, 1991]. Mass balance checks are performed following
OCa standardprocedures[Huyakorn and Pinder, 1983].
L(Ca)
= Oa-•-+ OaXaw(Ca-
HCw) (10)
The water phase equation is (8), and the solids phase Model Testing
equation is (9). Presentlyaccepted.practice
requiresthat a mathematical
AW model. The equationfor the air phaseis (10), while model be verified (to ensure that the model solves the
that for the water-solids phase is equations correctly)andvalidated(to ensurethat themodel
is conceptually correct).A newandinterestingperspective
OCw on this issue is raisedby Konikow and Bredehoeft [1992],
o a(C - HC = 0 (
ot who state that "validation per se is a futile objective,"
explaining thata modelcannotbe validated,but onlyproven
where the water-solid retardation coefficient is
not to be invalid.From our own experience,verificationofa
R s = 1 + (pbKa/Ow) (12) mathematical model is usuallypossibleonly in a limited
sensewhereanalyticalor otherprovensolutions areavail-
WS model. The equationfor the air-water phase is able. A successful comparison with anothermodelsimply
meansthat the two modelsgive the sameresults. We agree
generallywith KonikowandBredehoeft in thata complete
L(C,)= O,Rw
-•-+ OwXws
' (13) andunambiguous validation
of a modelincorporating
multi-
where the water-air retardation coefficient is
ple interactingprocessesmay be impossible dueto the
unavoidablenonuniqueness
of simulationresults.The pos-
Rw = • + (0•/0,H) (•4) sibilityof nonuniqueness
increases
withthe complexity
of
the model.The lack of generalvalidationdoesnot detract
The solidsphase equation is (9). from the value of the model, which is, above all, a toolto
Temperaturecan play a significantrole in vapor transport give insightinto complexnatural processes.
undercertainconditions[RathfeIderet al., 1991].Significant We will thereforeavoidthe useof theterms"verification"
temperaturevariationsin the soilor the soilgascan arisedue and "validation" and use instead "model testing" and
to the seasonaltemperaturegradient[Mendozaet al., 1990] "calibration,"whichwe believereflectmore accurately
or differencesbetweenthe ambientsoil temperatureand that whatactuallytakesplaceandleavesuswith a realisticsense
of the injectedair. Parametersthat may be sensitiveto these of the modeI's(andour own)limitations.
Theselimitations
variationsincludeHenry's constantand air viscosity.In this cause noproblem if oneisawareofthemandif themodel is
 ARMSTRONG ET AL.: NONEQUILIBRIUM MASS TRANSFER DURING SOIL VAPOR EXTRACTION 359

Table 1. Input Parameters for All Simulations

System Properties Model Testing Model Calibration

Length, m 0.5 1.524

Height, m 0.1 1.219
Temperature, øC 10 0
Applied pressure, Pa 200 3470
Permeability,
m2 1.7x 10-4 1.5x 10-1•
Porosity,% 40 seeFigure4
Watercontent,% 10 seeFigure4
Residual water content, % 8 8
Organiccontent, % 0.02 0.017', 0.08t
Bulkdensity,
g/cm
3 1.65 seeFigure
4
Transport/MassTransferProperties
Averagelinearair velocity,m/s 1 x 10-3 5 x 10-3 to 7 x 10-3
Longitudinal/transversedispersivity, m 0.01/0.001 0.05/0.001
Air-water
ratecoefficient,
s- • 10-4 seeFigure10
Water-solid
ratecoefficient,
s-• 10-4, 10-6 seeFigure10
Fluid Properties
Trichloroethylene
Molecular weight, g/mol 131.4 131.4
Diffusioncoefficient,
m2/s 7.6 x 10-6 7.2 x 10-6 to 7.4 x 10-6
Viscosity,Pa s 9.7 x 10-6 9.7 x 10-6
Henry's constant 0.17 see Figure 4
Koc, mL/g 126 126
Air
Molecular weight, g/mol 28.75 28.75
Viscosity,Pa s 9.73 x 10-6 9.73 x 10-6
*Lyman et al. [1982].
?Lee et al. [1988], Piwoni and Bannerjee [1989].

usedprimarily to gain insight into the interactions of the brief summary of the vapor extraction experiment that
variousphysical processesincluded in the model. providedthe data for the model, then test the sensitivityof
The numerical code was tested by comparison to a one- the model with respectto the parametersusingthe experi-
dimensionalanalytical solution for transport in a homoge- mental data, and finally calibrate the model againstthe data.
neouspartially saturated domain with kinetic partitioning The sensitivityanalysisstepprecedesthe calibration stepin
understeady flow. The analytical solution was derived and order to determine the importance of the physical parame-
codedby K. Tan (manuscript in preparation, 1993), follow- ters. A formal "validation" step prior to the sensitivity
ing the method presented by van Genuchten and Alves analysisis not performedsincethe resultswould clearly be
[1982].The numericalexperimentsimulatesthe extractionof nonunique.
trichloroethylene(TCE) vapor from a one-dimensionalcol-
umn containing fine sand at field moisture capacity. The Controlled Vapor Extraction Experiment
model allows for both rate-limited volatilization and sorp- A small-scalecontrolled vapor extraction experiment de-
tion, using the AWS formulation. Parametersused in the scribedby McClellan and Gillham [1990] is usedas a basis
simulationsare given in Table 1. Two casesare considered
whichdifferonly in the value of the water-solidsorptionrate
coefficient
(10-4 and 10-6 s-1 respectively)all other
parametersbeing the same. The TCE is assumedto be
initiallyat equilibriumin the vapor, dissolved,and sorbed
phases.
Normalized concentrations in the air, water, and sorbed
phases versus time calculated at the outflow end of the x A.•= 10'4s-•
-6 $-1
columnby the numericalandanalyticalmodelsare shownin
Figure2. The resultsshowexcellentagreementfor all three
phasesand both setsof kinetic sorptioncoefficients.The air
phaseconcentrationsfor both casesare identical, suggesting
,

