WATER RESOURCES RESEARCH, VOL. 36, NO.

9, PAGES 2493-2500, SEPTEMBER 2000

Correlation of colloid collision efficiencywith hydraulic

conductivity of silica sands
JianhongRen and Aaron Ian Packman
Departmentof Civil and ArchitecturalEngineering,Drexel University,Philadelphia,Pennsylvania

Claire Welty
Schoolof EnvironmentalScience,Engineering,and Policy,Drexel University,Philadelphia,Pennsylvania

Abstract. Columnexperimentswere conductedin the laboratoryto studythe relationship

betweenlocal-scalecolloidfiltration parametersand physicalheterogeneityas represented
by soil or rock hydraulicconductivity.Natural (polydisperse) sandwas sievedinto distinct
classesto producerelativelyhomogeneous porousmedia for the experiments.Silica
particles0.45/xm in diameterwere usedas the transportedcolloids.The column
experimentswere carriedout under carefullycontrolledchemicalconditions.The
hydraulicconductivityof eachpackedcolumnwasdeterminedusinga constant-head
permeameterarrangement.Conservativetransportparameters(dispersivityand effective
porosity)were obtainedusinga salt tracer. Comparisonof soluteand colloidbreakthrough
curvesindicatedthat particle depositionrateswere unsteadyin the column.This behavior
was analyzedusinga blockingfunctionwhich describesthe alterationof the sandsurface
due to the accumulationof depositedcolloids.By this method,clean-bedcollision
efficiencyfactorswere obtained for colloid filtration in each of the sand sizes.An inverse
relationshipwasobservedbetweenthe collisionefficiencyfactor and the grain sizeof the
collectormedium.This relationshipwas attributedto a variationof surfaceheterogeneity
with sandparticlesize.This theoryis supportedby the direct correlationof collision
efficiencywith surfaceheterogeneity parametersof the blockingfunction.The colloid
filtration data were usedto parameterizea linear correlationbetweenthe collision
efficiencyfactor and the naturallogarithmof the mediumhydraulicconductivity.The
collectorefficiency,normallycalculatedfrom theoreticalmodelsfor colloidtransportin
the vicinityof collectorgrains,was alsoshownto be a linear functionof the natural
logarithmof hydraulicconductivity.Correlationsof this type can be usedeffectivelyin
stochasticmodelingof colloidtransportthroughheterogeneous porousmedia.

1. Introduction constantionicstrength,pH, and colloidsurfacecharacteristics.

These data are used to parameterizethe correlationin the
Rehmannet al. [1999] recentlypresenteda new theoretical stochasticmodel and can be similarlyused in other models
frameworkfor modelingvirus and abioticcolloidtransportin requiring a relationshipbetween hydraulicconductivityand
heterogeneous aquifersusinga stochasticapproach.Motiva- filtration parameters.This approachcould also be used to
tion for developingthe model was twofold:(1) Colloidshave parameterizethe effectsof solutionchemistry,colloid surface
been shownto travellargedistances in aquifers,and (2) field- properties, and mineral heterogeneityin stochasticcolloid
scalemodelsdo not adequatelyrepresentthe interactionof transportmodels.
physicalheterogeneityand local-scalecolloid transport.Reh-
mann et al. [1999] coupledcolloid-filtrationtheory,originally
developedfor water filtration applications[Rajagopalanand 2. Background
Tien, 1976;Logan et al., 1995],with local-scaleequationsfor
Darcy flux and massconservationin porousmedia. Subsurface The relevantphenomenaaffectingcolloid transportin po-
heterogeneitywas modeledby consideringthe hydrauliccon- rousmedia includeadvection,dispersion,attachment,and de-
ductivitydistributionas a randomfield. To completethe cou- tachment. The governingequations for local-scalecolloid
pling, Rehmannet al. [1999] postulatedthat certain correla- transportthrougha one-dimensional columnare
tions could be expectedto exist between local-scalecolloid OC OC 02C Pb
filtration parametersand physicalheterogeneity(as repre- Ot+ Up -•--- OILU
p-•- matt s q-kdet -•-S, (1)
sentedby hydraulicconductivity).
Thispaperpresentsa setof laboratorydatathat supportsthe PbOS Pb
hypothesis that an inverserelationshipexistsbetweencollision n Ot= matte -- kdet
-•-S, (2)
efficiencyac and hydraulicconductivityunder conditionsof
where C is massper unit volume of suspendedcolloids,S is
Copyright2000 by the AmericanGeophysicalUnion. massfractionattachedto the solidsurfaces,
Vpis the mean
Paper number2000WR900163. colloid velocity, a L is local-scaledispersivity,n is effective
0043-1397/00/2000WR 900163$09.00 porosity,Pb is bulk densityof the porousmedium,mat t is the
2493
2494 REN ET AL.: CORRELATION OF COLLOID COLLISION EFFICIENCY

Table 1. Sand Size Classes applying(4) and (5). In practice,r• is calculatedthrough(6), X

Minimum Effective
is generallydeterminedby applying(3) to experimentaldata,
Sanda Diameter, •m Diameter,•m Diameter,
b •m and a c is then obtainedfrom (5). Dispersivity,effectiveporos-
ity, and meanpore watervelocitycanbe determinedby fitting
#60-70 250 212 231
the advection-dispersion equationto breakthroughdata from
#70-80 212 180 196
#80-100 180 150 165
running a conservativesolutethrougheach column,and hy-
#100-!20 150 125 137 draulic conductivityis determinedat a recordedtemperature
#120-140 125 106 116 for eachcolumnusinga constant-head permeametersetup.If
# 140-170 106 90 98 desired,the parameterkdetcouldbe determinedundera setof
, , ,

