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On The Late-Time Behavior of Tracer Test Breakthrough Curves
On The Late-Time Behavior of Tracer Test Breakthrough Curves
On The Late-Time Behavior of Tracer Test Breakthrough Curves
BTC and massrecoverycurveswith sorbingorganicsolutesin sionless]is the retardationfactor in the mobile (advective,
unsaturatedmedia. Cunninghamet al. [1997] were able to effective,
or kinematic)
porosity,
c [M L-3] is soluteconcen-
representthe Werthet al. [1997] data with a gammadensity trationwithintheadvective
porosity,
andF(x,t) [M L -3 T-1]
function of diffusion rate coefficients,while Haggertyand is the source-sinkterm for massexchangewith the immobile
Gorelick[1998] were able to approximatethe power law be- (matrix or diffusive) porosityand nonequilibriumsorption
havior with a lognormaldensityfunction of diffusionrate co- sites.From thispoint forward,we will adoptthe terminologyof
efficients.Both Cunninghamet al. [1997] and Haggertyand "mobile" and "immobile" domains and concentrations, which
Gorelick[1998] noted the inabilityof conventionalmodelsof refer to either sorptionor diffusion.We will employthe uni-
masstransfer to yield the appropriatepower law behavior. form initial conditions
Power law behaviorwith a slopeof 3/2 has been observedin
field data from the Grimsel, Switzerland, test site and has been c(x, t = 0) = Cim(X
, Z, t = 0): Co, (2a)
adequatelyexplainedwith conventional(singlerate) matrix
whereCim[M L -3] is soluteconcentration withintheimmo-
diffusion[Eikenberget al., 1994;Hadermannand Heer, 1996].
bile domain,which may, in the caseof diffusion,be a function
However,single-ratediffusionis onlyableto yield a powerlaw
of a secondspatialcoordinatez orientednormalto the mobile-
of exactlyt -3/2 andcanonlymaintainthisbehaviorslightly
immobiledomaininterface.We will alsoemploythe boundary
longerthan the mean immobile-domain residencetime (t, = conditions
a2/lSDa for spheres
anda2/3Dafor layers),whereD a is the
apparentdiffusivityand a is the half thicknessof the immobile c(x = O, t) = moa(t), (2b)
domain. Power law behaviorsuchas that observedby Farrell
andReinhard[1994];Werthet al. [1997],or MeigsandBeauhelm c(x -->•c, t) = Co, (2c)
[2001]cannotbe explainedwith conventionalsingle-ratedif-
fusion.Jaekelet al. [1996] showedthat power law BTCs can wheremo [M T L -3] is the zerothmomentof the BTC, Co
resultfrom a pulseinjectionof soluteand equilibriumFreun- [M L -3] is the initialconcentration
in the system,and8(t)
dlichsorption.Unfortunately,noneof the three data setsmen- [T -•] is the Diracdelta.The Diracinjectionis nevermetin
tioned aboveare explainedby this (the Meigs and Beauheim practice.However,aslongasthe durationof the pulseis much
tracerswere nonsorbing,and equilibriumFreundlichsorption shorter than the mean residence time in the immobile domain,
is insufficientto explainthe power lawsin the other data sets (2b) will be a sufficientlygood approximation.For a finite
[Werthet al., 1997]). pulseinjectionwith constantvelocitythe zerothmomentm o is
The purposeof this paper is to explorethe nature of tailing the injectedconcentrationmultipliedby injectiontime.
in mobile-immobile(dualporosity)tracertestBTCs for a wide For initial and boundaryconditions(2a)-(2c) then at late
varietyof linear masstransfermodels.Specifically, we havethe time,
followingobjectives: (1) developan analyticexpression for the c•c
late-time BTCs for transportexperiencinga distributionof
either first-ordersorptionor diffusiontimescalesand for both
O•L
•XX
<<C, t >>tad
, (3)
pulseinjectionsand mediawith nonzeroinitial concentrations,
(2) examinethe informationthat canbe providedby the late- wheretad[T] is the averageadvectiveresidencetime (equalto
time behaviorof the BTC, and (3) examineBTCs that exhibit LR,/v if velocityand retardationare constantin space).In
power law behaviorat late time and the implicationsfor mass other words,once the input pulse has advectedfar past the
transfer.Particularexpressions describingthe late-time BTCs point of observationL, then dispersionhasa negligibleeffect
for single-ratemodelswith both infinite and finite immobile on concentration.Figure1 (discussed in section3.2) showsthat
domains, as well as multirate models with first-order and dif- the late-timeresultwe obtain is valid independentof the dis-
fusion rate coefficientsdefined by lognormal, gamma, and persivity.Note that (3) is alwaysvalid (includingearlytime) if
powerlaw densityfunctions,are provided.Implicationsof the a• << L. Similarly,if the immobile domain has a long mean
residence time relative to advection, then at late time
late-timeslopesdefinedby theseequationsare discussed with
respectto masstransferprocesses, includingimplicationsfor c•c
estimates of the mean residence time in the immobile domain
ot
<< r(x, t), t >> t,,j t, >> tad, (4)
(or, equivalently,a characteristicmasstransfer time). The
powerlaw late-timebehaviorof BTCs in two SWIW testsfrom where t, [T] is the mean residencetime in the immobile
the WasteIsolationPilot Plant(WIPP) sitein New Mexicoare domain. At late time, concentrationsdo not changesignifi-
examined.
cantly with time, and changesof concentrationalong the
streamlineare determinedby exchangebetweenthe mobile
2. Mathematical Development and immobile domains. In other words, at late time, concen-
2.1. General Case: Late-Time Solution tration at any point in spaceis determinedonlyby the sum of
for Concentration
The massbalanceequationfor a soluteadvectingand dis- diffusionout of the immobile domain between the point of
persingin one dimension(i.e., alonga singlestreamtube) and injection and the point of interest. Note that from this point
interactingwith rockvia diffusion,linear equilibriumsorption, forward,it will be assumedthat t, >> tadand t >> tadunless
and/or linear nonequilibriumsorptionis otherwisestated.Therefore (1) may be rewritten:
v Oc
la(
ax ac )ac
= 37+ r(x,t), Ra Ox
= r(x, t), (s)
wherec [M L -3] is soluteconcentration,aL [L] is longitu- where we have assumed that there are no sources and sinks of
dinaldispersivity,
v [L T- 2] isporefluidvelocity,
Ra [dimen- fluid and velocitiesare steady(note, however,that v and R a
HAGGERTY ET AL.' BEHAVIOR OF TRACER TEST BREAKTHROUGH CURVES 3469
may
still
bevariable
solution
inspace).