thatair effluentconcentrationsare insensitivewith respectto

1 2
thesorptionratefor the parameters
usedhere.Massbalance
errors in the numerical model were less than 0.1%. The Time (hr)
resultssuggestthat the numericalmodel solvesthe govern- Figure 2. Model testing:Effluent concentrations
versus
ingequations
correctly. time,Xaw= 10-4 s-1 Linesdenote
ß
theanalytical
solution' ,

To relate the model to the real world, we first presenta symbols,the numericalsolution.
360 ARMSTRONG ET AL.' NONEQUILIBRIUM MASSTRANSFERDURING SOIL VAPOR EXTRACTION

clean 1.2
air air
entry /-A /•• exit
680 ß 540 200
ß
•-•.-
c- • 66O 770 ß 1360

ß 770 ß 1170 980

700 ß 940 ß 1680

o I I I !
o 1.5

Figure 5. Measuredair phase concentrationsat samplers

after9 daysof no pumping.Units are volumepercent,equal
to parts per million by volume divided by 10,000.
Figure 3. Box for vapor extraction experiment.

content. The porosity and bulk density of the soil were

for the site-specificmodeling. Only those aspectsthat are measured after completion of the experiment. The data are
directly relevant to the modelingare reviewed here; further shown in Figure 4.
details are given by McClellan [ 1991]. After 30 days of pumping, the effluent concentrationshad
The experiment was conducted with a steel box of dimen- dropped to 15 parts per million by volume (ppmv), and the
sions 1.5 m x 1.2 m x 0.45 m, (Figure 3) into which a fine pump was shut off. Soil gas concentrations measuredat the
sand at residual moisture content, uniformly mixed with a 12 samplingpoints at that time ranged from 0.3 to 70 ppmv.
known quantity of TCE, had been placed. The box was The sampled concentrations then rose to between 7 and 660
buried in the ground, with the top flush with ground surface, ppmv after I day, and to 530 and 2000 ppmv after 9 daysof
to maintain normal thermal conditions. Vapor extraction shutdown (Figure 5), indicating that a significant massof
using both continuousand pulsed pumpingwas performed TCE still remained in the box. However, the highest mea-
for approximately 90 days over a 100-dayperiod. By usinga sured gas phase concentration was less than 10% of the
controlled environment, complexities normally encountered saturation value. It was therefore concluded that the remain-
in the field due to soil heterogeneities,variable soil water and ing TCE was not likely present in the pure phase, but rather
contaminant distributions, and nonlinear air pathways, were in the dissolved phase retained by the soil moisture and
minimized. sorbed to the soil grains.
Air effluent concentrations were measured during periods The experimental data for the modeling were collected
of vapor extraction, and air phase concentrations were during the pumping which followed the 9-day shutdown
measured at selected times during periods of shutdown and period. To obtain the initial conditions, the data recordedat
equilibration using 12 samplers installed through the box lid. the 12 sampling probes (Figure 5) were used in the equilib-
Air pressures and temperatures were also measured at rium partitioning relationships to estimate the massremain-
selected times using probes. Time domain refiectometry ing in the box. After 46 hours of continuous pumping at a
probes were available to measure the in situ moisture constant flow rate, a series of three pulse tests (2 hours
equilibration, 1 hour of pumping) were run. The data subset
is shown in Figure 6.
The pump was subsequentlyleft in continuousoperation
].25 I
1.25 for another60 days with no effluent monitoring until theend
of the experiment. The massestimatedto be remainingin the
1.00
0.75 0.75 box basedon the samplerair concentrationsat that timehad
0.50 0.50 the potential to contaminate some 25,000 L of groundwater
0.25 - 0.25
to the drinking water limit for TCE (5 txg/L).
0.00 ' 0.00
0.38 0.42 0.46 0.50 1.35 !.45 1.55 1.65

Porosity Bulk Density{g/cm3)

experiments

1.25 .
• 1000 ß
•
!1.oo
.25 .
- • 1.oo
o

.
= 0.75 • 0.75 ' ß
• 1o0'
.m ß
'• 0.50 g 0.50 '
• ß '- 10
ca 0.25 ca 0.25 -
ß

0.00 ' ' I ' •' "" 0.0o , ] ', i' . ,

1
0.08 0.10 0.12 0.10 0.12 0.14 930 950 970 990
Time (kr)
Moisture Content Henry'sConstant

Figure6. Effluentconcentrations(not all pointsplottedl

Figure 4. Measured soil parameters after completion of usedforcalibration
andpulsetestsimulations [afterMcClel-
•experiment. lan, 1991].
 ARMSTRONGET AL.' NONEQUILIBRIUMMASSTRANSFERDURING SOIL VAPOREXTRACTION 361