conditionswhere the influentconcentrationis allowedto go to

aThesenumbersrefer to sievesizesusedto separatethe sandinto
each size class. zero and the experimentis run until the effluent colloid con-
bValueusedfor calculation
purposes,
takenasthearithmetic
mean centrationdecreasesto a negligiblevalue.
of the uppei'and lower boundsof eachsizeclass. Rehmannet al. [1999]postulatedthat a c shouldbe corre-
lated to soil grain size as representedby the soil hydraulic
conductivity.This conjecturewas based on the well-known
attachmentcoefficient,and k det is the detachmentcoefficient. observationthat lower-conductivitymaterials such as clays,
In thiswork•we will modellocal-scaleattachmentusingcolloid composedof small-diametergrains,havea larger surface-area-
filtrationtheory,ashasbeendoneby others[e.g.,Tobiasonand to-volume ratio than higher-conductivitymaterials such as
O'Melia, 1988; Bales et al., 1991, 1993; Saierset al., 1994; Schi- gravelsand would therefore be expectedto provide greater
jven et al., 1999;Loganet al., 1995;Martin et al., 1996].The opportunityfor colloid-graininteractions.The proposedeffect
filtration coefficientX has traditionallybeen determinedfrom on colloid transportis similarto, but independentfrom, pre-
viouslywell-studiedinfluencessuchassolutionproperties(ion-
C/Co = exp[-XL], (3) ic strengthandpH), colloidproperties(size,shape,andsurface
where C and Co are effluent and influentparticleconcentra- charge),and collectorgraincomposition.
tions,respectively, for a suspension passingthrougha column Rehmannet al. [1999]proposedthat the followingcorrela-
of lengthL. This equation,thoughinitially obtainedempiri- tion would be expectedto exist:
cally[Iwasaki,1937],representsa solutionto (1) for the caseof a c=a +bin(K) +3, (7)
a steadyreleaseof Co at x = 0, no detachment,and negligible
dispersion.Solutionsthat include dispersionhave been pre- wherea andb are experimentally determinedconstants, K is
sentedby de Marsily[1986]andMau [1992].In thisapproach the hydraulic conductivityof the porous medium, and 8 rep-
the parameterk att is givenby resentsan uncorrelatedrandomportion of ac that cannotbe
accountedfor by the variabilityin the In K field, that is, vari-
katt -- •.Vp. (4) abilitydue to solutionand colloidsurfaceproperties.A corre-
Classicalsingle-collector removal theory separatesphysical lation with In K waspostulatedbasedon a reparameterization
transportand particle-particleinteractionsas of the transportequationsof Rajagopalanand Tien [1976]in
terms of publishedrelationsbetweengrain size, effectivepo-
-n) rosity,and In K.
X= 2d acT, (5) Whereas numerouslaboratory studieshave demonstrated
the effect of solutionand colloidsurfacepropertieson ac for
whered is a representative (e.g.,mean)grain diameter,ac is a givenporousmedium [e.g., Tobiason,1989;Elimelechand
the collisionor stickingefficiencyfactor (the fractionof col- O'Melia, 1990; Liu et al., 1995; Nocito-Gobel and Tobiason,
loidsthat adhereto the soil grainsafter makingcontact),and 1996],the focusof thiswork is to isolatethe effectof grainsize,
r• is the single-collector
efficiency(the fractionof transported as reflectedby the bulk measuredpropertyof hydrauliccon-
colloidsthat comeinto contactwith the collectorgrains). ductivity,on ac. In this work, we have sievedsilicasandinto
The single-collector efficiency(r0 can be calculatedbased numeroussize fractionsand conductedparallel colloidfiltra-
on the physicsof particledeposition,that is, usingtheoryfor tion experimentswith the varioussandfractionsusingidentical
the processes of particlediffusion,inertial impaction,and set- colloid surfaceconditions,solutionchemistry,and flow rate.
tling [Rajagopalan and Tien, 1976]: Observeddifferencesin colloidbreakthroughcan thereforebe
attributedto the variationin the grain size(hydraulicconduc-
"'s B-•-
nvdpd
+As{
4H (rtv)1/8d15/8
dp tivity) of the sands.

3. Methods and Materials

+000338As[
(pp
- P)g]
ß 1.2
d2do.4 18/x (nv)•.2, (6) 3.1. Material Preparationand ExperimentalSetup
wheredpisthecolloiddiameter,
v isusually
takenasthepore Two 25 mm glasschromatography columns(Omnifit, Cam-
watervelocity,
H is the Hamakerconstant (10-20 J), /.• is bridge,England)with adjustableendpiecesand 100/xm frits
dynamicviscosityof water at experimentaltemperature,p is were usedfor the experiments.The columnswere packedwith
thesolution
density,
Pvisthebuoyant of thecolloids, an initiallypolydispersesandthat had been sievedinto distinct
density
BzisBoltzmann's
constant
(1.38x 10-23kgm2 s-2 K-l), g is sizeclasses.In this way we obtainednearly homogeneouspo-
accelerationdue to gravity,T is temperature(K) andA• is a rous media which had different grain sizesbut the same or
constant
for the medium,givenby 211 - (1 - n)S/3]/[2- nearlythe samemineralogyandsurfacecomposition.The sand
3(1 - n) 1/3+ 3(1 - n)s/3 - 2(1 - n)2] [Happel,1958]. sizesusedare listedin Table 1. While Littonand Olson[1993]
In principle,a c canbe determinedby inverting(1) andthen noted that sievingis not an optimal separationprocedurebe-
 REN ET AL.: CORRELATION OF COLLOID COLLISION EFFICIENCY 2495

Table 2. ExperimentalData for Each Sand Sizea

K, v, at., /•b Number
Sand Size m s-• cm min- • cm m-1 •cb •c c T$
d of Runs

#60-70 7.73E-05 5.51 0.23 0.45 3.26 0.15 0.13 0.0060

#70-80 6.71E-05 4.60 0.19 0.54 9.52 0.46 0.38 0.0058
#80-100 4.88E-05 4.73 0.15 0.52 11.03 0.39 0.35 0.0065
# 100-120 3.76E-05 5.25 0.19 0.47 16.09 0.33 0.32 0.0086
# 120-140 3.33E-05 5.31 0.25 0.46 33.10 0.50 0.45 0.0094
# 140-170 2.77E-05 4.69 0.21 0.53 46.12 0.68 0.65 0.0093

aValuesgivenareaveragesfor multipleruns.Read7.73E-05as7.73x 10-5.