Byintegration
forconcentration
atlate
time:
we
can
obtain
a • I •t Ik\ I•^D•(Pe=
1000)I-
c(x=L,t)= - •,(x)F(x,t)dx, (6)
I
where
L[L]is
thedistance
from
point
ofinjection
topoint
of 102 :
observationalong
spaceisvalid the
flow
because
at path.
late timeNote that
theintegration
the source-sink over [ 5
termchanges 100
very slowly relative to the advectiveresidencetime. If the
parameters
andfunctions
that compose
F(x, t) are spatially 10'210's 10's 10• 10"a 10'2 10'• 10ø 10•
uniform (the spatiallyvariablecaseis left for a future paper),
then this leavesus with a very simpleexpression for concen-
tration at late time:
Dat
c(x = L, t) = --tadF(t). (7) Figure 1. Late-time solution and full advection-dispersion
masstransfer (ADMT) solutions(Pe = 10 and 1000) for
Note that thisexpression
isvalid evenif the velocityfield is not sphericaldiffusion.
spatiallyuniform.From this point on, the dependencyof c on
x = L and t is assumedimplicitly.
mobile-domainconcentration that hasthe correctpulsesizeat
2.2. Source-Sink Term F(t)
early time and that is approximatelyzero at late time. Suchan
The source-sinkterm F(t) is the rate of loss or gain of approximationis availablein c = moB(t), where mo is the
concentrationto or from the immobile domain (lossat early zeroth momentof the injection.Note that this approximation
time and gain at late time). The source-sinkis commonly is usedonly for calculatingthe source-sinkterm and not as an
expressedas a derivativeof immobileconcentrations[e.g.,van approximationfor late-timeconcentrationitself. This approx-
Genuchtenand Wierenga,1976;Cameronand Klute, 1977],but imation works because at late time the source-Sink term does
for our problemit is more convenientto expressit as a con- not stronglyretain "memory"of the detailsof the input but
volution, followingCarreraet al. [1998]. For any linear mass onlyof the magnitudeof the input.That thisapproximation is
transfer problemwith uniform initial conditionsthe source- sufficientwill becomeapparentwhenthe resultsare compared
sink term at all times is to full numericalsolution.Employingthe propertiesof convo-
lution, (8) can now be expressed:
r(t) =
tOc(t-
z) Oc Og
o• g(*)d, = • *g= c* • + cgo-cog
F(t)---mo•-
0#
cog, t >>tad ta>>tad. (9)
The generalformof the memoryfunctionis (modifiedfrom
whereg(z) is a "memory
function"
to be defined[T-•], the Carreraet al. [1998,p. 182])
asteriskrepresentsthe convolutionproduct,go is the memory
functionat t = 0 [T-•], and co [M L -3] is the initial
concentration. Note that the Laplacetransformof (8) is com- g(t) = ab(a)e -ø•tda, (10)
monlyusedin analyticalsolutions[e.g.,Villermaux,1974;Car-
rera et al., 1998;Cunninghamahd Roberts,1998;Hollenbecket
of (8) is mosteasily wherea is a rate coefficient
al., 1999]andthatthe right-hand-side [T -•] and b(a) is a density
derived in theLaplaCe domain. Equation (8) hasbeenex- functionof first-orderrate coefficients[T]. Note two differ-
pressedexplicitlyin the time domainby, for example,Peszyti- encesbetweenour definitionof the memoryfunctionand that
ska[1996]andCamera et al. [1998],andresultsin anintegro- of Carreraet al. [1998,p. 182,Equations(15) and (16)]. First,
partialdifferentialequationwhensubstituted backinto (1). our memory function #(t) includesthe constantsthat are
Thememory function #(t) maybephysically interpretedasthe placed before the source-sinkterm in Carrera et al.'s mass
capacitycoefficient(•3tot(seeAppendixA)) multipliedby the balanceequation.Second,althoughCarreraet al. [1998] ex-
residencetime distributionin the immobiledomain,givena press(10) as a discretefunction,the more generalexpression
Diracpulseat thesurface. of #(t) is propor- is as a continuousfunction,allowingfor densityfunctionsof
Thederivative
tional to what is commonlycalled iri statisticalphysicsthe diffusionrate coefficients,etc. Various densityfunctionsb(a)
probabilityof firstreturnor distribution times are given in Table 1 along with the correspondingmemory
of firstpassage
[e.g.,Bouchaudand Georges, 1990,pp. 271-272]. function#(t). Note that using(15) from Carreraet al. [1998,p.
We desireto finda closed-form forthesource- 182]is equivalentto usingour (10) for diffusionin a finitelayer
eXPression
sinktermin (8), accurateat late time,that maybe substituted (seeTable 1).
into (7). We recognizethe followingcharacteristics
of F (t)' (1) We note that (10) is the Laplacetransformof ab(a), where
At earlytime the functionrepresents rapidlossfrom a high- t substitutes
for the Laplacevariable.We alsousethe property
concentration pulsein the mobiledomainto the immobile of the Laplacetransform[e.g.,Roberts andKaufman,1966,p. 4]
domain,and (2) at late time the functionrepresentsslowgain Og
to the mobiledomain(whichhasverylow concentration) from •{a2b(a)}
= at' (11)
the immobile domain. To obtain a solution that is accurate at
late time, we therefore require an approximatefunctionfor where •{ ) indicatesthe Laplacetransform.
3470 HAGGERTY ET AL.' BEHAVIOR OF TRACER TEST BREAKTHROUGH CURVES
finite
layer • (2j- 1)2-z2
j=l
aa- 4 •-• • 2/3tot
j=l
•- exp- 4 a2t 3•-•
infinite
layer
b lim (2j- 1)2w2Ra
a--• a ot-
= 4 •-• Ra
Diffusion: 4/•tot Da Da
cylinder
c • • • Ot
--///2
j=l
•- E4/•tøt
j=l
•-exp
--uf
•t
Diffusion: 6/•tot Da Da Da
sphere • j-Y-•
&a- j2w2
j=l
•- E 6/•tot
j=l
•- exp &• t 15•
must be obtainednumerically
lognormal * 8•to
t In (2j- 1)2-z
2 -/x
Da/a
2d • • (2/--
1)2rra
exp
-- 2o
•
Gamma
• (2j--1)2wxr(•/)c•
D./a2d 3,(2j exp--3,(2j
Ci)2w2
j=l
E2/•totTT/
Z])2712 Tt
•(2j
-1)27r
2q-1-7-1
0 --l)'y T/<•
3(T} >1
T}l n=l
Employing(7), (9), (10), and (11), we can now write an functionsb(a) using# (t) suppliedin Table 1. SeeAppendixB
approximationfor concentrationat late time: for two notesregardingthe useof (12).
