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Lectura 7. Transport of Zinc in An Aquifer
Lectura 7. Transport of Zinc in An Aquifer
73100
' and site densitiesfor the reactionsare obtainedby optimizing
fits to experimentaldata obtainedwith site-specific materials
MASSACHUSETTS
[Westallet al., 1995;Davis et al., 1998]. In definingthe set of
I
reactions,the objectiveis to determinea reasonablysmall set
o
,•,,,,
, • ,
50 KILOMETERS
, , , 41
of reactionsthat describethe influenceof variable chemistry
o 50 MILES
on adsorptionrather than to try to achievean accuratede-
scriptionof the microscopicchemicalreactionsin the system.
Thus the parametersof these SCMs shouldbe regarded as
70o32 ' 49" 70ø32 ' 28"
KITTREDGE ROAD
semiempiricalparametersapplicableonly to the site-specific
materialsand range of chemicalconditionsusedin the exper-
iments.
The semiempiricalSCM approachhasbeen successfully ap-
41 ø38 '27"
SLUDGE SEWAGE- plied to modelingreactivetransportunder variablechemical
)ISPOSAL BEDS
DRYING PADS
conditions.Kohleret al. [1996]obtainedaccuratepredictionsof
the influenceof fluoride concentrationand pH on the trans-
ZERO METERS
DOWNGRADIENT
port of uranium(U) throughcolumnspackedwith silica.Sim-
ilarly,Meeussenet al. [1996] usedthis approachto model the
transportof fluoridein laboratorycolumnexperiments.In both
cases,temporal and spatialvariabilityin pH had a major im-
pact on the shapeof breakthroughcurves,and the transport
modelsincorporatingSCMs gave excellentpredictions.Stol-
lenwerk[1998]successfully appliedthis approachto predicting
the effectsof vertical gradientsin pH and concentrationsof
competingadsorbinganionson the transportof molybdatein
a large-scalegroundwatertracer test. The approachhas also
been incorporatedinto reactivetransportmodelsapplied to
41 ø38' 06"
streams[Runkelet al., 1999].
The purposeof this paper is to presentthe resultsof a field
study illustratinghow variable pH in groundwaterstrongly
influencesthe mobility of an adsorbingmetal ion and to show
how incorporationof the semiempiricalSCM approachinto a
0 FEET 500 1,000
["•:•
ß EXTENT OF SEWAGE PLUME reactive transport model [after Yeh and Tripathi, 1991] can
(1994)
0 100
METERS
200 300 accountfor the influence of variable pH on adsorptionand
therefore on transport.
ß F343 LOCATION OF MULTILEVEL
SAMPLER OR CLUSTER OF
OBSERVATION WELLS
• MEDIAN
AND
RANGE
OF
GROUNDWATER
DIRECTION
(1993-1994)
FLOW
2. Site Characteristics
Figure 1. Site map showinglocationsof the sewagedisposal 2.1. Hydrologic and Physical Characteristics
beds,sludgedryingpads,selectedsamplingsites,line of section The field siteis locatedon westernCape Cod, Massachusetts
for the longitudinalprofile in Figure 2, approximatearea of (Figure 1). A regionof the aquiferis contaminated with sew-
sewagecontamination[Savoieand LeBlanc, 1998], hydraulic
age effluent emanatingfrom a sewagetreatmentfacility that
gradientdirection,and point usedto calculatedistancedown-
gradientfrom the sourcein Figure 2. servesthe Massachusetts Military Reservation(MMR). The
aquiferis composedof glacialoutwashdepositsof mediumto
coarsesandsand gravelsthat typicallycontainlessthan 1% silt
and clay [LeBlancet al., 1991; Davis et al., 1993a]. Quartz
other solutesinducedby adsorptionof reactivesolutes,which comprises90-95% by weight of the sediments,with most of
can have a major impacton their transport[Scheideggeret al., the remainderconsistingof feldsparsand ferroaluminosilicate
1994;Kohleret al., 1996;Meeussenet al., 1996]. minerals[LeBlancet al., 1991; Costonet al., 1995].The sedi-
A new semiempiricalapproachto modelingthe influenceof mentstypicallyhavelessthan 0.01% organiccarbon[Barberet
adsorptionon contaminanttransportunder variablechemical al., 1992]. Sedimentgrainsare coatedwith poorly crystalline
conditionshas recently been proposed[Westallet al., 1995; hydroxypolymers containingiron (Fe) and aluminum (A1)
Davis et al., 1998]. The approachis based on using surface [Costonet al., 1995].