bValuesare determined
frominitialbreakthrough.
CValuesare obtainedfrom blockingfunctionsolution(seesection4.1).
dValues
arecalculated
fromequation
(6).

causeit can changethe particle surface,this methodologywas was usedfor all experiments.The differencein head between
required to yield large quantitiesof separatedsand.Further- the two constant-headtankswas adjustedto achievethis flow
more, the sandwas cleaned extensivelyaccordingto the fol- rate for eachrun. This flow was chosenfor experimentalcon-
lowing procedurein order to remove surfaceimpurities.The venienceeven though it is much higher than typical ground-
sandwassoakedin 10% HC1 overnight.Milli-Q water (18 mgl water velocities.Trends of filtration versushydraulicconduc-
cm, Millipore Corp.,Bedford,Massachusetts) wasthenusedto tivity observedin thesecolumnexperimentsare also expected
rinsethe sandto pH 6-7. The cleanedsandwasdried at 105øC to occurat the lowervelocitiestypicallyfound in groundwater,
and stored in a clean container covered with aluminum foil. thoughthe parametersof the correlationmaybe different.The
The colloidal particles used in the experimentswere an temperature was recorded after each hydraulic conductivity
industrialsilica,0.45/am in diameter,manufacturedby Nissan measurement.All experimentswere carried out between 21ø
ChemicalIndustries,Ltd. (Tokyo, Japan).These colloidsare and 25øC.Valuesof hydraulicconductivity for eachsandsize
nowbeingextensively usedin laboratoryfiltration experiments are providedin Table 2.
becauseof their simple compositionand uniform size; their
surfacechargecharacteristics havebeenreportedbyJohnsonet 3.3. Tracer Test for Characterizationof Sand Dispersivity
al. [1996] andHong et al. [1997].Downwardflow throughthe and Porosity
columnwas controlledby two constant-headtanks. Fluid was Sodiumchloride(NaC1)wasusedasa conservative tracerin
pumped continuouslyby a MasterFlex Microprocessorpump order to determine the d.ispersivity
and effectiveporosityof
drive (Cole-ParmerCompany,Vernon Hills, Illinois) to the each packedcolumnof sand.The inflow solutewas injected
upper tank in order to provide an overflowto maintain the continuously
at a concentration
of 117mgl-•. Saltconcen-
constant head. The differential head between the two constant- trationswere determinedby measuringsolutionspecificcon-
head tankswas determinedusinga pair of manometers. ductance using a Cole-Parmer 01481-61 conductivitymeter
with a micro-flow-throughcell. The inflow and outflow con-
3.2. Hydraulic Conductivity Measurement centrations of NaC1 were obtained from the calibrated stan-
Hydraulic conductivitywas calculatedfrom Darcy's law: dardcurveof the measured
specific
conductance.
Dispersivity
Q/A = -Kdh/dx, where Q is the volumetricflow rate (de- was determinedby fitting the effluentbreakthroughcurveto
terminedby collectingeffluentover a giventime period),A is the following solution of the one-dimensional advection-
the cross-sectionalarea of the column, and -dh/dx is the dispersionequation:
hydraulicgradient (typically measuredas the difference in
headoverthecolumnlengthL). A flowrateof 12mL min-•
Co
C=-•- (x-vt
erfc I Co x
•-exp
x/4aLvt/
x+vtI,
(•-f•)erfc(•4aLv
(8)
Time, min
0 5 10 15 20 where v was calculated as v = L/tso and tso is the time at
1.2 which50% of the solutehasleft the column.(All other vari-
ableswere definedpreviously.)CXTFIT codeversion2.0 was
usedfor the curvefitting[Torideet al., 1995].Effectiveporosity
- t was calculatedfrom n - Q/vA. The tracer testswere always
0.8 _

_
_
.x conductedindependentlyof filtrationexperiments, but the col-
0.6 umnswere not disturbedbetweentestssothat the packingwas
A o o preserved.A typicalbreakthroughcurveis shownin Figure 1.
0.4 o o o
o
The smoothbreakthroughcurveindicatesthat the columnwas
0.2
• NaC! packed homogeneouslyand had no significantpreferential
- • • Colloid
flow paths.The dispersivityand effectiveporosityof eachsand
&l , , , I , , , , I , , , , I , • , , size are given in Table 2.
0 5 10 15 20
Pore volumes 3.4. Filtration Test

Figure 1. Typicalsoluteand colloidbreakthroughcurvesfor In order to conduct filtration experimentswith carefully

sand #100-120. controlledsolutionchemistry,the sandcolumnwas saturated
2496 REN ET AL.: CORRELATION OF COLLOID COLLISION EFFICIENCY