At thispointwe reemphasize the restrictionson (12). These
C -- tad CO# -- /T/0 are as follows:(1) Time is much greater than the advection
time; (2) the meanresidencetime in the immobiledomainis
much greaterthan the advectiontime; and (3) time is much
= tad (Co+ amo)ab(a)e -"tda,
greaterthan the durationof the injectionpulse,meaningthat
an impulse(Dirac) functionis a valid approximationto the
injection.In a spatiallyvaryingvelocityfield, restrictions(1)
= tad•J•{(½
0 + amo)ab(a)}. (•2) and (2) mean that both time and mean residencetime in the
immobile domain must be much greater than the sum of ad-
Equation (12) was verified againsta numericalmodel. The vectiontime acrossa controlplaneand the standarddeviation
numerical model solved the full advection-dispersionmass of that advectiontime. In particular,a power law distribution
transfer (ADMT) equations(i.e., (1)) for severaltypes of of advectiontimes(suchasinvokedby, for example,Berkowitz
source-sink terms, F. These numerical solutions are discussed and Scher[1997]) would invalidatethe use of (12).
in section3 and shownfor severalcasesin Figures 1-4. The
2.3. Mean Residence Time in Immobile Domain
numericalsolutionrequirednoneof the assumptions required
to develop(12). One of the criteriafor useof (12) is that the meanresidence
All formsof (12) are equivalentand are usefulin different time in the immobiledomainbe muchgreaterthan the advec-
ways for understandingthe late-time behavior of BTCs. We tion time. This section outlines the calculation of this mean
expectthat in most applicationsonly one of Coor m o will be residencetime, aswell asprovidingan effectiverate coefficient
nonzero;however,(12) holdstrue regardlessof the valuesof that may be usedin an "equivalent"first-ordermodel of mass
the initial concentrationin the porous medium Co and the transfer.
zeroth temporalmomentof the input pulsemo. Note that the The residence time distribution in the immobile domain
late-time concentrationcan be calculatedfor variousdensity givena Dirac impulseat the surfaceis 9(t)//•to t. The mean
HAGGERTY ET AL.: BEHAVIOR OF TRACER TEST' BREAKTHROUGH CURVES 3471
residencetime (or characteristicmasstransfertime) is there- [1998]make the sameassertion.In the caseof sphericalblocks
fore the densityfunctionis
ta: J•to-•t#(t)dt
(13)
=••1
b(o/) 613tøt
• o/-j2,rr2
: j•--•-•2 -•- (18)
where J•tot[dimensionless]
is the capacitycoefficientof the
--
1 b(.)
•tot
dO/. spherical
blocks,
D a [L2 T-1] is theapparent
diffusivity,
and
a [L] is the radiusof the sphericalblocks.This densityfunc-
tion is a seriesof Dirac deltaswith monotonicallydecreasing
It canbe shown[e.g.,Cunningham andRoberts,1998]that the weight.The harmonicmean of (18) is the well-knownlinear
zeroth,first,and secondtemporalmomentsof the BTC are the drivingforceapproximation
15 Da/a2 [e.g.,Glueckauf,
1955],
samefor anydensityfunctionof rate coefficients
providedthat and the mean residencetime in the spheresis thereforet• =
the mean residence time in the immobile domain is the same.
a2/15Da. The memoryfunctionis
Thereforethe besteffectiverate coefficient(i.e., the one that
yieldsthe samezeroth,first,and secondmomentsof the BTC)
is the harmonicmean of the densityfunction,since
#(t)= •• 6j•to
j=l
tDa (_j2zr2Da
• exp •¾t). (19)
1 •b(a)
= = . Readers familiar with diffusion in sphericalgeometrywill
recognize(19) as proportionalto the massflux out of spheres
initiallysaturatedwith a uniform soluteconcentrationandwith
Notably, the harmonic mean may be zero for some densi•
a boundaryconcentrationof zero [e.g., Crank, 1975, p. 91;
functions,meaningthat the mean residencetime in the immo-
bile domain is infinite. Note that an infinite mean residence
Grathwohlet al., 1994].
The resultinglate-time approximationfor concentrationin
time doesnot require infinite sizeor infinite capaci• in the
immobile domain. The harmonic means for a number of den-
the mobiledomain(with initial concentrationof zero) is given
by substituting(19) into (12):
si• functionsb(a) are shownin Table 1.
100
9(t)= --½tot
• (3't+ 1)-7. (22)
"-, ' .... n:1.5 !
I
Therefore the late-time concentration in the mobile domain is
10'•
givenby
• I ',•'••mslope rt(rt
++1)1)
½=m0tadCtøt3'2
(3't 7+2' (23)
10• Note that when 3't >> 1, the BTC followsa powerlaw:
[ .................................... :.... • c • t -7-2 (24)
10'2 104 10ø 10• 102 10a 10'•
The samelate-timepowerlaw behavioris alsoexhibitedwith a
density function of diffusion rate coefficients.Note that a
Figure 2. Late-time solution and full ADMT solution for powerlaw BTC (c • t -k) withk < 3 wouldindicatean
gammadistributionof first-orderrate coefficients. infinitesecond(and higher)temporalmomentand an infinite
mean residence time in the immobile domain.
Figure2 showsthe late-timeapproximation in (23) nondi-
harmonicmean rate coefficientfor this caseis zero, meaning mensionalized by the transport terms. We have normalized
that the meanresidencetime for verylargeblocksapproaches time by the mass transfer rate 3'.Figure 2 also shows a solution
infinity. to the ADMT equationswith STAMMT-L [Haggertyand
Third, the locationof the BTC peak in the ADMT solution Reeves, 2000]formo = 1 x 104skgm-3, tad= 1 X 104S,3'----
may lie anywhereon the late-time approximationcurve,de- 1 x 10 -4 s-•, r/: 0.5,½tot: 1, anda Pecletnumberof 1000.