SensitivityAnalysis
Under the presentstateof the art, somedegreeof model
calibrationto measureddata is still necessaryin order to
determine case-specific
kineticmasstransfercoefficients,as
suitabledirect relationships between these coefficientsand
theprimarymediumandfluidparametershavenot yet been
conclusively established. Brusseau [1991] made some o 0.01 ........................................................................
progress
by usingthe assumption
of rate-limiting
diffusion
withinthe liquidphaseto postulatea relationship
basedon a
diffusionpath length and an effectivediffusioncoefficient,as a. o.oo1{ , ' t '
hasbeen donefor rate-limited sorption[e.g., Brusseauet al., 0 5 !0
1991]. The universality of such relationships, however, Time (hr)
remainsunproven in view of the potential temporal and 1.0
spatialscaledependenciesof the relevantphysicalparame-
ters [Brusseauand Rao, 1989]. For example,the sorption
coefficientreported for the same chemical in the same soil Total Mass
hasbeenfound to vary over more than an order of magnitude
[e.g., Curtis et al., 1986;Ball and Roberts, 1991].
Prior to calibration it is useful to obtain a feel for the
sensitivityof a model with respectto the controllingparam-
eters. Because the soil porosity, moisture content, and Mass in Soil Water
densitywere measured, these factors were consideredfixed
with regard to model testing. The sensitivity analysis was b o.o •-, , • , .....{
0 5 10
therefore focused on the three model types (AWS, AW,
WS), on the kinetic parameters (volatilization coefficient Time (hr)
ranging
from10-4 to 10-6 S-1, sorptioncoefficient
ranging
from10-5 to 10-6 s-l), andthe soilorganiccontent(0.02 Figure8. Influence
ofnonequilibrium
process,
(foc= 0.1%)forcaseA2(AWSmodel,
highO_f
Xa•,= 10-5 s
and 0.1%). The other parameters are as listed in Table 1. Aws= 10-5 s-1),caseB2(AWmodel,Aaw= !0-5 s-•,
The numerical model representingthe box (see Figure 3) equilibriumsorption),and case C2 (WS model, equilibrium
volatilization,
i,,s = 10-5 s-i) - (a) Effluentconcentration
versus time. (b) Phase mass versus time.

1 ...........
caseC1 uses a rectangulargrid with 15 elementsin the horizontal

S i ----- direction and 16 elements in the vertical direction, with

nodesplacedto coincidewith the samplerlocations(Figure
5). The boundaryconditionsare a zero mass flux with
o 0.01 specifiedpressure(equalto atmosphericpressure)at the
inlet end and a zero concentrationgradient with specified
pressure(equalto the appliedvacuum)at the outletendof
0.001
the box. The initial condition is a homogeneousdistribution
0 5 10 of contaminant,with partitioningbetweenthe vapor, dis-
Time (hr) solved,andsorbedpha.ses assumedto havereachedequilib-
rium.
Resultsare presentedas graphsof normalizedair effluent
concentrationat the outletplotted againsttime, and as total
mass and massin the soil water, also plotted againsttime
(Figures7 and8). In the massplots,the differencebetween
the total mass and the mass in the soil water is the sorbed
mass,the massin the air phasebeingsmallin comparison.
The basecasefor the sensitivityanalysisis the AWS case
where volatilizationand desorptionare assumedto be kinet-
ically controlledwith equalrate coefficients.
This caseis
similar to the scenariosused in the modeltesting. In consid-
0 5 10 eringthe sensitivitywith respectto the kineticpartitioning
Time (hr) mechanisms,the two extreme casesare the AW and WS
formulationswhere one of the partitioningprocesses(sorp-
Figure7. Influenceof nonequilibrium
process,
loworganic tion and vo!atilization, respectively) is assumedto occur
carbon(OC) (foc = 0.02%) for caseA1 (AWS model, instantaneously. Followingthe relevantliterature[e.g., Ly-
&aw= 10-5 s-1 Aws= 10-5 s-1) caseB1(AWmodel, Aa.,v man et al., 1982; Piwoni and Bannerjee, 1989], we also
= 10-5 s-1 equilibrium
sorption)andcaseC1(WSmodel,
equilibrium Aws= 10-5 s-l)- (a) Effluentconsidertwo organiccarboncontentvalues,f,,c = 0.02%
volatilization,
concentration
versustime. (b) Phasemassversustime. (low)andfoc = 0.1% (high),resultingin twovaluesof the
362 ARMSTRONG
ET AL.' NONEQUILIBRIUM
MASSTRANSFER
DURINGSOILVAPOREXTRACTION