with NaC1by leachingit with at least40 pore volumesof 100
mM NaC1 before each experiment.The effluent solutionsof
the preequilibratedsand columnshad pHs between 6.1 and
6.5. Filtration experimentswere conductedwith uniform 0.45
/xm colloidalsilica(MP4540 obtainedfrom NissanChemical
Industries,Ltd.). Silicasurfacesare negativelychargedunder
our experimentalconditions.Preliminary experimentswith
thesecolloidsin a 5 mM NaC1backgroundsolutionyieldedno
filtration, indicatingthat the sandcollectorsurfaceswere ef-
fectivelycleaned.More precisely,it can be saidthat the sand
surfacespresenteda net repulsivechargeand had no hetero-
geneoussurfacepatcheslarge enoughto producelocally fa-
vorableconditionsfor colloidcapture.To encouragefiltration
of the silicacolloids,electrostaticrepulsionwas hinderedby
increasingthe solutionionic strengthto the valuesreported
here. A columnlength of 6 cm was chosenin order to obtain
reasonablecolloidbreakthroughcurvesfor the range of sand
sizes used.
The colloidalsilicasuspension
was dilutedwith a 100 mM
NaC1solution
to a concentration
of 50 mgL -• andstirredfor
around 1 hour before beinginjectedinto the column.At time
t - 0 the influentwas switchedfrom the backgroundelectro-
lyte solutionto the colloidalsuspension.Both the background
electrolyteand the particlesuspension were maintainedat the
samehead sothat therewasa smoothtransitionto the particle
feed. The silicasuspension waspumpedcontinuouslyuntil the
effluent attained a roughlyconstantconcentration.The con-
centrationof the colloidal suspension was measuredby UV-
visiblelight spectrophotometer at 300 nm wavelengthbasedon
a previouscalibration.This is similar to the method used by
Packmanet al. [1997].Duplicateor triplicateexperiments were
conducted for each sand size.
portionsof the experiments,classicaldispersionand clean-bed
filtrationcannotaccountfor the observedcolloidbreakthrough
curve.Accordingto recentliterature[e.g.,Johnsonet al., 1996;
Johnsonand Elimelech,1995;Songand Elimelech,1993;Kallay
et al., 1987],collectorsurfaceheterogeneitycanusuallyexplain
this anomalouscolloid depositionbehavior.The gradual in-
creasein particle concentrationafter the initial breakthrough
indicatesthat the depositedcolloidspreferentiallyblockedfa-
vorable attachment sites on the sand surface. This causes a
decreasein the collisionefficiencyfactor over time. The ob-
servedblockingbehaviorwill be analyzedin section4.1.
4.1. Determination of Clean-Bed Collision Efficiency
Factors
On the basisof our observationof nonidealbreakthroughof
the silicacolloids,we analyzedthe colloiddepositiondynamics
usinga blockingfunctionin orderto obtainclean-bedfiltration
coefficientsfor our comparativeanalysisof the effect of sand
grain size.Note that it is not proper to use the final observed
effluent concentrations to calculate filtration coefficients. The
clean-bedcollisionefficiencyfactor a c canbe obtainedfrom a
classicalbreakthroughcurve, that is, one which immediately
comesto a steadyeffluent concentration.When a nonsteady
breakthroughis observed,the dynamicaspectsof particledep-
osition must be considered.That is, the collisionefficiency,
filtration coefficient,and attachmentcoefficientwill all vary
with time, dependingon the availabilityof favorabledeposition
sites.Neglectingdetachment,(1) and (2) canbe writtenin the
followingform:
OC OC 02C fm O0
-- -•-Up
Ot
-• = OIL
UpOX2 ,rrp
20t' (9)
O0

4. Filtration Results and Discussion m•-= crcKpxrrp2CB(O), (10)

A typicalcolloidbreakthroughcurveis shownin Figure1. As wheref is the specificsurfacearea of collectors,
f - 3(1 -
expected,colloidswere consistently observedto be transported n)/(nrc), rc isthecollector
radius,
m issingle-particle
mass,
rp
throughthe columnfaster than the tracer becauseof the size is particleradius,0 is the fractionalsurfacecoverageof collec-
exclusioneffect [Kretzschmar et al., 1997].Note that the solute torgrains,
Kp istheparticletransfercoefficient,
Kp = •qq/4,q
breakthroughcurve attainsa constanteffluent concentration is the approachvelocity(Darcyvelocity)equalto Q/A, and
after approximately3 pore volumes.However,the colloidcon- B (0) is the dynamicblockingfunctionwhichaccountsfor the
centrationin the effluent still increaseslong after this time. alteration of the collector surface due to colloid accumulation
Since the flow conditions are identical in the solute and colloid
[Johnson and Elimelech,1995;Johnsonet al., 1996].The dep-
ositionterm is here quantifiedby the fractionalsurfacecover-
age of collectorgrainsrather than the massof retainedparti-
cles.Langmuiriandynamicblockingtheorycan be appliedto
Time, min
0 40 80 120 160 200 240 280 analyze blocking behavior [Johnsonand Elimelech, 1995],
yieldingan analyticalsolutionfor the effluentparticleconcen-
tration:

Coexp(crcKpxrrp213Co,/m)
C(x', ,) =
exp(ad(p•rrp213Cor/m)
+ exp(ad(dCx
') - 1'

0.4
• tt• -
0 Colloid
- - Alpha=0.15 where/3is the excludedareaparameter,/3-- 1/0max,0maxis the
•. .... Alpha=0.28
jamminglimit (obtainedfrom the experimental dataaccording
f -, to the proceduredescribedby Johnsonand Elimelech[1995],
, = t - x' andx' = L/vp aretransformedtimecoordinates,
0 50 1• 150 2• 250 Vpistheinterstitial
particlevelocity
nowexplicitly
calculated
as
Pore volumes
Vp= q/n[2 - (1 - rp/ro)2],ro istheaverage
poreradius,
Figure 2. Colloid breakthroughwith blockingfunctionsolu- ro = (1.1969n - 0.1557)rc, and a c is specificallythe initial
tionsfor differentvaluesof the collisionefficien• factor(ac) (clean-bed)collisionefficiencyfactor.
for sand g100-120. An estimatedclean-bedcollisionefficiencyfactor a c was
 REN ET AL.: CORRELATION OF COLLOID COLLISION EFFICIENCY 2497