complexation models(SCMs),whichhavebeenhighlysuccess- Regionally,groundwaterflow is to the south,but locallythe
ful in modelingthe influenceof variablechemistryon adsorp- flow directionis from the sewagetreatment facilitytoward the
tion in laboratorysystems[e.g.,Stumm, 1992]. This approach easternshoreof AshumetPond(Figure 1). Groundwaterflow
involveswriting massactionexpressions betweenthe dissolved is nearlyhorizontal. Approximately 25 cm yr-• of arealre-
speciesand surfacesites,suchas chargeresultsin a smallvertical componentto flow aswell as
Mn+q->S/OH = >SiOM(n-I)+q-H +, (1) in the accumulationof a lensof pristinegroundwateron top of
the sewageplume, the thicknessof which increaseswith dis-
where >SiOH representsone of a seriesof adsorptionsites tance awayfrom the sewagetreatmentplant [LeBlanc,1984;
with differentaffinityfor the metalion Mn+. Reactionswith LeBlancet al., 1991].The magnitudeof the hydraulicgradient
different stoichiometriesmay also be required. Mass action isapproximately 1.7m km-•; seasonal fluctuations
in theflow
quotients,which have the sameform as equilibriumconstants, system resultin smallvariations
(approximately0.2mkm-•) in
KENT ET AL.: MODELING THE INFLUENCE OF VARIABLE pH 3413
the magnitudeof the gradient as well as in a 15ø annual fluc- with trace-metal-gradenitric acid. Samplesfrom observation
tuation in flow direction[LeBlancet al., 1991;McCobbet al., wells (which have 0.6-m-longscreensand are constructedof
1999]. The resultsof two large-scalenatural gradient tracer polyvinylchloride)were collectedwith stainlesssteelsubmers-
tests showedthat the averagegroundwaterflow rate in the ible pumpsbut were otherwisetreated similarly.Samplingand
studyareaisapproximately
0.4m d-•, in goodagreement
with handlingdid not resultin significantlevelsof contaminationof
that calculatedfrom the hydraulicgradientand with valuesof groundwatersampleswith Zn or other metal ions [Savoieand
the hydraulicconductivitymeasuredin aquifer pumpingtests LeBlanc, 1998]. Site identifiersand nominal distancesdown-
[LeBlancet al., 1991;Hesset al., 1999;Davis et al., 2000c]. gradientfor the MLS or well clustersalongthe line of section
The MMR sewagetreatmentplant dischargedeffluent to shownin Figure 1 are as follows(sitesidentifiedby hyphened
disposalbedsfrom approximately1938until Decemberof 1995 alphanumericdesignationsare MLS in the tracer test array
[LeBlanc,1984;LeBlancet al., 1999].As of 1994,the plumeof describedby LeBlancet al. [1991] and Davis et al. [2000c]):
sewage-contaminated groundwateremanatingfrom the plant S469(62 m), F577 (105 m), F586 (152 m), F343 (195 m), 12-13
was900-1700 m wide, greaterthan 5500 m long,and 30-45 m (216 m), 24-12 (239 m), 30-11 (262 m), 33A-11 (277 m), 37-12
thick [SavoieandLeBlanc,1998].There is little informationon (292 m), 41-11 (310 m), 44-11 (324 m), 48-09 (342 m), 51-08
effluent loading rates to the disposalbeds prior to the late (355 m), 54-10 (369 m), 57-09 (383 m), 60-09 (397 m), 62-10
1970s.LeBlanc [1984] used water supplyrecordsand other (405 m), and 64-10 (415 m).
historicaldata to estimateeffluent dischargerates,whichfluc- Detailed discussions of the analytical methods are given
tuated considerablyover the historyof the plant. The highest elsewhere.Concentrationsof dissolvedZn and other inorganic
loadingrateswereapproximately
6.8 x 106 L d-1 duringthe soluteswere determinedby inductivelycoupledplasmaatomic
period 1941-1945,after whichtime the loadingratesdecreased emissionspectrometry[Costonet al., 1998]. Concentrationsof
considerably. Recordsover the 20-yearperiodprior to shutoff dissolvedZn were determinedto a precisionof approximately
of the plant in 1995showeddischargeratesin the range0.4- 10% at concentrations lessthan 2 txM [Costonet al., 1998]and
1.9 x 106 L d-1 [LeBlanc
et al., 1999]. 5% at higherconcentrations [Daviset al., 2000a].Valuesof pH
There are a total 25 disposalbeds(Figure 1); the historyof were determinedto a precisionof approximately0.03 pH units
their use prior to the late 1970sis unknown.It is likely that using methods optimized for poorly buffered, low ionic
nearlyall bedswere usedduringthe period of highestloading strengthsamples[Kentand Maeder, 1999].