distributioncoefficient(Ka). The higherfoc value means Calibration

that a greatermassfractionof the totalcontaminant
massis
Themodelrequires
twokineticmasstransfer
coefficients,
stored in the sorbed phase. onefor rate-limitedvolatilizationandone for sorption.From
The responseto the low-carboncasesis shownin Figure the conceptualmodel it is clear that each of these will
7. The assumption of equilibriumsorption(caseB1, AW depend on the characteristicsof the porous medium that
model)producespracticallythe sameeffluentconcentration tendto makethe processto someextent diffusioncontrolled.
(Figure7a) as the fully kineticcase(caseA1, AWS model) Heterogeneity is such a characteristic. The kinetic mass
because of the limitation of the rate at which mass can enter
transfercoefficientswill therefore be site specificand must
the air phase.Much longersimulations wouldbe requiredto be obtained by model calibration.
showthe influenceof the rate-limitedsorptionin the AWS
model. Both models show an early drop in effluentconcen- Parameters
tration and massafter the contaminantinitially presentin the Valuesof the first-orderrate coefficientsfor TCE reported
first porevolume of air is removed.The rate-limitedbehav- in the literature range over several orders of magnitude,
ior is evident in the flatnessof the effluentcurve (Figure 7a) indicatinga strongsite dependenceof these parameters.The
and the massretained in the system(Figure 7b). In contrast, sorptionrate coefficientreported on the basisof experiments
equilibrium volatilization (case C1, WS model) takes longer usingTCE andBordensandrangesfrom 8.3 x 10-4 s-! to
to reachthe tailed portionof the curveand then dropsoff 1.4 x !0-3 [Lee et al., !988]to 5.6 x 10-8 s-1 [Goltzand
significantlyfaster becausemassis removedfrom both the Roberts, 1986]. For the air/water kinetic coefficient, Choand
air and the water. Mathematically, this effect is due to the Jaffe[1990]obtainedfittedvaluesof 5.6 x 10-7 s-1 to 8.3x
air-water retardation coefficientR• (see (13)). 10-4 $-1 in the courseof TCE volatilizationexperiments.
The relative distribution of dissolved and sorbed phase Rate constantsdeterminedfrom column experimentsinvolv-
massis practically identical for the AWS (caseA1) and AW ing two-phase flow of air and TCE-contaminated water
(caseB 1) models, indicatingthat air-water partitioningis the ranged
from4.2 x 10-5 s-1 to 9.7 x 10-5 s-1 [LeStrange,
dominant process for the parametersand timescalechosen 1990]. Brusseau [ 1991] suggeststhat rate-limited behavior is
here. The WS model has a much faster mass removal rate, observable when the ratio of the rate coefficient to the
retaining mass only in the sorbed phase. As the fraction of inverse of the advective residence time is between 0.01 and
mass stored in the soil increases relative to the water mass, 10. Applying this range to the box experiment data means
the AWS and WS systems are expected to become more that the kinetic volatilization coefficient for the experiment
similar to each other. should
be in therange10-5 to 10-2 s-1.
The responseof the high-carboncasesis shownin Figure The limited experimental data, which are typical of field
8. The air effluent curves (Figure 8a) here are all qualitatively
similar and do not differ greatly from the corresponding
low-carbon curves (Figure 7a), except that the WS model
10ø-
(case C2) now tails more. Most significantly, the mass
retainedfor all three cases(Figure 8b) is substantiallyhigher
in comparison to the low-carbon case (Figure 7b) becauseof
the increase in sorbed mass. The higher tail concentration
for the W S model is a result of the increased gradient • 10-•-
between the soil and water phases. These results indicate
that the volatilization rate can have a significantinfluenceon
effluent tailing and mass retention. Clearly, this influenceis
not easily observable on the basis of the air effluent curves
alone.
a
10-• ' I ' I
The influence of the air-water kinetic coefficient is shown o 5 lO
in Figure 9, where '•a• is varied over 1 order of magnitudeon Time (hr)
either side of the value used in caseA2 (Figure 8), keeping
,•wsconstant
at 10-5 s-1. Astheratecoefficient
decreases, 1.o]
the effluent concentration also decreases(Figure 9a), and the
slope of the tailed part of the effluent curve flattens. The
masscurves(Figure 9b) illustratethis effectmore graphically
in the form of stronger tailing and lower mass removal
resulting from the lower kinetic coefficient.
The sensitivity analysisshowsthat nonuniquenessmay be
a problem in SVE modeling. As shown by Figures 7-9,
different cases having different mass retention characteris-
tics can produce very similar effluentcurves. Therefore the b 0.o , I .., •-•
equilibriumpartitioningparametersand the concentrationor 0 5 10
mass in at least two phasesmust be known. Unfortunately, Time (hr)
the effluent concentration is usually the only information
Figure 9. Influence of volatilization coefficient, AWS
available in SVE applications. This information is insuffi- model,'•ws= 10-5 s-1 forcaseA2('•a•,= 10-5 s-i), case
cient to assessthe kinetic parameter(s) or the progressof a A2a('•aw= 10-6s-i), andcaseA2b('•aw= 10-4 s-l)- (a)
cleanupbecausethe massretainedin the systemcanstillbe Effluent concentrationversus time. (b) Phase mass versus
highwhile the effluentconcentration
is low. time.
 ARMSTRONG
ET AL.' NONEQUILIBRIUM
MASSTRANSFER
DURINGSOIl_/VAPOR
EXTRACTION 363