4.2. Correlation Between Filtration Parameters

and Hydraulic Conductivity
O00 0 0 0 0 0 0
0.8 A A A A Our datafor the singlecollectorefficiencies
(r/) andcollision
& X 0 X efficiencies(ac) of the varioussandsare plottedversusIn K in
0.6 AA
AA Figure 4. Interrun variabilityis expressedthrougherror bars
representing+_1standarddeviation.Variability in hydraulic
0.4
conductivityresultsfrom different degreesof packingin the
+ V+ V individualcolumnexperiments.Packingfactorsalso affect fil-
q' + V
#70-80 .•- #120-140 tration behavior,and someerror is expectedfrom subtlevari-
0.2
.•..+0 10 20 30
X

40
#80-100

50
V

60
#140-170

70 80
ations in colloid and sand characteristics.
In the conventionalseparationof a c and r/ the effect of
Time, min changingsand diameter appearsin the collector efficiency.
Inspectionof (6) for r/showsa strongdependence on both the
Figure 3. Typicalcolloidbreakthroughcurvesfor eachsand
size. graindiameterand the porosityof the medium.Rehmannet al.
[1999]used(6) andpublishedestimatorsfor hydraulicconduc-
tivity to determinethe relationshipbetweenr/and In K. This
calculatedusing(3)-(6) and the valueof C/Co at the time of analysisindicatedthat r/* = [3(1 - n)/2d]v• shouldbe a
initialbreakthrough(i.e., at approximately 4 porevolumes,but linear functionof In K for constantpore water velocity,with a
thisdependedon the shapeof the breakthroughcurve).Since second-orderdependenceon v. We found r/ to be a strong
the breakthroughs were unsteady,C/Co continuedto increase function of grain diameter and that r/has a negativecorrela-
after the initial breakthrough,indicatingthat colloid deposi- tion with the natural logarithm of hydraulicconductivity,as
tion graduallyfilled locallyfavorablefiltrationsites.If (3)-(6) shownin Figure4a. The correlationbetweenr/and In K canbe
are applied to this type of breakthroughcurve, then time- parameterizedas
varyinga c and )t are found. For the breakthroughcurve in -0.032 - 0.0039 In K, (12)
Figure1 the collisionefficiencyfactordecreased from an initial
valueof 0.33 (at 4.4 pore volumes)to a final valueof 0.13 (at with r = 0.95. We found no need to account for variations in
56 pore volumes,the end of sampling).This showsthat a pore water velocity,as the run-to-runvariationof pore water
considerableerror may be introducedif the dynamicdeposi- velocitywaslessthan 20% in our experiments(and Rehmann
tion behavioris ignored.An alternate estimateof the clean- et al. [1999] sawonly a mild effect from order-of-magnitude
bed a c can be obtained by analyzingthe unsteadybreak- variationsin velocity).The correlationbetweenr• and In K
through, that is, by fitting the experimentaldata with the reflects the fact that grain size and porosity of the porous
blockingsolution(equation(11)), as shownin Figure 2. The mediumcontrolboth the collectorefficiencyand the hydraulic
blockingprocedureyieldsa bestfit valueof a c = 0.28 for the conductivity. However,the linear correlationwith In K is not
breakthroughcurve shownin Figure 1.
apparentfrom (6), and thus our result shouldbe usefulfor
Values of the clean-bed filtration coefficient )t and collision
groundwatermodelerswho seek to relate colloid transport
efficiencyfactora c estimatedfrom the initial breakthroughare parametersto hydraulicconductivity.
given in Table 2 for each sand size alongwith valuesof a c Interestingly,we alsoobserveda grain sizedependencebe-
obtainedusingthe blockingfunction.The reportedvaluesrep- yond what is predictedby conventionalfiltration theory. As
resent averagesof multiple individualruns, as indicated in theorizedin our previousstochasticanalysis[Rehmannet al.,
Table 2. Note the general agreementbetween the two esti- 1999],our data indicatea negativelinear correlationbetween
mates of the clean-bed a c. For comparison,typical break- collisionefficiencyac and the natural logarithmof hydraulic
throughcurvesfor each sandsize are plotted togetherin Fig- conductivity,as shown in Figure 4b. On the basis of these
ure 3. The effectof changingsandsizeis immediatelyapparent results,we have been able to parameterizethe correlationas
in the breakthroughcurves,though it is difficult to directly follows:
assess the effecton ac becausethe physicaldepositionparam-
eters,r•, n, etc., alsochange. ac = - 3.1- 0.341n K, (•3)

0.011 ''' I'' '1' '' I'' '1' '' I '' '1' ''* C• 1
O.Ol ''' I''' I''' I' ' ' 1' ' ' I ' ' ' I ' ' '•
=- . - . R= 0.95
2 0.8 ___ß.... y=-3-0.34x
R=
0.82 ..]
0.009
• 0.6
0.008

• 0.4
0.007
0.006 .9 0.2
.,

0.005 '111I , , ,', , , ' ,, , '1, 1•,i•'l•'

, , ,' o 0
-,,, I ,,, I, , ,I,,, I,,, I,,, I,, ,

- 10.6 -10.4 -10.2 - 10 -9.8 -9.6 -9.4 -9.2 -10.6 -10.4 -10.2 - 10 -9.8 -9.6 -9.4 -9.2
(b) lnK

Figure 4. Correlationof (a) collectorand (b) collisionefficiencyfactorswith hydraulicconductivity.