pendenton the relativevaluesof tadandDa/a2. We see from (24) andFigure2 that the late-timedouble-log
Last, we note that it is possibleto estimateboth ½totand slopeof concentrationwill be -(rt + 2). For comparisonto
Da/a2 byusingthelate-timeapproximation asa typecurve,if publishedvalues,Connaughton et al. [1993]estimatedvaluesof
the break in slope is present.The capacitycoefficient½tot rt in the range of 0.17 to 0.37 for a gammadensityfunctionof
wouldbe estimated fromtheverticalshift,whileDa/a2 would first-order rate coefficients, while Peditand Miller [1994]esti-
be estimated from the horizontal shift. mated r/ = 0.11 from their experiments; Culveret al. [1997]
estimatedrt = 0.023 to 0.054 for their columnexperiments;
3.3. Gamma Density Function of First-Order Deitschet al. [1998] estimatedr/from 0.092 to 350 in 15 ex-
Rate Coefficients
perimentswith differentmaterials,with the majorityhavingrt
Gamma densityfunctionsof rate coefficientshavebeenused below1. Kauffmanet al. [1998]estimatedr/= 0.60 and 0.84 in
to representmultirate masstransferin severalpapers.Cun- twocolumnexperiments. Werthet al. [1997]foundvaluesof rt
ninghamet al. [1997] developedthe mathematicsof a gamma equal to approximately 0.5 for a gamma densityfunction of
densityfunctionof diffusionrate coefficients,while Werthet al. diffusion rate coefficients. Note that almost all of these esti-
[1997]appliedthismodelsuccessfully to severalmass-fraction- mated rt (i.e., those below 1) will lead to an infinite mean
remainingdata sets.Connaughton et al. [1993]useda gamma residencetimewithin the immobiledomain.Consequently, the
densityfunctionof first-orderrate coefficientsto modelrelease variance of the breakthrough times will be infinite with these
of naphthalenefrom soil, while Pedit and Miller [1994] em- models.Late-time behavior associatedwith gamma density
ployeda gammadensityfunctionof first-orderrate coefficients functions is discussed further in section 4.2.
to examinediuronsorption.Other examplesincludeAhn et al.
[1996],Chen and Wagenet[1997], Culveret al. [1997],Sahoo 3.4. Lognormal Density Function of Diffusion
and Smith[1997],Deitschet al. [1998],Kauffmanet al. [1998], Rate Coefficients
Lordenet al. [1998],andStagerandPerram[1999].The method Lognormaldensityfunctionsof rate coefficientshave also
we are usingis applicableto both typesof densityfunctions, been usedto representmasstransferin natural systems. Pedit
and the key relationshipsfor both are given in Table 1. Al- andMiller [1994],Backesetal. [1995],Haggerry [1995],Culveret
though the early-time behaviorwill differ between gamma al. [1997], and McLaren et al. [1998] all used a lognormal
densityfunctionsof first-order and diffusionrate coefficients, densityfunctionof first-orderrate coefficients
to modeluptake
the late-time slopewill be identicalfor the samevalue of and releaseof sorbingsolutesin soils.Peditand Miller [1995]
The gammadensityfunctionof first-orderrate coefficients is and Haggerryand Gorelick[1998] used a lognormaldensity
function of diffusion rate coefficients to model diffusion of
•tot
sorbingsolutesin soils.As is true for the gammadensityfunc-
b(a)= 3'T(r/)
aT-'e
-"/•, (21)
tionsof rate coefficients, the behaviorof bothlognormalmod-
where3'[T-x] isthescaleparameter andrt [dimensionless] is elsisverysimilar,especiallyat late time andlargevariances.In
theshapeparameter.The harmonicmeanof (21) is0 if r/is less our analysishere we will employonly a densityfunctionof
than 1, a fact that is of particularimportancefor applications. diffusion rate coefficients:
As a consequence, the mean residencetime in the immobile
domainwouldbe infinite.(Thisis alsotrue for gammadensity
functionsof diffusionrate coefficients.)If rt is greaterthan 1,
-- Daexp - 20.2 , (25)
the harmonicmeanof (21) is (r/- 1)3'.
The memoryfunctionis b*-•- ',,,•=
0.a2
HAGGERTY ET AL.: BEHAVIOR OF TRACER TEST BREAKTHROUGH CURVES 3473
In (Da/a2), respectively,
in a lognormaldistribution.
The 10=
equivalentdensityfunction of first-order rate coefficientsis ADMT((• = 5)
I 100
givenby Haggettyand Gorelick[1998]'
=. 10'2
• 10'•
b(0/)
=.j•l'j27r5
(2/- 1)2o-o/ 5/2slope
• 104
{ I (40/) 12}
ßexp -
In (2j- 1)2rr
2 - tx
20.2 '. (26)
10'4ø
10-42
10 104
5
I Os
Theharmonic meanof (26)is3 exp(ix - o2/2).Consequently,
the effectiveratecoefficient
is approximately
0.22o2 ordersof
magnitudesmallerthan the geometricmean. For large 0-the Figure 3. Late-time solution and full ADMT solution for
effectiverate coefficientis approximatelyzero, and the mean lognormaldistributionof diffusionrate coefficients.The value
residencetime in the immobiledomainapproaches infinity.In e• is the geometricmean of the distributionand has units of
the limit of verylarge0-the densityfunctionis log-uniformand
isequivalent
to a powerlawdensityfunctionwith--•0/-•. Aswe
shallseein section3.5, this corresponds
to a late-time BTC of
.-..t-2.
equivalent density function of diffusion rate coefficients.
The Laplacetransformof (26) must be done numerically. Again, althoughthe early time behaviorwill differ for power
The result may then be insertedinto (12). After taking the law densityfunctionsof first-order and diffusionrate coeffi-
secondderivativein time (numerically),the late-timeapprox- cients,the late-time slopewill be identicalfor the samevalue
imation for a concentrationBTC is shownin Figure 3 for of k. For the sake of brevity,we showonly the power law
variousvaluesof 0-.The time axisof Figure3 is normalizedby densityfunction of first-order rate coefficients.
the geometricmean of (21), and concentrationis normalized A truncatedpower law densityfunctionmay be written as
the sameaspreviously.Figure 3 alsoshowsthe solutionto the follows:
ADMT equationsin the presenceof a lognormaldensityfunc-
tion of diffusionrate coefficients.The ADMT equationswere
solved using STAMMT-L [Haggettyand Reeves,2000] for
b(0/) = /3tot(k
k-2 --k-2
2)0/k_3,k>0 k4=
0/max -- 0/min
2, (27a)
mo = 1 x 104 Skgm-3, tad= 1 x 104 s,e• = 1 x 10-4 S-•,
0-: 5, /3tot --- 1, and a Peclet number of 1000. Note that the 0/min • 0/ • 0/max,
late-time slopesfor the lognormaldistributionlie between 2 where0/ma x [T- 1] isthemaximum ratecoefficient,0/min [ T- 1]
and 3 for a largerangeof time, providedthat 0-is greaterthan is the minimumrate coefficient,and k is the exponent.The
approximately3. value of 0/mi
n may be zero if k > 2. The reasonfor choosing
Publishedvalues of 0- for lognormaldistributionsof rate to write the powerlaw ask - 3 will becomeapparentshortly.
coefficientsare typicallylarger than 3 [e.g.,Pedit and Miller, If k = 2, the densityfunctionmay be written
1994, 1995; Culveret al., 1997; Haggettyand Gorelick, 1998;
Haggettyet al., 2001], suggesting that masstransferrate coef- 3tot
ficientshavelargevariabilityin naturalmedia.With suchlarge b(0/) = 0/-1. (27b)
valuesof 0-we would expectto seelate-time slopeson double-
log BTCs after a pulseinjectionbetween2 and 3.