SVE applications, consistof stratigraphic and hydraulic E+04-

parameters, as well as air effluentconcentrations.
Dataon
therelativephasedistribution of themassin thesystemwere
notavailable.There wasalsosomeuncertaintyin the mass • E+0a-

presentat the startof the 46-hourextractionperiod,since

soilprobescouldnot be takendueto theirdisruptiveeffect. '• E+O•-
The need to use calibration to determine two kinetic
coefficients
on the basisof onesetof reliabledata,plusthe
• E+01-
uncertaintyin the initial mass,indicatesthat uniqueness o

cannotbe assured.Nevertheless, sincethe modelresponds

differentlyto the different parameters, a successfulfit to the E+00 • t ......................
experimentaldata provides some confidencethat the con- o io
Time (hr)
trolling processesmay be modeled adequatelywith the
kineticmodel.Under theseconditionsthe simulations give 3O

qualitativeinsight into the controllingmechanics,but not

quantitativepredictionsof massdistributionand removal.
Except for the dispersivities and rate coefficientsthe
requiredphysical parameter values were either directly
measuredor obtained from measurementsmade during
natural-gradientvapor transportexperimentsusingsimilar
Borden vadose zone sand [Hughes, 1991]. Dispersivity
values were selected after simulations showed that the
modelwas insensitiveto this parameter.The input parame-
tersare listedin Table 1, while the porosityandbulk density
values are shown as functions of depth in Figure 4. The
depth dependence of these two parameters is likely a con- Time (hr)
sequenceof the hand tamping of the soil which may have led
to greater compaction of the lower soil lifts. Figure 10. Comparison of simulated to experimental re-
The air permeability was calculated from the volumetric sults, continuous pumping for case D I (AW model, lower
flow rate, cross-sectional area, and steady state pressure Ka, haw= 2 x 10-5 s-l, equilibrium sorption)andcaseD2
gradientmeasuredduringthe experiment, while the spatially (AWSmodel, higherKa, Aaw= 4 x 10-5 s-•, X•s = 5 x
variable moisture content and temperature were directly mass 10-5 s-l). (a) Effluentconcentration versustime. (b) Phase
versus time.
measuredin the box. The organic carbon content, Henry's
constant, the diffusion coefficient, and viscosity were ob-
tainedfrom Hughes [ 1991]. For the relative air permeability
function the Brooks-Corey relationship [see Mendoza and A model simulation using the assumedkinetic parameters
Frind, 1990a],with a pore size distributionindex of 2, gave gave an approximatelyuniform concentrationacross the
the same result as the equation of Parker et al. [1987]. The domain at 9 days. The simulated effluent curve (not shown)
air velocity was approximately 0.005 m/s, which is some- displayed the characteristic tailed shape, but the initial
whathigherthan flow ratestypically encounteredin the field values were noticeably lower than the measured effluent
except very near an extraction well. values.This suggestedan error in the estimationof the initial
For the purpose of the calibration, two cases, having mass distribution in the model. Since better measurements
valuesof the distributioncoefficientfor sorptionof 0.02 and for the dissolvedand sorbed phase concentrationswere not
0.1mL/g, respectively,were againselected.The lowervalue available, it was decided to determine the initial concentra-
wouldbe obtainedby the organiccarbonmethodof Lyman tion by calibration.With an increaseof 25% of the initial
et al. [1982],while the higheris approximatelythe measured concentrationsthe model matched the early effluent concen-
value for TCE in sand [Lee et aI., 1988;Piwoni and Banner- trations quite well. This increaseis justified as it represents
jee, 1989].The two approachesresultin a fivefolddifference the possiblemarginof error in the samplingon accountof
in sorbed mass. nonequilibrium. Since the response due to a change in the
initial conditionsis characteristically different from that due
Initial Condition to a changein the kinetic parameters, it was felt that the
In order to estimate the initial condition, air phase con- overall calibration will not be compromised by this addi-
centrationsmeasuredat the 12 samplingpoints (Figure 5) tional degree of freedom.
wereassumedto be representative
of the spatialdistribution
ContinuousPumping
of the dissolved and sorbed TCE in the domain. The phase
distributionof mass was obtained by kriging the sampled The model was first usedto simulatethe 46-hour period of
valuesand usingthe equilibriumphaserelationships.The continuouspumping.The simulatedeffluentcurvesfor case
equilibriumassumption was usedbecausethe systemhad D1 (low retardation, equilibrium sorptionassumed)and case
beenat restfor 9 dayspriorto commencement of pumping; D2 (high retardation, kinetic sorption assumed)are com-
the variabilityof the measuredconcentrations,however, paredto the measureddata in Figure 10a.(All casesinves-
suggestedthat phasepartitioningmighthavestill beenoc- tigated are defined in the figure captions.) The model
curring.Samplemeasurement precisionwas estimatedat matchesthe early and late time data reasonablywell for both
10--20%[Hughes., 1991]. cases, but it producesa much sharpertransition from the
364 ARMSTRONG
ET AL ' NONEQUILIBRiUM
MASSTRANSFER
DURINGSOILVAPOREXTRACTION