rates. From the late 1970s to 1984, the beds numbered 1-4 Field testsshowedthat Zn detectedin groundwatersamples
were usedexclusively [LeBlanc,1984]and individualbedswere wasneitherpresentasstrongcomplexesnor boundto colloidal
loadedfor severalweeks,throughoutwhich time effluentwas or particulatematter. One hundredpercentof Zn in ground-
ponded,prior to manuallyredirectingflow to a differentbed water samplescouldbe removedby Chelex(the use of brand
[Vaccaroet al., 1979].From 1984 to 1995, disposalwas auto- or product namesin this article is for identificationpurposes
maticallyrotatedbetweenbedsnumbered5-12 every3 hours, onlyand doesnot constituteendorsementby the U.S. Geolog-
and minimal pondingoccurred.Up until 1984, liquid sludge ical Survey),whichis a cationexchangerwith a highaffinityfor
wasspreadout on the unlineddryingpadslocatednortheastof divalent transition
metalions[Reaetal., 1991,1996;Kentand
beds 9-12; after 1984 plastic liners were placed under the Maeder, 1999; Davis et al., 2000a]. Concentrationsof Zn in
dryingsludge. unfiltered groundwaterwere not statisticallydifferent from
those in samplespassedthrough filters with nominal pore
2.2. Chemical Characteristics
diameter cutoff values of 0.1, 0.4, or 8.0 /•m [Kent, 1998].
Contrastingchemicalconditionsbetween sewage-contami- Water samplescollectedusingextremelylow pumpingrates
nated and ambient groundwatergave rise to longitudinaland had Zn concentrationsidentical to those collectedat higher
vertical gradients in groundwater chemistry. The ambient pumpingrates,within experimentalerror [Kent,1998].
groundwatersurroundingthe sewageplume had high concen-
trations of dissolvedoxygen,pH valuesin the range 5.3-5.8, 4. Distribution of Zn Contamination
and low concentrations of dissolvedsalts[LeBlancet al., 1991;
Hess et al., 1996; Kent and Maeder, 1999]. Sewage-contami- 4.1. Dissolved Zn and pH
nated groundwaterunder the disposalbedshad high concen- The distributionof dissolvedZn along a longitudinalcross
trations of nitrate; concentrationsof dissolvedoxygen de- sectionis shownin Figure 2. Dots indicate the locationsof
creasedwith depth [Smith et al., 1991a]. Biodegradationof samplingpoints.Distancedowngradientto each samplinglo-
organicmatter in conjunctionwith solutetransportawayfrom cation was calculatedfrom the center of the set of disposal
the disposalbedsresultedin the depletionof dissolvedoxygen bedsin whichthe crosssectionoriginates(seeFigure 1).
throughoutthe plumeandthe depletionof nitrate,followedby Data from an MLS located near the edge of one of the
the accumulation of dissolved Fe(II), in the coreof the plume disposalbeds, 62 m downgradientof the center of the beds
[Smithet al., 1991b;Kent et al., 1994].These biodegradation (S469 in Figure 1), show that Zn contaminationnear the
reactionsstronglyinfluencedpH valuesin the sewageplume sourceextended13-15 m deep in the aquifer (Figure 2). In
[Abramset al., 1998;Abramsand Loague,2000b]. contrast,analysisof the overallwater quality showsthat the
sewage-contaminated zonewas25-30 m thick at this location
[Hesset al., 1996;LeBlanc et al., 1999]. Zinc concentrations
3. Groundwater Sampling and Analysis observedthroughout the vertical profile were in the range
Groundwatersampleswere collectedas describedin detail 0.4-1.5 IxM. Assaysof the sewageeffluent showeddissolved
elsewhere[Savoieand LeBlanc,1998].Briefly,water samples Zn concentrations in the range0.4-2/•M [Vaccaroet al., 1979;
from multilevelsamplers(MLS) (for a description,see Le- E. C. Jordan,Inc., 1986;SavoieandLeBlanc,1998],whichisthe
Blanc et al. [1991]) were collectedusing peristalticpumps, samerangeasobservedin groundwater underthe disposalbeds.