Error
barsrepresent_+1 standarddeviationof data from multiple columnrunswith each sandsize.Variability in
thesedata is expectedbecauseof natural factorssuchas the packingof the columns.
2498 REN ET AL.: CORRELATION OF COLLOID COLLISION EFFICIENCY

0.25

0
00 E1 (>x
R + y=0.1+3.8x R=0.92
0.2
0.8 'O
• 1313
13
ø•oo
- DO X x
0.6 ß
• 0.15
-o• + _

x
-

_x + o •60-70 -
0.4 +• • n •70-80
• • xo •80-1•
•100-120
0.05
0.2
•• •• •120-140
•140-170

0 0.2 0.4 0.6 0.8 1

0 10 20 30 40 50 60 70 80
Collision efficiency factor
True, m•
Figure 7. Correlationof jamminglimit with colloidcollision
Figure 5. Breakthroughcurvesfrom Figure 3 renormalized efficiency.Error barsrepresent_+1 standarddeviationof data
to showrelativebreakthroughs(C/Cfinal).The degreeof un- from multiplerunswith eachsandsize.The directlinear cor-
steadiness increaseswith decreasingsandgrain size. relationindicatesthat the observedtrend of collisionefficiency
with hydraulicconductivity (Figure4) is dueto thevariationof
surfaceheterogeneitywith grain size.
with r = 0.82. Owing to the controlled conditionsof the
experimentsusedto obtain (13) (silicacollectormedia, con-
stantcolloidsurfacecharge,solutionpH, and ionic strength) nismresponsible for thisbehavior.Essentially, we believethat
we expectthe term t5from (7) to be zerofor thisdata set.The ac varieswith grain sizebecausethe sandsurfaceheterogene-
observedscatteraroundthe correlation(13) is attributableto ity also varies with grain size. This can be seen by careful
variationsin columnpacking,measurementlimitations,and examinationof Figure 3: the breakthroughcurvesof the larger
otherexperimentalerrors.The degreeof correlationis greater sands(lower sieve number) are relativelysteady,while the
in (12) thanin (13) because,/is a calculatedparameter,while breakthroughcurvesof the finer sandsare increasinglyun-
ac is determinedexperimentally. The degreeof correlationin steady.This behaviorcan be emphasizedby renormalizingthe
(13) seemsquite reasonablegiventhe limited numberof ex- breakthroughcurvesusingthe final observedeffluentconcen-
perimentsand the scattertypicallyobservedin measurements tration, as shownin Figure 5. Further, the variationof heter-
of X or ac. ogeneitywith grain size can be analyzedquantitativelyusing
The parametersof the correlationof a c and In K (in this appropriateparametersfrom the blockingfunction(equation
case,a = - 3.1 andb - - 0.34) are expectedto varywith the (11)). The grain surfaceheterogeneityis characterized by the
solutionconditions,colloidcomposition,and the composition jamming limit 0.... which is the maximumattainablesurface
and shapeof the medium grains.For example,higher ionic coverageof depositedcolloidsor the initial heterogeneityof
strengthresultsin more filtration, higher collisionefficiency, the sandsurface.Figure 6 showsthe variationof 0ma,, with both
and changesthe parametersof the correlation(a and/orb). grainsizeandIn K. Thoughthere is considerable scatterin the
However,we believethat a relationshipof this form should data, surfaceheterogeneityclearlyvarieswith sandsize.More
generallyhold for any physicallyheterogeneousporousme- significantly,0maxis very well correlatedwith ac as shownin
dium. Correlationsof this type shouldbe extremelyusefulto Figure7. This indicatesthat the observedvariationin collision
representthe effect of heterogeneous media in modelsfor efficiencycan be directly attributed to surfaceheterogeneity
colloidtransportunder field conditions. effects.While thistypebehaviorhasbeenobservedpreviously
for soluteinteractionswith natural sediments[e.g.,Barberet
4.3. Variation of Surface HeterogeneityWith Grain Size al., 1992;Barber, 1994], we believe that this is the first clear
Rehmannet al. [1999]theorizedthat a c shouldshowa grain demonstration of this effect for colloid filtration.
sizeeffectbasedon typicalobservations of colloidtransportin It seemsappropriatenow to revisitthe classicfiltrationthe-
the field. Our data provideadditionalinsightinto the mecha- orypresentedin (3)-(6). Conventionally, anobserved filtration

0.25

a 0.2

ßg o.s
.,,• ß
• 0.15
._• o.1
•0.05
ß i iii
• ,i • , I I ?
ii ill III '' I I II I
005 0
80 100 120 140 160 180 200 220 240 -10.6-10.4-10.2-10 -9.8 -9.6 -9.4 -9.2
Graindiameter,gm InK

Figure 6. Correlationof jamminglimit (surfaceheterogeneity) with sandgrain sizeand hydraulicconduc-

tivity. Error bars represent_+1 standarddeviationof data from multiple columnrunswith eachsandsize.
 REN ET AL.: CORRELATION OF COLLOID COLLISION EFFICIENCY 2499