steeppart to the tailedpart of the effluentcurve.This bothcasesgivea reasonable

fit to the datain the tailedpart
transitiontakes place relativelyquickly(<4 hours).The of the curve, the rate-limited transfer of mass into the
differenceis mademoremarkedin the plot by the useof a advectingair seemsto be adequately representedby either
logarithmicscalefor concentration.Attemptswere madeto set of kinetic parameters. The model was found to be
improvethe fit for the early timeperiodby adjusting
indi- relatively insensitiveto the value of the sorptionparameter
vidual element permeabilitiesto accountfor heterogeneous over the length of the simulations.
moisture distribution, but these were unsuccessful.The The massplots (Figure lib) are characterizedby a series
effect is apparently not due to advective transport. of plateauscorrespondingto the nonpumpingperiodsanda
A better model fit to the early part of the curve was seriesof small drops correspondingto the pumping periods.
obtainedby increasing the partitioning by several The most interestingaspectis that despitethe relatively
coefficient
ordersof magnitude,but this cameat theexpenseof a poorer largevariationsin air phase concentration,the actual mass
matchof the longtail. A similareffectwasseenby Lamarche removed during a pumping pulse is small.
[1991]while usingthe lumpedfirst-orderapproachto simu-
late NAPL dissolution. As stated earlier, the first-order Implications
kineticapproachrepresentsan approximation
to the sumof The resultsof the calibrationto the McClellan [199!] data,
the active processesthat may actually be occurringat both for the continuousand the pulsed pumping scenarios,
different rates and timesca!es.Notwithstandingthe error in indicate that the model is generally able to reproduce the
the transition part, the first-order approximationgives a measuredresults,althoughthe calibrationitself is nonunique
goodrepresentationof the two mostdistinctivecharacteris- with respectto the valuesof the kinetic parametersobtained.
tics of the curve, namely, the steepdescentfrom the initial The effluent concentrations do not appear to be sensitive
concentration, and the long tail which slowly approaches with respect to these parameters. In contrast, the mass
zero. remaining in the system in the various phases is highly
The total massremainingfor both cases,as simulatedby sensitivewith respect to the kinetic parameters. This raises
the model, is presentedin Figure 10b. Although the effluent somequestionswith respectto the reliability of cleanuptime
curves for the two cases are virtually identical, the mass estimates based on effluent data only.
curves are very different, illustrating that matching the Since the calibration is valid only over the limited time
effluent data is a necessary but not a sufficient requirement periodof the originalexperiment, the ability of the modelto
for model validation. Essentially all of the massin each case
was retained in the dissolved and sorbed phases. Although
the effluentcurves were similar, the massplots (Figures10b)
- measured
show that the higher Kd (case D2) causesabout 3 times as ............ D1
much mass retention over time as the lower K d (caseD1). "' D2
The sorption reaction was found to have relatively little
effect over the timescales simulated. In either case the mass
curves show that only a fraction of the initial contaminant •1oo
mass has been removed from the domain after the 40-hour
venting period. Clearly, the effluent concentrationsalone
cannot provide this information.
• •o
Pulsed Pumping
The model was applied to simulate the pulsed pumping
experimentperformedimmediatelyfollowingthe 46 hoursof
continuous extraction. As describedearlier, the experiment • o 2
consisted of three sets of pulses, each having a 2-hour Time (hr)
equilibration period with no pumping,followed by a 1-hour
extraction period. Model output from the 46 hours of con- 12-

tinuouspumping(seeabove) was usedas the initial condition

for the pulsed pumping simulations.Two cases are simu-
lated' D 1 (AW model) and D2 (AWS model). The values of
the air-waterkineticcoefficientusedrangefrom !.9 x 10-5
s-• for caseD1 to 3.9 x 10-5 s-• forcaseD2;thesorption
coefficientfor case D2 is 5.0 x 10-5 s-•.
The simulated effluent curves are compared to the mea-
sured data in Figure 1la. A linear scale is used to highlight
the wide change in concentrations over a short time. The
curves are discontinuous because effluent is not measured in b o,0 , i
2 , 4i , i
6
the interim period between the pumping. Case D1 (AW Time (hr)
model,foc estimatefor Kd, firsttwo cyclesshown)matches Figure 11. Comparisonof simulated to experimental re-
the effluent tail reasonably well but falls somewhat short of
sults, pulsedpumpingfor case D1 (AW model, lower K•,
reachingthe peak after vapor recovery.For caseD2 (Figure
kaw= 2 x 10-5 s-1, equilibrium sorption)andcaseD2
11a)the modelgivesa goodfit for boththe peakandthe tail
(AWSmodel,higher Kd, ,haw= 4 X 10-5 s-1, Aws= 5 X
portionsof the effluentcurve,although
the simulations
are 10-5 s-I). (a) Effluentconcentration
versustime.(b) Phase
slightlylow immediately
followingthepumpstart-up.Since mass versus time.
 ARMSTRONG
ET AL.' NONEQUILIBRIUM
MASSTRANSFER
DURINGSOILVAPOREXTRACTION 365