filtered (0.45-/•m nominal pore size), and acidifiedto pH 2 Downgradientfrom the disposalbeds,Zn wasobservedonly
3414 KENT ET AL.: MODELING THE INFLUENCE OF VARIABLE pH
14-
12-
o
10-
8-
6;
4-
2-
-2
0 100 150 200 250 300 350 400
near the upper boundaryof the sewage-contaminated zone tancedowngradient wasobservedin thisregionof the aquifer
(Figure 2). At distancesgreaterthan 195 m downgradient, [LeBlancet al., 1999].The increasein pH wasdrivenby deni-
increasedspatialresolutionprovidedby an extensivearrayof trificationand Fe reduction[Abramset al., 1998]aswell asby
MLS [LeBlancet al., 1991;Davis et al., 2000c]facilitatesde- adsorptionand ion exchangereactionsbetweensolutesand
tailed definitionof the featuresof the Zn-contaminatedregion. mineral surfacesites[Stollenwerk and Parkhurst,1999]. Shal-
There wasa regionof uncontaminated groundwaterabovethe lowerin the aquifer,whereZn contamination wasobserved up
Zn-contaminatedregion. The upper boundaryof the Zn- to 400 m downgradient from the source,no consistent increase
contaminatedregioncoincidedwith the upperboundaryof the in pH with distancedowngradient was observed.At a given
sewage-contaminated zone [Davis et al., 2000b]. The Zn- location,pH valuesincreasedwith depth acrossthe upper
contaminatedregionwas2-4 m thick. The highestconcentra- boundaryof the sewageplume. Values of pH at the upper
tionsof dissolved Zn (greaterthan8/•M) wereobservedin the boundaryof the Zn-contaminatedregionrangedfrom 5.4 to
thickestpart of the Zn-contaminated region.The leadingedge 5.8, and thoseacrossthe lowerboundarywere from 5.8 to 6.0.
of the Zn-contaminatedregion was sharp and was located The data in Figure 2 comefrom a synopticsamplingcon-
approximately 400 m downgradient. In contrast,conservative, ductedin AugustandSeptember,1997,whichis almost2 years
nonreactiveconstituents of the sewageplumeformeda diffuse after cessationof the source.As expected,basedon the aver-
leadingedgegreaterthan 5500 m downgradientof the source agegroundwaterflowvelocityand time sincesourcecessation,
[Savoieand LeBlanc,1998]. decreasesin boron (B) concentrationand other conservative,
Concentrationsof dissolvedZn under the disposalbeds nonreactive solutes present in the sewage-contaminated
were consistentlylower than those observed at locations groundwaterbut absentin uncontaminated groundwaterwere
greaterthan 195m downgradient (Figure2). For example,out observedat locationswithinapproximately 250m of the source
of 145 samplescollectedin the Zn-contaminatedregion at duringthistime [LeBlancet al., 1999].However,no significant
S469betweenSeptember1995(whenit wasfirstsampled)and changesin pH profiles,Zn concentration profiles,or redox
September1997, the highestZn concentrationobservedwas gradientsalongthis crosssectionwere observedduringthis
2.4 /•M, and only nine sampleswith concentrations above2 time [Kentand Maeder,1999;LeBlancet al., 1999].Dissolved
/•M were observed[KentandMaeder,1999].Possiblecausesof Zn and pH profilesobservedin the disposalbedsat S469in
higherconcentrations of Zn downgradientof the sourcethan 1997(Figure2) are similarto thoseobservedat MLS located
at the sourcewill be examinedin subsequentsectionsof this in the set of disposalbedsto the west (S318) in samplings
paper. conductedover a period of severalyearsprior to sourceces-
Contourlinesin Figure2 showthe distributionof pH values sation[Reaet al., 1991, 1996;Savoieand LeBlanc,1998;Kent
in the Zn-contaminatedregion.Deeper in the aquifer,where andMaeder,1999].Comparison of the distributionof dissolved
Zn contaminationwas observedonly near the source,pH val- Zn greaterthan 195 m downgradient shownin Figure 2 with
ues increasedsteadilywith distancedowngradientfrom less one obtainedfrom a muchmore detailedsamplingconducted
than 6.0, at 62 m downgradient,to greaterthan 6.6, at 195 m in 1993,two yearsprior to sourcecessation, showsno signifi-
downgradient (Figure2). No furtherincreasein pH with dis- cantdifferences[Kentet al., 1999].Data from 1997were used
KENT ET AL.: MODELING THE INFLUENCE OF VARIABLE pH 3415
insteadof thosefrom the 1993samplingfor two reasons.First, sorptionof Zn, and no dissolutionof Fe, was observedwhen
by 1997, installation of additional MLS and well clusters groundwaterat pH of 4.5 was injectedinto the Zn-contami-
nated region [Wilkieet al., 1998].