In(0/ma•i,XmlnX
)
The late-time concentration in the mobile domain is
An alternativedensityfunctionthat hasbeenlesscommonly
used to describemasstransferin groundwaterand soilsis a
C :
motad[3tot(k
--2)f•....
k-2
(0/ma
0/k-le-at
x -- 0/min)
k-2
mln
, k>0 k4=2.
(28)
powerlaw densityfunction.Hatanoand Hatano [1998]useda For arbitrary(noninteger)valuesof k, (28) must,in general,
powerlaw densityfunctionof waitingtimesin the contextof a be evaluatednumerically.However,the mostimportantpoint
continuous-timerandomwalk to model the sorptionof radio- about(28) is that
nuclidesin a columnexperiment.Powerlaw densityfunctions
of waitingtimeshavefrequentlybeenusedin statisticalphysics c ---t -k, -• 0/•-n•n. (29)
to describeanomaloustransportbehavior[e.g.,Bouchardand
Expressedin words,the slopeof the BTC is k for times much
Georges,1990; Scheret al., 1991]. Frequently, such density
functionsarise from diffusionor rate-limited sorptionon a
greaterthan0/max
-• andmuchlessthan0/•,•nfor all valuesof k.
fractal geometry.A particularadvantageof a power law dis-
At timesgreaterthan0/•,•n,the slopegoesto infinity.
tribution, within the context of this work, is that it allows us to It is possibleto presentclosed-formsolutionsfor many spe-
investigatepower law BTC behavior for a larger range of
cific casesof (28); we will providethe solutionsfor the cases
k = 1, k = 2, and k = 3. First, let us define three other
late-time slopes.
variablesin terms of 0/ma
x and 0/min
i
As with a gammadensityfunction,it is possibleto define
both a densityfunctionof first-orderrate coefficientsand an q'= 0/maxt
, (30a)
3474 HAGGERTY ET AL.: BEHAVIOR OF TRACER TEST BREAKTHROUGH CURVES
(k-3)
• •m• k>3 Note that there is nothingthat physicallyprecludesa late-
time slopebetween2 and 3 beingmaintainedto infinite time
The exactexpression is givenin equation(34). Note that all approx- (i.e., 2 < k < 3 ast -• oc).A slopeof k -< 2 to infinitetime,
imationsare valid only if ,•t >> 1 (i.e., if the ratio of O/ma
x is much however,would require an infinitelylarge immobile domain
greaterthan O/min)'
(i.e., infinite capacity).Therefore a slopeof k -< 2 cannotbe
maintainedfor infinite time (for this reason,k = 3/2 is pos-
siblewithdiffusion
butonlyuntila timeof •a2/Da).
•t • o/max/o/min, (30b) The late-time behaviorof concentration,as givenby (31)-
2 (33),isshownin Figure4 for o/min
= 10-5 o/max'
Figure4 also
O/max
k•-2 showsthe solutionto the ADMT equationsin the presenceof
2 a powerlaw densityfunctionof rate coefficients.The ADMT
o/p : 2 (30c)
O/max
k--2. equationswere solvedusingSTAMMT-L [Haggetty andReeves,
In (Xt)' 2000]formo = 1 skgm-3, tad----1 S,o/max = 1 S-1, o/min
= 1X
10-s s-1, k = 1, •tot -- l, anda Pecletnumberof 1000.
Notethatap is a functionof o/.... o/min,
andk andisusedfor
the purposeof simplifyingthe followingequationsonly. 3.6. Summary of Late-Time Slopes
Usingthesevariables,the late-timeconcentrationfor k = 1
is therefore Figure5 providesa summaryof late-timeslopesfor several
of the models presented.Late-time slopesare given versus
C= motad•toto/p2(e
-•/x'- e-*)r-•. (31) nondimensional time. Note that a BTC with advection and
If k - 2, then the densityfunction is log-uniform,and the dispersionwill masksomeportionof the slopesshownin Fig-
late-time concentration is ure 5 at earlier times.The slopesgivenin Figure5 will onlybe
presentwhen t >> tad.A powerlaw slopeis a constantat late
time, suchas providedby the gammaand power law density
c= m0tad•toto/p
e • + 1 --e r + 1) r- . functions.Note that conventionaldiffusionmodelis equivalent
If k = 3, then the densityfunctionis uniform, and the late- to the lognormaldensityfunctionwith (r - 0. The slopein the
time concentration is conventionalmodel is 3/2 until approximatelythe mean resi-
dencetime in the immobiledomain(a2/3Da for one-
2E
e-v/x,
r2+•-•
C--motad•toto/p2r+2)-e-*(r2
(•2t2 + 2r+ 2)
(33)
106
From the aboveequationswe seethat a family of curvesis re-
quiredfor eachvalueof k sinceboth o/rain
and o/maxappearin all 104
equations.However,inspectionof theequations indicates
thatthe • ADMT (k = 1)
curves
foreachvalueofk willbeidentical
untilt approaches 102
The harmonicmeanof the densityfunction(27a) and (27b) is
10o
o/min/\t
In(X,)Xt-1' k= 2, • k=l
o/max k = 3, (34)
• =•=0.•
In (X,)' k=2
(k- 3)•.•-2 _ 1 otherwise.
o/min
(k- 2) Xt
i-3- 1' 10'•
3/2 slope
4. Applications to Tracer Tests and Discussion C/C0 10-3
4.1. WlPP Tracer Tests [-] H19S1-1
Slope
0
-1
..
•_uamma
•
%• '%,•,•k=1
'• Power law 10'5
I-.....