representlong-termvapor extractionremainsas yet un- spondingto zero air velocityis the time requiredfor com-
tested.Recentexperimental
datafromcolumnvaporextrac- plete massremovalby pure diffusion,known as passive
tion tests [Grathwohl, !992; Rauh, 1992]have shown that remediation.Clearly, applyingeven a low airflowrate to the
effluenttailing can extend over very long times. For exam- passivescenariowill result in a rapid decreasein cleanup
ple,the Grathwohlexperiment
showed50%of the initial time. Further increases in the flow rate, however, bring
massremainedafter more than 1500pore volumesof air had diminishingreturns in terms of improvementsin cleanup
passedthroughthe column,while the Rauh experiment time.
requiredover 40,000 pore volumesto remove97% of the A critical point can be defined beyond which the kinetic
mass.Recent work by El-shenawy [1992] showedthat the mass transfer process becomes controlling, and mass re-
first-orderrate constantapproachmay not be optimalfor moval will be essentiallyindependentof the airflow rate.
verylong-termbehavior,butthatinsteada time-varying
rate Sincethe transitionis a gradualone, the choiceof the critical
coefficient,possibly of exponential form, should be used. value is somewhatsubjective.Figure 12 showstwo possible
Thephysicalbasisfor sucha form of ratecoefficientremains critical points,one selectedby inspectionbasedon cleanup
asyet unclear. time, and the other calculated from a dimensionless relation-
shipdevelopedby Gierkeet al. [1992]. Gierke et al. consid-
ered the range of optimum airflow rates in terms of air
Analysisof Pumping Strategy volumeextracted;the relationshipis developedby equating
The rate of mass removal under kinetic conditions de- the masstransferred by partitioningto the mass•transported
pendson the airflowrate and on the rate-limitedtransferof by advectionand involvessoil aggregatecharacteristicsand
massfrom the dissolvedand sorbedphasesto the air phase. otherphysicalparameters. The lower Darcy velocitywould
As the air velocity increases,the masstransportedby a unit remove 99% of the TCE contamination in about half the
volume of air decreases, and hence the efficiency of the extractedair volumeas comparedto the highervelocity.
systemdecreases.On the other hand, pumpingat a faster The optimumcleanupefficiencyis evidentlyattainedwhen
rate may lead to a faster rate of extraction and a shorter the flow rate is such that the air residence time just allows
cleanuptime. Thus a trade-off exists between efficiencyand the kinetic partitioningprocessto approachequilibrium.
cleanuptime. This would hold for idealized conditions. In the field, soil
OptimumAirflow Rate and moisturecontentheterogeneitieswill likely control the
A seriesof simulationswere performedto investigatethe airflow regime and therefore the cleanup by SVE. The
relationshipbetween the airflow rate and the time taken to optimumairflowrate will then be the smallestflow rate that
can create the desired zone of influence.
meet a target of 99% mass removal. In real situationsthe
cleanuptarget will be higher since essentiallyall of the Efficiencyof PulsedPumping
contaminant must be extracted in order to meet drinking
water standardsfor VOCs. The numerical experiments were Pulsedpumpingis sometimessuggestedas a meansfor
conductedassuminga domainand soil similarto thoseused
improvingthe extractionefficiencyby reducingenergyre-
quirements [Keelyet al., 1987;Crow et al., 1987;Grathwohl
inthe box experiments.The contaminantwasassumedto be
et al., 1990]. In order to determine the mass removal
initially at phase equilibrium and uniformly distributed
efficiencyunder a pulsingregime, two pulsed pumping
throughoutthe domainat approximatelyhalf of the theoret-
ical saturation. The rate coefficient was assumed to remain
scenarioswere investigated.The pumping schedulesand
corresponding flow rates used were as follows: (1) 2 hours
constantover the full rangeof concentrations andvelocities.
The time taken to reach the cleanupgoalundercontinuous
pumping at 5 m/h, 8 hoursoff; and (2) 1 hourpumpingat 5
m/h, 4 hoursoff; eachgivingan averageDarcy flow rate over
pumping is plottedagainstthe Darcy velocityin Figure12.
the full cycleof 1 m/h. These scenariosare comparedto a
Therangeof velocitiesis between0.14and0.001cm/s(other
continuouspumpingscenariousing 1 rn/h (i.e., the same
parameters are as for caseD2, Figure 10).The curvehastwo
averageflow rate as the pulsedpumpingscenario),and a
distinctparts,a slowpart in whichthe air residence timeis further continuouspumpingscenariousing5 m/h (i.e., the
long,allowingthe partitioningprocessto equilibrate,anda rateof thepumping portionof the pulsed•umpingscenarios).
fastpart in which kineticmasstransferis the controlling The massremainingin the systemas a functionof timefor
process.For the slow part the limitingtime value corre- the abovecasesis plottedin Figure 13. It is evidentthat the
2- to 8-hourcycle removesmassat the slowestrate. The 1-
600- to 4-hourcycleis somewhatmore effective.However, the
continuous
pumpingschemeusingthe sameaverageairflow
rate removes mass faster than either of the two pulsed
• 500- CriticalPointaccording
to Gierkeet al., i992 pumpingschemes.As expected,the fastestmassremoval
rate is achievedwith the higher flow rate; however, in that

•
o
zl-00
cal
Point case5 timesas muchair is pumpedfor only a marginalgain
in the mass removal. Therefore this scheme is the least
efficient of the schemestested. Overall, it is clear that a slow
.•,1
but continuouspumpinggivesthe best massremovalperfor-
mance.
3O0 I i The superiorperformance
of continuous
but slowpumping
0.0 0.05 0.1.
is due to the fact that diffusive mass transfer between phases
Darcy Flux (cm/s) is maximizedby maximizationof the concentrationgradient
Figure 12. Time for 99% massremovalversusflow rate. at all times. Pulsingcausesthe gradientto be less than the
366 ARMSTRONG
ETAL.:NONEQUILIBRIUM
MASSTRANSFER
DURINGSOILVAPOREXTRACTION

.Appendix
2-8 hr. cycle,1 m/hr.avg.
• /
The developmentof the numerical solution of the govern.
1-4 hr. cycle,1 m/hr.avg. ing equationsincorporatingnonequilibriummass transfer
between the air, water, and sorbed phases follows the
continuous,1 m/hr. approachof Leismannet al. [1988]. A brief outline of the
0.5-
procedure
for the threemodeltypesis givenbelow.In each
continuous,5 m/hr. case,a singlematrix equation for the air phaseresults.