greatlyimprovedthe spatialresolutionwithin the first 195m of
the disposalbeds[Hesset al., 1996;LeBlancet al., 1999].Sec- Manganese(Mn) and Cu, whichlikely adsorbonto the sed-
ond, the pH data from the 1997 samplingwere more accurate iments under the prevailing chemicalconditions,have been
and precisethan thosefrom the 1993sampling. observedin the sewage-contaminated zone, but it is unlikely
that competitionwith thesesoluteshad a primaryinfluenceon
4.2. Zn Adsorption and Aqueous Speciation Zn mobility.The upper boundaryof the regionwhere Mn was
Extractionsof sedimentsampleswith hydroxylaminehydro- observedoverlappedwith the lower boundary of the Zn-
acid(B. A. Rea, contaminatedregion [Daviset al., 1993b];Mn concentrations
chloride[Reaet al., 1991]or 1-M hydrochloric
U.S. GeologicalSurvey,Menlo Park, California,unpublished ashigh as 10/.rM were observedin the Zn-contaminatedregion
data,2000) showedthat therewasa largemassof Zn boundto at distancesgreater than 350 m downgradientof the source
the sedimentsin the regionswith detectableconcentrationsof [Daviset al., 2000c].It is unlikelythat Mn at theseconcentra-
dissolved Zn. Sediment-bound Zn in excess of natural back- tionscouldcompetesignificantly with Zn becausesurfacessites
groundZn wasobserVedonlywheredissolvedZn wasdetected generallyhavea muchloweraffinityfor adsorbingMn than Zn.
in the groundwater[Rea et al., 1991]. Comparisonsof the For example,surfacecomplexationconstantsfor Mn adsorp-
concentrations of sediment-bound Zn and dissolved Zn show tion on silica and alumina, as well as those estimated for
that greaterthan 95% of the Zn was sediment-bound[Rea et adsorptionon hydrousferric oxide, are 25-400 times lower
al., 1991]. than those for Zn adsorption[Dzombakand Morel, 1990;
Solubilitycalculations
usingfield datashowedthat all known Benyahyaand Gantier, 1999]. In contrastto Mn, Cu adsorbs
Zn-containingsolidswereundersaturated by at leasta factorof muchmorestronglythanZn [Daviset al., 2000c].Copperwas
10 [Reaet al., 1991,1996].Solidsconsideredin the calculations observedat similar concentrationsand over the same depth
includedZn oxides,hydroxides,hydroxycarbonates, and phos- rangeasZn underthe disposalbeds[Kentand Maeder,1999].
phates(thermodynamic data fromPerezandNancollas[1984] However, Cu concentrationsdecreasedmore rapidly than
andZacharaet al. [1989]).Extensivelaboratorystudiesshowed thoseof Zn with distancedowngradientfrom the sourceand
that adsorptionof Zn onto hydroxypolymercoatingson min- wereeverywherebelowdetection(0.1 •M) at distances greater
eral grainswas the dominant chemicalreaction between Zn than 150 m downgradient[Kentand Maeder,1999].
and the sediments[Costonet al., 1995;Fuller et al., 1996]. The entire Zn-contaminatedregion was located within a
Laboratoryexperimentaldata were usedto calibratea surface muchlargerregioncontaminatedwith phosphate(PO4) [Kent
complexation modelfor Zn adsorptionon the sediments[Davis andMaeder,1999;Daviset al., 2000c].Like Zn, a largemassof
et al., 1998]that predictedvaluesof the massof adsorbedZn sediment-boundPO4 was observedwherever there was dis-
in good agreementwith the massof sediment-boundZn de- solvedPO4 [Walteret al., 1996].Whether or not adsorbedPO4
terminedfrom the extractiondata [Daviset al., 2000b]. influencesZn adsorptiononto these sedimentsis unknown,
The presenceof adsorbedZn in the Zn-contaminatedregion althoughthere is someevidencethat it may enhanceZn ad-
and its absencebelow it were corroboratedby the resultsof sorption on hydrousferric oxide [Ghanem and Mikkelsen,
field transportexperiments.Two experimentsinvolvedinject- 1988].Sedimentsusedto characterizeZn adsorptionhad sed-
ing Zn complexedwith the strongmetal-ioncomplexingagent iment-bound
PO4 b•causetheyweretakenfromthe sewage-
ethylenediaminetetraacetic acid (EDTA) and excessfree contaminatedzonebelowthe Zn-contaminatedregion[Coston
EDTA into, and directly below, the Zn-contaminatedregion et al., 1995].This shouldhelp accountfor anypossibleeffectof
[Daviset al., 2000c;D. B. Kent et al., Effect of adsorbedmetal adsorbedPO4 on Zn adsorption.