coefficient(X) is separatedas the productof a physicaltrans- havior with grain size shouldalsobe consideredeven for sed-
port parameter(r•) and a physicochemical collisionefficiency imentsthat have a relativelyhomogeneousmineralogicalcom-
(ac). Lacking detailed knowledgeof the complexparticle position.When the r•a filtration model is used,it is important
transportprocesses verynear collectorsurfaces,
we calculater• to note that grain sizevariationscan affect both r• and a c.
basedon theoryfor noninteracting"hard-sphere"transportin Even though this studyused a simple colloid-collectorsys-
an idealizedporousmediumand then shiftall uncertaintyto an tem, a correlationof the form suggestedby Rehmannet al.
experimentaldeterminationof ac. However,the resultspre- [1999] is expectedto be generallyobtainableand can be ap-
sented here indicate that considerable care must be used when plied in other models.This type of correlationshouldbe es-
applyingthistheoryto naturalheterogeneous sediments.Our peciallyusefulfor modelsof colloidtransportin groundwater,
results show that physicalheterogeneityof the medium, as where the medium is typicallyextremelyheterogeneousand
reflectedby grainsizeor hydraulicconductivity, mayalsoimply sedimentsare often characterizedin terms of hydrauliccon-
differing degreesof particle surface heterogeneity.Correct ductivityrather than grain size.To be applied,our methodol-
analysisof overall colloid transport behavior then requires ogyshouldbe implementedfor flow ratesmore representative
considerationof the effect of both grain surfaceheterogeneity of field conditionsand for more complexchemicalconditions
(via a blockingfunctionor similar)and larger-scale heteroge- and particle compositions.
neity of the medium(e.g.,with a stochastic model).Codepen-
denceof physicaltransportparametersand surfacechemical
Notation
parameterson grainsizemustalsobe considered. Finally,it is
importantto note that we observedtheseeffectsfor cleaned a experimentallydeterminedconstant(correlation
silicasands;variationof mineralogicalcompositionwith grain parameter).
size in natural sedimentsimpliesthat theseeffectsshouldbe A cross-sectional area.
evenmoresignificantfor the analysisof colloidtransportin the As constantrelating single-collectorcolloid capture to
field. net capture in a porousmedium.
b experimentallydeterminedconstant(correlation
parameter).
5. Summary and Conclusions B(0) dynamicblockingfunction,representingthe effect
Column experimentswere carried out in the laboratoryto of accumulatedcolloid deposition.
studythe relationshipbetweenthe collectorgrain sizeand the Bz Boltzmann's constant(1.38x 10-23kgm2 s-2 K-•).
collisionefficiencyfactor for colloid filtration. Uniform clean C massper unit volume of suspendedcolloids.
sandswere usedas the porousmedia, and simplesilicaparti- Co influent particle or soluteconcentration.
cleswere usedasthe transportedcolloids.An initiallynonuni- d representativegrain diameter,typicallytaken as the
form silica sand was sieved into various size fractions in order mean diameter.
to produceuniform sandsof differentsizesbut the samebulk dp colloiddiameter.
composition. The sandswere then cleanedto removesurface f the specificsurfacearea of collectors,equal to
impurities.Chemicaleffectswere madeconstantin all exper- 3(1 - n)/(nrc).
imentsby controllingthe columnpH and ionic strength. # accelerationdue to gravity.
Colloid breakthroughcurvesshoweddynamicfiltration be- h head.
havior, which had to be analyzed in order to meaningfully H Hamakerconstant
(10-20 J).
comparethe experimentalresults.Clean-bedcollisioneffi- matt attachmentcoefficient.
ciencyfactorswere obtainedfor eachexperimentby two meth- kdet detachmentcoefficient.
ods: first, by using the effluent colloid concentrationat an K hydraulicconductivity.
estimatedinitial breakthroughtime and, second,by fitting a Kp particletransfercoefficient,
equalto •q/4.
blockingfunctionto the entire breakthroughcurve.The colli- L columnlength.
sionefficiencyfactorsderivedfrom the two methodsgenerally m single-particlemass.
agreedwell. The clean-bedcollisionefficiencieswere,however, n effectiveporosity.
foundto be significantlydifferentfrom thosebasedon the final q approachvelocity(Darcy velocity)equal to Q/A.
effluent colloidconcentrations,indicatingthat a significanter- Q volumetric flow rate.
ror would have been introduced if ideal filtration had been ro the averagepore radius,ro equal to (1.1969n -
assumed. 0.1557)rc.
Both the collectorand collisionefficiencyfactorswere found rc collectorradius.
to be negativelycorrelatedwith the natural logarithmof the rp particleradius.
mediumhydraulicconductivity, asproposedbyRehmannet al. S mass fraction of colloids attached to the solid
[1999].With our filtrationdatafrom the varioussands,we were surfaces.

able to parameterizethe r• versusIn K and ac versusIn K t time.

correlationsfor our colloid-sandsystem.The correlationof r• T temperature.
with In K is implicitin the Rajagopalanand Tien [1976]colloid v mean pore water velocity.
transportmodel,thoughit is not directlyobtainablefrom the Vp interstitial
particlevelocity,
equalto q/n[2 - (1 -
standardequationsfor r• becauseof the complexdependence r. lro)].
of grain size,porosity,and hydraulicconductivity.The corre- x' transformed
timecoordinate,
equalto L/vp.
lation of ac with In K canbe attributedto a variationof grain ac collisionefficiencyfactor.
surfaceheterogeneitywith grain size. Sorptionbehavior has aL local-scaledispersivity.
been shownto varywith grain sizein the field, and the results /3 excludedarea parameter,equal to 1/0max.
presentedhere indicatethat similarvariationof filtrationbe- • uncorrelatedrandom portion of a c.
2500 REN ET AL.: CORRELATION OF COLLOID COLLISION EFFICIENCY

r• single-collectorefficiency. Kretzschmar,R., K. Barmettler, D. Grolimund, Y. D. Yan, M. Bork-