10-s '' .... •
105
ii
lOe
t[s]
3/2
•• "• ..•.q=0.5
q=1.5
the data.
canbe seenfrom Figures6a and 6b, the late-timebehaviorof nitelythick,the powerlaw behaviorwith k lessthan 2 mustend
both BTCs is essentiallypower law. The Hll-1 BTC has a at some time. However, without information external to the
slopeof about2.123after2.5 x l0s s (69hours).Theslopeof tracertest data the time at whichthe powerlaw behaviorends
the Hll-1 BTC appearsto becomemore negativeafter about (and thereforethe mean residencetime in the immobiledo-
3 x 106$ (830hours),butthismaybe dueto a 70%increase main) cannotbe known.
in the pumpingrate at that time. In addition,the accuracyof 4.2.3. Case 3: Power law behavior ends within experimen-
the datais relativelylowafter2 x 106S,makingslopecalcu- tal timescale. The third scenariois that the power law be-
lations uncertain.The H19Sl-1 BTC has a constantslopeof havior endswithin the experimentalobservationtime. An ex-
about2.165from5 x l0s s (139hours)to theendof thetest. ampleof this is the conventionaldiffusionmodelwith a slope
Note that conventional(singlerate) diffusioncanonlyprovide of 3/2 at intermediate time. In this case an effective rate coef-
a constantlate-time slopeof 3/2, which is shownfor compar- ficient or mean residence time in the immobile domain can be
isonin Figure 6a. estimated.The mean residencetime will be larger for smaller
The late-timebehaviorof the SWIW testswasinterpretedby slopesandfor verysmallslopeswill approachthe inverseof the
Haggerryet al. [2001] usinga lognormaldensityfunctionof time at which the power law behaviorends.Note that case3
diffusion ratecoefficients(D,•/a2).As shownin thatpaper,a cannotbe modeled by a gammadensityfunction becausea
lognormaldensityfunctiondoesan excellentjob of represent- gammadensityfunctiondoesnot allowfor an end to the power
ing the entire BTC (with o-= 3.55 for Hll-1 and o-= 6.87 for law behavior.
H19Sl-1). However,on the basisof the BTC data alone it is 4.2.4. Case 4: Power law behavior with k > 3. The fourth
not possibleto rule out other densityfunctionsof rate coeffi- scenariois that the BTC hasa slopegreaterthan 3. In thiscase
cients, includinga gamma densityfunction or a power law the mean residencetime can be estimatedeven if the power
densityfunction. law behavior extends to infinite time. This is because the har-
monic mean of a power law densityfunctionis nonzeroand
4.2. Implications Power Law BTC Behavior dominatedby the value of a.... providedthat k > 3.
We note againthat both the gammaand power law density Which scenario do the WIPP SWIW tracer tests fit? On the
functionsresult in power law BTCs at late time, with the basisof the BTC data alone, H19Sl-1 must be either case 1 or
relationshipk - r• + 2. The conventionaldiffusionmodel case2. Sincethe powerlaw behaviorextendsto the end of the
also causespower law BTCs with a slope of 3/2 prior to t - data set,it is not possibleto estimatethe mean residencetime
a2/D,•.Therearefourimportant scenarios for suchpowerlaw of the immobile domain.We know only that the mean resi-
behavior. dence time must be at least the inverseof the experimental
4.2.1. Case 1: Power law behavior to infinite time and k < 3. time(i.e.,-1.9 x 106S).H11-1,however,
maybecase3. If the
The first scenariois that the BTC behavesas a powerlaw over markedchangein slopeat approximately 3 x 106S is not
all time (i.e., the slope of the BTC would be power law to primarilydue to the increasein pumpingrate, then Hll-1 is
infinite time) and that the slopeis lessthan 3. It is important case3. However,if thisis an artifactof the increasein pumping
to note that (1) this is physicallypossibleprovidedthat the rate,then Hll-1 maybe case1 or 2. Giventhe datauncertainty
slopek is alsogreaterthan 2 and (2) severalpaperseffectively afterapproximately
2 x 106s (560hours)andthefactthatwe
invokecase1 by assuminga gammadensityfunctionand find- have not investigatedthe caseof time-varyingpumpingrate,
ing estimatesof r/less than 1 [e.g., Connaughton et al., 1993; we remain uncertain as to which case Hll-1 fits.
Pedit and Miller, 1994; Culver et al., 1997; Werth et al., 1997; Models of the two breakthroughcurveswere constructed
Deitschet al., 1998;Kauffmanet al., 1998;Lotden et al., 1998]. andare shownin Figure6c. In bothcasesa gammadistribution
In case 1 the mean residence time in the immobile domain of rate coefficients was used to model mass transfer, which
mustbe infinite. Consequently,there can be no effectivesin- yieldsa powerlawBTCwithlate-time
behavior
of t-"- 2 (i.e.,
gle-ratemodelthat is equivalentto the multiratemodelin the slopeof k = r• + 2). In additionto masstransferthe model
waythat a single-ratefirst-ordermodelis approximatelyequiv- simulatedadvectionand dispersionradially awayfrom a well,
alent to a conventionalsingle-ratediffusionmodel.No single- a brief restingperiod, and advective-dispersive transportback
rate (either firstorderor diffusion)modelcanyieldthe same to the well (more detailson the transportcode are givenby
secondor highertemporalmomentsasthe multiratemodel.In Haggerry et al. [2000, 2001]). SinceHl l-1 exhibitsan average
fact,anysingle-ratemodel(eitherfirstorderor diffusion)fit to late-timeslopeof 2.123 (measureddirectlyfrom the data),we
data will have parametersthat are a function of the experi- modeledit with r• = 0.123. The only estimatedparametersin
mental observationtime (i.e., the experimentlength). thismodelwere 3' (3.05 x 10-5 s-I), the advective
porosity
4.2.2. Case 2: Power law behavior longer than experimen- (0.0158),andthe dispersivity(0.151m). SinceH19Sl-1 exhibits
tal timescale and k < 3. The second scenario is that the an averagelate-timeslopeof about2.165,we modeledit with
powerlaw behaviorendsat a particulartime that is beyondthe r• = 0.165.Again, the onlyestimatedparametersin this model
experimentalobservationtime andthat the slopeis lessthan 3. werey (2.96x 10-4 S-•), theadvective
porosity
(0.0679),and
In this case the mean residence time in the immobile domain the dispersivity
(0.115m). In bothmodelsall otherparameters
cannot be ascertainedfrom the experimentaldata alone. In were taken from field measurementsand the modelof Haggerry
other words,it is impossible,basedsolelyon the BTC data, to et al. [2001,Tables 1 and 3]. In both Hll-1 and H19Sl-1 the
estimate an effective rate coefficient: The effective rate coef- late-time behavior of the data could have been modeled with
ficientcouldbe eitherundefined(asin case1) or simplylonger only a singleestimatedparameter,advectiveporosity.How-
than the inverseof the experimentaltime. ever,the otherparameterswere estimatedto fit the peak of the
If the slopek is lessthan 2, then the power law behavior BTC.