contaminantson the transport of Zn- and Ni-EDTA com- Aqueousspeciationof Zn wasdominatedby either free Zn
plexesin a sandandgravelaquifer,submittedto Environmental or veryweakcomplexes (seesection3). The lackof importance
Scienceand Technology, 2000; hereinafterreferred to as sub- of stronglycomplexingorganicsis consistent with low concen-
mitted manuscript,2000]. Belowthe Zn-contaminatedregion trations and the oxidized, recalcitrant nature of dissolved or-
the massof Zn in the tracer cloud decreasedwith transport ganiccarbon(DOC) in the sewage-contaminated zone. Con-
distanceas a result of displacementof Zn from EDTA com- centrationsof DOC in the Zn-contaminatedregionwere 0.5-3
plexesby Fe(III) dissolvedfrom the sediments.The reaction mg C L-• [BarberandKeefe,1999].TheselowDOC concen-
was thermodynamically favorablebut was slow. Most of the trationsresultedfrom the extensiveoxidationof organicsdur-
free EDTA initially dissolvedA1, which, along with Zn, was ing the treatmentprocess,in which 90% of the effluentwas
subsequently displacedoverseveralmonths,duringwhichtime recycledbackthroughthe sewagetreatmentplant to maintain
the tracer cloudswere transportedtens of meters. In the Zn- minimuminfluentcriteria [Thurmanet al., 1986].The sewage
contaminatedregion the massof Zn in the tracer cloud in- treatmentplant haslikely operatedin this mode sincethe late
creasedadjacentto the injectionasa resultof desorptionof Zn 1940s,when the high sewageloadingscharacteristicof the
from sedimentsby the excessEDTA, and subsequentlyre- initial yearsof operationof the plant abruptlydecreased[Le-
mainedrelativelyconstantasthe tracercloudwastransported Blanc, 1984].Even if DOC concentrations were higherin the
downgradient.AdsorbedZn on the sedimentsdecreasedthe past,the absenceof Cu, whichis knownto form strongcom-
thermodynamicaffinityof the displacement of Zn from EDTA plexeswith sewage-derived organics[Kentand Maeder,1999],
complexesby Fe (D. B. Kent et al., submittedmanuscript, in the downgradientportionof the plumesuggests that mobi-
2000).Desorptionof Zn by free EDTA wasfast,as shownby lizationby organicligandswasnot a primarycontrollingfactor
the completeremovalof adsorbedZn from sedimentsadjacent in the currentlyobserveddistributionof Zn. The strongcom-
to the injection ports by free EDTA during the injections, plexingagentsEDTA and nitrilotriaceticacid (NTA) have
which lastedonly a few hours(D. B. Kent et al., submitted beendetectedin the sewage-contaminatedzonebut at concen-
manuscript,2000). In anothertracertest,rapid, extensivede- trationslessthan 1 •M [Barber,1998]. Speciationof EDTA,
3416 KENT ET AL.: MODELING THE INFLUENCE OF VARIABLE pH
qz,
t•= 0.0014m/d boundary;the lower boundaryis consideredto be a flow line
and is modeled as a no-flow boundary. The downgradient
C/,i•:
TCO1=1mM,
pH
=5.65,
Sulfate
=100
gM
I
boundaryis assigneda constant-head.DissolvedZn is input
uniformlyalongthe upgradientboundary(exceptfor the up-
permostnode)on the basisof the observationsof Zn contam-
inationunderthe disposalbeds(e.g.,Figure2). This formula-
tion obviatesthe need to attempt to simulatevertical flow
underthe disposalbedsresultingfrom effluentloading.
The simplified,steadystate,flow fieldwascomputedfrom
the groundwaterflow equationand Darcy'sLaw:
I'
0m
=o
Oh/Oz
=0 400m
V-(•. Vh) = 0
// K
½= • = - •- Vh,
(2a)
(2b)
Figure 3. Conceptualmodeland initial andboundarycondi-
tions used in most two-dimensional simulations. whereh is head;K is the hydraulicconductivitytensor;c-/isthe
specificdischargevector;• is the velocityvector;and 0 is the
effectiveporosity.Equations(2a) and (2b) are solvednumer-
NTA, and anyother strongcomplexingligandswaslikely dom- ically,subjectto the boundaryconditionsgivenin Figure 3, as
inated by Cu under the disposalbedsand by Fe at distances describedelsewhere[Yeh,1987].
greater than approximately100 m downgradientfrom the Mass transportequationsfor each componentj are written
source[Kentand Maeder, 1999;Davis et al., 2000c].Local in the form
perturbationsin the distributionof Zn contaminationhave
resulted from tracer tests involvingthe injection of EDTA _
[Daviset al., 1993b,2000; D. B. Kent et al., submittedmanu- 0-•-=-V. (•Cj)+ V. (D-VC/) j = 1,Nc (3a)
script,2000],but the samplinglocationsselectedfor construct-
C/= T/- Sj, (3b)
ing the crosssectionshownin Figure2 were selectedto min-
imize this effect. whereTi, C•, andSi are the total analytical,
totaldissolved,
and total adsorbedconcentrations,
respectively,
of component
5. Transport Modeling j; Nc isthetotalnumber
of components;
andD isthedisper-
sioncoefficienttensor,which dependson the longitudinaland
5.1. Modeling Objectives
transverse verticaldispersivities
(aL andatv, respectively) and
The overall modelingobjectiveis to examinethe utility of • [e.g.,Bear, 1972]. Molecular diffusionis assumedto be in-
the semiempiricalSCM approachto describethe influenceof significantcomparedto mechanicaldispersionfor this aquifer
variable pH on adsorptionand therefore on the transportof [Garabedianet al., 1991].The set of transportequations,sub-
sewage-derived Zn. To this end, the modelis usedto compare ject to the boundaryconditionsshownin Figure 3, and chem-
resultsof simulationsusing one-siteand two-siteSCMs, to ical reactionsare solved numerically as describedelsewhere
examinethe interplay between dispersionand adsorptionon [Yehet al., 1995].The discretization usedfor eachsimulationis
spreadingof Zn, to examinehypotheses aboutthe influenceof shown in Table 1. Peclet numbers are less than 2 in all simu-
source-history on the distributionof Zn contaminationin the lations(Tables1 and 2).