AWS Model

The transport equation (10) is time weighted to give

n+l n
Ca -Ca n+l
0.0 L(Ca) = Oa + O.X.w[e(Ca _ /4r(7n+l ]
lOO At

Time (hr)
+ (1 - e)(C•n - HCn•)] (A1)
Figure 13. Comparisonof pulsedandcontinuous
pumping
schedules' mass remaining versus time. as are the partitioning equations (11) and (12), giving

possiblemaximum duringthe periodwhen the pumpis shut

down and the system equilibrates.Maximization of the
Ow(•; +O
aXaw[E(C•
+1--
HCwn+l)
concentrationgradient alsoexplainswhy short-cyclepulsing
is better than long-cycle pulsing,sincethe former resultsin + (1 - e)(Can - HCw)] - OwXws
shorter periods of suboptimal diffusive mass transfer. Kd
Clearly, the optimal schemefor pulsedoperationefficiency
correspondsto the limiting casewhere the shutdownperiod
approaches zero, i.e., continuous pumping. (A2)

Conclusions
Under conditions such as thoseof the emplacedbox exper- P•
= Ow•ws
S Cn+l
At Kd
w

iment, the extraction of volatile organiccompoundsfrom the

aqueousand sorbed phasesin the vadosezone is controlledby
nonequilibriumphasepartitioning.Thesefindingsapplyto field (A3)
situationswhere high extraction rates are used. Under most
field conditions, high airflow rates suchas used in the experi- where n and n + 1 refer to two successive time levels, and
ment might be attained near extractionwells, while at greater
distances from the well the rates would be lower.
s is the time weightingfactor (e = 1 for fully implicit scheme,
e = 0.5 for Crank-Nicolson scheme).
The experimental data indicate that under the given con-
Equations (A2) and (A3) are rearranged to obtain expres-
ditions, air-water mass transfer is the dominant process, ß n+l n+l n+l
s•onsfor Cw and Cs . The resultingequationfor Cs
although more mass distribution data would be required for
unambiguousidentification. The first-orderapproximationof
issubstituted intothatforC•+ 1, whichisthenrearranged to
give
the mass transfer process appears to be reasonable for
relatively short term simulations of up to hundredsof pore A2
volumes. The kinetic coefficientsdependon the site condi-
tions, and it appears that they are best obtained by model
calibration. For uniqueness of calibration the contaminant
A 1A2 + A3 OaXaw
At(eC•
+!
+(1
-e)Ca
n)
mass distribution in at least two of the three phasesshould
be known. If the data are limited to effluent concentrations, + Ow-(1 - e) Oa•aw AtH + OwAwsAtpb
as is the case in most field situations, a unique calibration
cannot be obtained.
The experiments show that for a given set of physical (A4)
parameters, a critical airflow rate exists beyond which
increasesin the flow rate bring about no significantdecreases
in cleanup time. The critical value can be found from the 1
relationship between cleanup time and airflow rate. C•+• {OwXw
sAtKa[e_•
A2
Pulsed pumping is shown to be less efficient than contin-
uous pumping at an equivalent averagerate, at least for the + [PbKa- OwX•sAt(1 - e)]C•} (A5)
cases investigated. The reason is that continuouspumping
maximizes the diffusive mass transfer of contaminant from Equation
(A4)issubstituted
forC• +1in (A1).Aftersome
the water to the air phase by maintainingthe concentration algebraic
manipulation
thetime-weighted
transportequation
gradient at a steady maximum value. becomes
 ARMSTRONG
ETAL.:NONEQUILIBRIUM
MASSTRANSFER
DURING
SOILVAPOR
EXTRACTION 367

The sorbedconcentration at the new time level is again

calculated
explicitlyusing

Cs
n+l=OwAws [ Kd
n+l Kd
Ate•-Ca +(1-e)-•-C2

+[PbKa-
(1-e)OwAws
At]Cf}(pbKa
+eOwXws
At)
-! (A17)

In each of the abovecasesthe time-weightedequation

(A6) involvingthespatialterm(theair phaseequation)is spatially
weightedusingthe standardGalerkin finite element method
where [Huyakorn and Pinder, 1983], and the resulting matrix
equation
issolved
fornodalvaluesof C• +1 . Sincevaluesof
A 1 = 0 w + eOaAawAtH (A7) C•+• andC• +• arecalculated
explicitly,
onlyonematrix
solution is needed.
A 2 = poKa + eOwAwsAt (A8)
Acknowledgments..Thefinancial support of the Natural Sciences
A 3 = ePbKdOwAwsAt (A9) and ResearchCouncilof Canadais gratefullyacknowledged.The
first authorwishesto acknowledgethe valuablecontributionsof J.
AW Model Crois6 and P. Grathwohlduringhis stay at Stuttgart.Finally, we
wishto thankthe anonymous reviewersfor theirhighlyconstructive
A similarprocedureappliedto (10) and (13) resultsin suggestions.

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