either must end at some time or the slope must steepento It can be seenthat both modelsare very good representa-
greaterthan 2. Suchis the casewith conventionaldiffusionand tionsof the SWIW data, particularlyat late time. It is worth
a slopeof 3/2. Becausethe immobiledomain cannotbe infi- notingthat the parameterr• determiningthe late-timeslopeof
HAGGERTY ET AL.: BEHAVIOR OF TRACER TEST BREAKTHROUGH CURVES 3477
the BTCs wassimplyread from the data and not fit. This good coefficient estimated from the BTC will be a function of ex-
representationof the late-time data emphasizesthree points: perimentalobservationtime. Again,for a BTC from a medium
(1) The late-time approximationis a good tool for analyzing with initially nonzero but equilibrium concentrations,the
BTCs; (2) the approximationdoes not depend on uniform equivalent BTC goesast -k +•.
velocity;and (3) the approximationdoes not depend on a Sixth,if a BTCexhibits
powerlawbehavior
(c ---t -•') to the
Dirac injectionpulseor negligibledispersionto work well. end of the experiment,then one of two casesmustexist.If k -<
3, thenthe meanresidencetime (and effectiverate coefficient)
cannot be estimated from the BTC. The mean residence time
5. Conclusions
mustbe at leastthe experimentalobservationtime and could
With improvementsin experimentaland analyticaltech- be infinite. If k > 3, then the mean residencetime (and its
niques,breakthroughcurves(BTCs) are now availablefrom inverse,the effectiverate coefficient)can be estimated.
many laboratoryand field experimentswith severalordersof Seventh,the late-time approximationdoes not strictly de-
magnitudeof data in both time and concentration.The late- pend on severalof the assumptions usedin its derivation.The
time behaviorof BTCs is criticallyimportantfor the evaluation approximationwas able to adequatelycharacterizea distribu-
of rate-limitedmasstransfer,especiallyif discriminationbe- tion of masstransferrate coefficientsfrom a single-wellinjec-
tween differentmodelsof masstransferis desired.Double-log tion-withdrawal tracer test, which has conditions of radial
plots of BTCs are particularlyhelpful and commonlyyield time-varyingflow, significantdispersion,and a nonpulse-type
valuable information about mass transfer. injection.
We have sevenprimary conclusions. First, we derived a
simpleanalyticalexpression for late-timeBTC behaviorin the
presenceof masstransfer.Equation (12) givesthe late-time Appendix A: Notes on the Density Function b(ct)
concentrationfor any linear rate-limitedmasstransfermodel We addtwonotesregardingthe densityfunctionb(a). First,
for either zero-concentrationor equilibriuminitial conditions. a usefuldefinitionis that of the zerothmomentof the density
The expressionrequiresthe advectiontimescale,the zeroth function of rate coefficients:
momentof the injectionpulse,the initial concentration in the
system,and the memoryfunction#(t) be known.Note that
cautionis advisedin using(12) if the varianceof tad is large
(suchasin a stronglyheterogeneous velocityfield). We expect
fo
©b(a)
da
=•tot, (A1)
that (12) will be exploitedto understand
breakthrough curves where/3tot [dimensionless]
is commonlyknownasthe capacity
from field and laboratoryexperiments, as well as to develop coefficient[e.g.,Haggerryand Gorelick,1995]. The capacity
criteriafor designingbetter tracerteststo meet specificgoals coefficient is the ratio of mass in the immobile domain tO mass
(e.g.,estimatingmasstransferrate coefficients). in the mobiledomainat equilibrium;in the absenceof sorption
SeCond,the memoryfunction#(t) is proportionalto the it is the ratio of the two volumes.
residencetime distributionin the immobile domain given a Second,we note without derivationthat the Laplace trans-
unit impulseat the surfaceof the immobile domain. This form of the densityfunctionof rate coefficientsis a particularly
memoryfunctionis simplythederivative of theLaplacetrans- usefulfunctionby itself. This functionis proportionalto the
form of the densityfunctionof rate coefficientsdescribingthe massfraction remainingin the immobile domain, where the
immobiledomain.Consequently,the late-time concentration initial conditions are uniform concentration in the immobile
is proportionalto the first or secondderivativeof the Laplace domainandthe boundaryconditionon the immobiledomainis
transformof the densityfunctionof rate coefficients. zero concentration.The massfraction (M/Mo) remainingin
Third, the effective rate coefficientthat yields the same the medium(both mobileand immobiledomains)at late time
zeroth,first,and secondBTC temporalmomentsas doesthe is therefore
full densityfunctionis the harmonicmeanof the densityfunc-
tion of rate coefficients.
However,for anydensityfunctionof
ratecoefficients
withpowerlawa•- 3 asa -• 0 andwherek <
3, the harmonicmean is zero. Consequently,the mean resi-
dence time in the immobile domain is infinite, and there is no
M(t)•{b(a)} fo
©b(a)e-"tda(A2)
M•-=•1+/3to--' 1nt-•tot '
singleeffectiverate coefficient.This appliesboth to density
functionsof diffusionrate coefficientsand densityfunctionsof whereM(t) is the massat anytime andMo is the totalinitial
first-order
ratecoefficients. havebeen mass.
Manysuchdistributions In other
Words,
themass
fraction
remaining
within,
for
invoked in the literature. example, a column after several pore volumes have been
Fourth,if theBTC(aftera pulseinjection) goesas•t -• as flushedthroughit, is calculatedsimplyby findingthe Laplace
t -• c•, thenthe underlyingdensityfunctionof rate coefficients transformof the densityfunctionb(a).
mustbe • a•-3 asa -• 0. Thisholdsfor density
functions
of
both first-order and diffusion rate coefficients. For a BTC from
a medium with initially nonzero but equilibriumconcentra- Appendix B: Notes on Application
tions,theequivalent
BTC goesast •-•, of Equation (12)
Fifth, if the slopeof a BTC (after a pulseinjection)goesto Equation (12) presentsan interestingtheoreticaldevelop-
k as t -• • and k -< 3, then the mean residence time in the ment for two reasons.First, the late-time behavior of the BTC
immobiledomainis infinite. (This is a corollaryto the third is easilyobtainedfor a wide varietyof densityfunctionsb(a)
and fourth conclusions.) Consequently,there is no singleef- usingany comprehensive table of Laplace transforms.Equa-
fectiverate coefficientin thismedium.A secondconsequence tion (12) is simplerfor first-ordermasstransferthanthe equa-
is that any single-rate(either diffusionor first order) rate tions developedby Vereecken et al. [1999].The equationalso
3478 HAGGERTY ET AL.: BEHAVIOR OF TRACER TEST BREAKTHROUGH CURVES
Hatano, Y., and N. Hatano, Dispersivetransport of ions in column theoreticalaspectsof solutediffusionin sphericaland nonspherical
experiments:An explanationof long-tailedprofiles,WaterResour. aggregates,Soil Sci.,133(6), 342-349, 1982.