aquifer,and to illustratehow temporalvariationsin pH result- 5.2.2. Chemical processes. The principal chemicalpro-
ing from sourcecessationcaninfluencethe fate of Zn contam- cessinfluencingZn transportis assumedto be adsorptiononto
inationin the aquifer.A two-dimensional verticalcross-section the sediments.A singlereactionwith the stoichiometry shown
model achievedthese objectivesby allowingfor inclusionof in (1) adequatelydescribesthe pH effect observedin labora-
both the pH gradientand the principalhydrologicprocesses. tory batchstudiesof Zn adsorptiononto the sediments[Davis
5.2. Model Setup et al., 1998].Adding a secondsurfacesitewith the samereac-
tion stoichiometry resultsin an SCM that fits both the pH and
5.2.1. Hydrologicprocesses. A simplifiedrepresentation
Zn-concentration effect [Daviset al., 1998].In this paperwe
of the hydrologicsystemis usedto simulategroundwaterflow
comparethe performanceof the one-siteand two-siteSCM in
and solutetransport(Figure 3). The two-dimensional vertical predictivesimulationsof the Zn-contaminatedregion of the
cross section is specified along a hypotheticalflow plane. aquifer. The one-siteSCM has the form
Steady, horizontal flow is specified along the upgradient
boundary.Uniform areal rechargeis specifiedacrossthe upper
Table 2. Base-CaseParametersfor Flow and Transport
Model
Table 1. Discretization Used for One- and Two-
Dimensional Simulations Parameter Value Source
Zn2++ >SwOH- >SwOZn+ + H +, logSQswozn.(6b) temporal fluctuationsin pH on the transportof Zn. This is
accomplishedby changingthe H2CO3/HCO•- concentration
Massactionexpressions analogousto (5) are written for each ratio at eachnodealongthe upgradientboundaryasneededto
adsorptionreaction in (6). Four parametersmust be deter- give the desiredpH. However, there is another effect that
mined forthetwo-siteSCM:themass action quotientsSQSsOZnneedsto be considered.Laboratory and small-scalefield ex-
andSQs•,oz n andthetotalsitedensities SsOHq: (S•OHq: = perimentsconductedin and around the sewageplume have
S>ssOi-i + S>ssOZn)and SwOHT(SwOHT= S>s,•oi-i+ shownthat adsorptionsiteson sedimentsurfacesact to buffer
S>s,•ozn). Typically,
fitsusingthe two-siteSCM havebeen the pH [Kentet al., 1994;Stollenwerk,1995;Royand Dzombak,
found to be superiorto thoseusingthe one-siteSCM, espe- 1997;Wilkieet al., 1998],in agreementwith studiesconducted
ciallyfor adsorptiondata collectedover a wide rangeof metal in other groundwaterand surfacewater systems[Appeloet al.,
ion adsorptiondensitiesin laboratorybatchsystems[Dzombak 1990;Scheidegger et al., 1994;Broshears
et al., 1996;Toranet al.,
andMorel, 1990;Waiteet al., 1994;Daviset al., 1998]aswell as 1998].Bufferingof pH by the aquifer sedimentsshouldhave
reactivesolutebreakthroughin transportexperiments[Kohler the effect of diminishingthe rate at which pH fluctuations
et al., 1996]. propagatethroughthe system.Attempting to simulateaccu-
Speciationcalculationsindicatethat the aqueousspeciation rately the pH-bufferingpropertiesof aquifer sedimentsis be-
of Zn is constantover the range of pH and other chemical yondthe scopeof our modelingobjectives.Instead,an ad hoc
conditions observed in the Zn-contaminated region. Free approach,basedon the followingchemicalreaction,is usedto
Zn2+ comprises approximately 95%of thetotaldissolved Zn, simulatepH bufferingby surfacesiteson the sediments:
andZnSO4øcomprises theremainder [Costonetal., 1995].The
formationof ZnSO4
ø is described
by the reaction >AH = >A- + H +, logSQ^. (9)
Zn2+q-SO42-=ZnSO4
ø, logQznso4, (7a) where >AH and >A- simulateimmobile pH buffering sites.