0 fractionalsurfacecoverageof collectorgrains. ovec,and H. Sticher,Experimentaldeterminationof colloid depo-
sitionratesand collisionefficienciesin naturalporousmedia, Water
0max jamminglimit (maximumsurfacecoverageof Resour.Res.,33(5), 1129-1137, 1997.
depositedcolloids). Litton, G. M., and T. M. Olson,Colloiddepositionrateson silicabed
X filtrationcoefficient,m-•. media and artifactsrelated to collectorsurfacepreparationmeth-
Ix dynamicviscosityof water at experimental ods, Environ. Sci. Technol., 27, 185-193, 1993.
temperature. Liu, D., P. R. Johnson,andM. Elimelech,Colloiddepositiondynamics
in flow throughporousmedia: Role of electrolyteconcentration,
p densityof solution. Environ. Sci. Technol., 29, 3021-3031, 1995.
Pb bulk densityof the porousmedium. Logan, B. E., D. G. Jewett, R. G. Arnold, E. J. Bouwer, and C. R.
pp buoyantdensityof the colloids. O'Melia, Clarification of clean-bed filtration models, J. Environ.
r transformed
timecoordinate, equalto t - L/vp. Eng.,121(12),869-873, 1995.
Martin, M. J., B. E. Logan, W. P. Johnson,D. G. Jewett, and R. G.
Arnold, Scalingbacterial filtration rates in different sized porous
Acknowledgments. This work was supportedby a Drexel Univer- media,J. Environ.Eng., 122(5), 407-415, 1996.
sity GraduateAssistantship to J.R., NSF Career Award BES-9875784 Mau, R. E., Particletransportin flow throughporousmedia:Advec-
to A.I.P., and NSF HydrologicSciencesgrant EAR 9725086to C.W. tion, dispersion,and filtration, Rep. KH-R-53, Calif. Inst. of Tech-
nol., Pasadena, 1992.
Thanksare givento Doug Jerolmack,a Drexel Universityundergrad-
uate student,who carriedout severalof the columnexperiments,and Nocito-Gobel,J., and J. E. Tobiason,Effects of ionic strengthon
to Chris Barry for use of his tools and instrumentation.The authors colloiddepositionand release,ColloidsSurf.A, 107, 223-231, 1996.
would also like to thank Laura Toran, Laura McDowell-Boyer,and Packman,A. I., N.H. Brooks,and J. J. Morgan, Experimentaltech-
two anonymousreviewerswhose commentshelped us improve this niques for laboratory investigationof clay colloid transport and
filtration in a steam with a sand bed, Water Air Soil Pollut., 99,
manuscript.
113-122, 1997.
Rajagopalan,R., and C. Tien, Trajectoryanalysis
of deep-bedfiltration
References with the sphere-in-cellporousmediamodel,AIChE J., 22(3), 523-
533, 1976.
Bales, R. C., S. R. Hinkle, T. W. Kroeger, K. Stocking,and C. P. Rehmann,L. L. C., C. Welty, andR. W. Harvey,Stochastic
analysisof
Gerba, Bacteriophageadsorptionduringtransportthroughporous virus transportin aquifers,WaterResour.Res.,35(7), 1987-2006,
media:Chemicalperturbationsand reversibility,Environ.Sci. Tech- 1999.
nol., 25, 2088-2095, 1991. Saiers,J. E., G. M. Hornberger,and L. Liang,First- and second-order
Bales,R. C., S. Li, K. M. Maguire,M. T. Yahya, and C. P. Gerba,MS-2 kineticsapproaches for modelingthe transportof colloidalparticles
and poliovirustransportin porousmedia:Hydrophobiceffectsand in porousmedia,WaterResour.Res.,30(9), 2499-2506, 1994.
chemicalperturbations,WaterResour.Res.,29(4), 957-963, 1993. Schijven,J. F., W. Hoogenboezem,S. M. Hassanizadeh,and J. H.
Barber,B. B., Sorptionof chlorobenzenes to Cape Cod aquifer sedi- Peters, Modeling removal of bacteriophages MS2 and PRD1 by
ments, Environ. Sci. Technol., 28, 890-897, 1994. dunerechargeat Castricum,Netherlands,WaterResour.Res.,35(4),
Barber, B. B., E. M. Thurman, and D. D. RunnelIs, Geochemical 1101-1111, 1999.
heterogeneityin a sandand gravelaquifer:Effect of sedimentmin- Song,L., and M. Elimelech,Dynamicsof colloiddepositionin porous
eralogyand particlesizeon the sorptionof chlorobenzenes,
J. Con- media:Modelingthe role of retainedparticles,ColloidsSurf.A, 73,
tam. Hydrol., 9, 35-54, 1992. 49-63, 1993.
de Marsily,G., QuantitativeHydrogeology,
Academic,SanDiego,Calif., Tobiason,J. E., Chemicaleffectson the depositionof non-Brownian
1986.
particles,ColloidsSurf.,39, 53-77, 1989.
Elimelech,M., and C. R. O'Melia, Kineticsof depositionof colloidal Tobiason,J. E., and C. R. O'Melia, Physicochemical
aspectsof particle
particles in porous media, Environ. Sci. Technol.,24, 1528-1536, removalin depthfiltration,J.Am. WaterWorks Assoc.,80(9), 54-64,
1990. Dec., 1988.
Happel,J., Viscousflowin multiparticlesystems: Slowmotionof fluids Toride,N., F. J. Leij, and M. T. van Genuchten,The CXTFIT codefor
relativeto bedsof sphericalparticles, AIChE J., 4(2), 197-201,1958. estimatingtransportparametersfrom laboratoryor field tracer ex-
Hong, S., R. S. Faibish,and M. Elimelech,Kineticsof permeateflux periments,version2.0,Res.Rep.137, U.S. SalinityLab.,Agric. Res.
declinein crossflowmembranefiltrationof colloidalsuspensions, J. Serv.,U.S. Dep. of Agric., Riverside,Calif., 1995.
ColloidInterfaceSci., 196, 267-277, 1997.
Iwasaki, T., Some notes on sand filtration, J. Am. Water WorksAssoc.,
A. I. Packmanand J. Ren, Department of Civil and Architectural
29, 1591-1597, 1937. Engineering,Drexel University,3141 ChestnutStreet, Philadelphia,
Johnson,P. R., and M. Elimelech,Dynamicsof colloiddepositionin PA 19104.(apack@drexel.edu; sg96628u@drexel.edu)
porousmedia: Blockingbasedon random sequentialadsorption, C. Welty, School of EnvironmentalScience,Engineering, and
Langmuir,11, 801-812, 1995. Policy, Drexel University, 3141 ChestnutStreet, Philadelphia,PA
Johnson,P. R., N. Sun, and M. Elimelech,Colloid transportin geo- 19104.(welty@drexel.edu)
chemicallyheterogeneousporousmedia: Modeling and measure-
ments, Environ. Sci. Technol., 30, 3284-3293, 1996.
Kallay,N., M. Tomic,B. Biskup,I. Kunjasic,andE. Matijevic,Particle
adhesionand removalin modelingsystems,XI, Kineticsof attach-
ment and detachmentfor hematite-glass systems,ColloidsSurf.,28, (ReceivedNovember3, 1999;revisedApril 21, 2000;
185-197, 1987. acceptedMay 17, 2000.)