Res.,34(5), 1027-1033,1998. Rasmuson,A., The effect of particlesof variable size, shape and
Hollenbeck, K. J., C. F. Harvey, R. Haggerty, and C. J. Werth, A propertieson the dynamicsof fixed beds,Chem.Eng. Sci., 40(4),
methodfor estimatingdistributionsof masstransferrate coefficients 621-629, 1985.
with applicationto purgingand batchexperiments,J. Contam.Hy- Roberts,G. E., and H. Kaufman,Tableof LaplaceTransforms, W. B.
drol., 37(3-4), 367-388, 1999. Saunders,Philadelphia,Pa., 1966.
Jaekel, U., A. Georgescu,and H. Vereecken,Asymptoticanalysisof Ruthven,D. M., andK. F. Loughlin,The effectof crystalliteshapeand
nonlinearequilibriumsolutetransportin porousmedia, WaterRe- size distribution on diffusion measurements in molecular sieves,
sour.Res.,32(10), 3093-3098,1996. Chem.Eng. Sci.,26(5), 577-584, 1971.
Kauffman, S. J., C. H. Bolster,G. M. Hornberger,J. S. Herman, and Sahoo,D., and J. A. Smith,Enhancedtrichloroethenedesorptionfrom
A. L. Mills, Rate-limited transportof hydroxyatrazinein an unsat- long-term contaminatedsoil usingtriton X-100 and pH increases,
urated soil,Environ.Sci. Technol.,32(20), 3137-3141, 1998. Environ.Sci. Technol.,31(7), 1910-1915, 1997.
Lafolie, F., and C. Hayot, One-dimensionalsolutetransportmodelling Scher,H., M. F. Shlesinger,andJ. T. Bendler,Time-scaleinvariancein
in aggregatedporousmedia, 1, Model descriptionand numerical transportand relaxation,Phys.Today,44(1), 26-34, 1991.
solution,J. Hydrol.,143(1-2), 63-83, 1993. Stager,M.P., and G. P. Perram, Long-term desorptionof trichloro-
LePage,W. R., ComplexVariablesand theLaplaceTransform for En- ethylenefrom flint clayusingmultiplexedopticaldetection,Environ.
gineers,McGraw-Hill, New York, 1961. Pollut.,104(3), 397-400, 1999.
Lessoff,S.C., and L. F. Konikow, Ambiguity in measuringmatrix Valocchi, A. J., Use of temporal moment analysisto study reactive
diffusionwith single-wellinjection/recoverytracertests,GroundWa- solute transportin aggregatedporousmedia, Geoderma,46(1/3),
ter, 35(1), 166-176, 1997. 233-247, 1990.
Lorden, S. W., W. Chen, and L. W. Lion, Experimentsand modeling van Genuchten,M. T., and P. J. Wierenga, Mass transfer studiesin
of the transportof trichloroethenevapor in unsaturatedaquifer sorbingporousmedia, 1, Analyticalsolutions,Soil Sci. Soc.Am. J.,
material,Environ.Sci. Technol.,32(13), 2009-2017, 1998. 40(4), 473-480, 1976.
McLaren, R. G., C. A. Backes,A. W. Rate, and R. S. Swift, Cadmium Vereecken, H., U. Jaekel, and A. Georgescu,Asymptoticanalysisof
and cobalt desorption-kinetics from soil clays:Effect of sorption solutetransportwith linear nonequilibriumsorptionin porousme-
period,Soil Sci.Soc.Am. J., 62(2), 332-337, 1998. dia, Transp.PorousMedia, 36(2), 189-210, 1999.
Meigs,L. C., andR. L. Beauheim,Tracertestsin a fractureddolomite, Villermaux, J., Deformation of chromatographicpeaksunder the in-
1, Experimentaldesignand observedtracer recoveries,WaterRe- fluenceof masstransferphenomena,J. Chromatogr.Sci., 12, 822-
sour.Res.,in press,2001. 831, 1974.
Meigs,L. C., R. L. Beauheim,and T. L. Jones(Eds.), Interpretations Villermaux,J., Theory of linear chromatography, in PercolationPro-
of tracer testsperformedin the Culebra dolomite at the Waste cesses:Theoryand Applications,NATO ASI Ser. E, edited by E.
Isolation Pilot Plant site, Rep. SAND97-3109, Sandia Natl. Lab., Rodriguesand D. Tondeur,vol. 33, pp. 83-140, Sijthoffand Noord-
Albuquerque,N.M., 2000. hoff, Rockville, Md., 1981.
Neretnieks,I., and A. Rasmuson,An approachto modelingradionu- Wagner,B. J., and J. W. Harvey,Experimentaldesignfor estimating
clidemigrationin a mediumwith stronglyvaryingvelocityandblock parametersof rate-limitedmasstransfer:Analysisof streamtracer
sizesalong the flow path, WaterResour.Res., 20(12), 1823-1836, studies,WaterResour.Res.,33(7), 1731-1741,1997.
1984. Werth, C. J., J. A. Cunningham,P. V. Roberts, and M. Reinhard,
Pedit, J. A., and C. T. Miller, Heterogeneoussorptionprocessesin Effects of grain-scalemass transfer on the transport of volatile
subsurfacesystems,1, Model formulationsand applications,Envi- organicsthroughsediments,2, Column results,WaterResour.Res.,
ron. Sci. Technol.,28(12), 2094-2104, 1994. 33(12), 2727-2740, 1997.
Pedit, J. A., and C. T. Miller, Heterogeneoussorptionprocessesin
subsurface systems,2, Diffusionmodelingapproaches, Environ.Sci. R. Haggerty,Departmentof Geosciences, OregonState University,
Technol.,29(7), 1766-1772,1995. Corvallis,OR 97331-5506.(haggertr@geo.orst.edu)
Peszyfiska,M., Finite element approximationof diffusionequations S. A. McKenna andL. C. Meigs,Geohydrology Department,Sandia
with convolutionterms,Math. Comput.,65(215), 1019-1037,1996. NationalLaboratories,P.O. Box 5800, MS-0735,Albuquerque,NM
Rao, P.S. C., D. E. Rolston,R. E. Jessup,and J. M. Davidson,Solute 87185-0735.(samcken@nwer.sandia.gov; lcmeigs@nwer'sandia'gøv)
transportin aggregated porousmedia:Theoreticalandexperimental
evaluation,Soil Sci. Soc.Am. J., 44(6), 1139-1146, 1980. (ReceivedOctober4, 1999;revisedMay 4, 2000;
Rao, P.S. C., R. E. Jessup,and T. M. Addiscott,Experimentaland acceptedJuly 17, 2000.)