for which
The massaction quotient and the total concentrationof im-
mobilepH buffering
sitesare setequalto logQi42co3
and1
•/Zn'¾SO4Cznso4
0 mM (equalto the TCO2), respectively.The pH at eachnode
Q ZnSO4
-- Kznso4
-- = , (7b) throughoutthe spatialdomainis calculatedat eachtime step
•/ZnSO4Czn2+Cso•
-
based on the interactionsof solute transport and the mass
whereKznso
4is thethermodynamic
equilibrium for actionequationscorresponding
constant to reactions(8), (9), and (4) or
theformation
ofZnSO4
øand3'Zn,
3'SO4,
and3'ZnSO4
areactivity (6). Adsorptionsites(>SiOH) andpH-bufferingsites(>AH)
coefficientsof the subscriptedspecies. were treated independently.
This modelingapproachassumesthat local equilibriumwith 5.2.4. Parameter estimation. Flow and transportparam-
respectto adsorptionreactionsis achievedfaster than the eter values used in most simulationsare given in Table 2.
timescaleof transport.Batch studiesconductedwith aquifer Values for the hydraulicconductivityand anisotropyratio are
sedimentsfrom the site have shownthat Zn adsorptionis fast takenfromLeBlancet al. [1991]andare usedin all simulations.
enoughto justifythe localequilibriumassumptionand that Zn Values of ai• and OtTVare taken from the resultsof a large-
adsorptionis reversibleoverthe experimentaltimescales(days scaletracer test [LeBlancet al., 1991;Garabedianet al., 1991].
to weeks)[Costonet al., 1995].As discussedin section4.2, the Similarvalueswere obtainedin a subsequent large-scaletracer
results of field tracer tests where free EDTA or low-pH testconductedat the samesite[Hesset al., 1999].Althoughthe
groundwaterwas injected into the Zn-contaminatedregion transportdistancein the currentapplicationis abouttwicethat
indicatedthat desorptionof Zn wasrapid and reversible.The of the tracertests,thesevaluesare consideredto be asymptotic
validityof the local equilibriumassumptionhasbeen demon- [Garabedianet al., 1991]and thereforeare assumedto apply.
stratedpreviouslyin laboratorytransportexperimentswhere Thesevalueswereusedin all simulations exceptthosein which
adsorptionis the only important chemicalreaction and flow the sensitivityof the model resultsto dispersivityvalueswas
rateswereof the orderof 1 m d-• or less[HinzandSelim, assessed.
1994;Gerritse,1996;Kohleret al., 1996;Buenoet al., 1998]. Parametersfor the equilibriumchemicalmodel are derived
5.2.3. Imposing the pH gradient. Inclusion of the entire from laboratorybatchexperimentaldata for Zn adsorptionon
networkof redox and adsorptionreactionsthat influencethe the sediments,which, along with a detailed discussionof pa-
3418 KENT ET AL.: MODELING THE INFLUENCE OF VARIABLE pH
6 6.5,
15years
L '""...
2-site,
cx ";..¾ pH
5.65,
15years
L -
2-site,
cx -
---- 1-site,cx
L -
dispersivityresultsin increasedspreading.At pH 6.5 the higher
dispersivityresults in more spreadingall along the leading
----
- 2-site,
1-site,
..... cx
LL "...•
10Xc••i......
2-site,
10XCXL, edge, due to the diminishedimportanceof strong sites on
adsorptionat Zn concentrationsabove 1/xM at pH 6.5. Thus
both physicaland chemicalprocessesact to control the con-
\ _
centrationsat the leading edge, and their relative importance
changeswith changingchemicalconditions.This further illus-
trates the utility of the SCM approach;achievingtheseresults
would have been much more cumbersomehad K a or isotherm
parametersbeen usedto describeadsorption.
.'.. I , , , , I ..... %1 ,•,.- -- ..
0
0 50 100 150 200 250 5.5. Influence of Source History on Distribution of Zn
Distance downgradient,meters Contamination
Figure 5. Fifteen-year, one-dimensionalsimulationsat pH Field data from the downgradient portion of the Zn-
5.65 and 6.5 usingone-siteSCM with aL (base-caselongitudi- contaminated zone showregionswith Zn concentrationssev-
two-siteSCM with O/L,andtwo-siteSCM with eral timesthoseobservedunder the disposalbeds(Figure 2).
nal dispersivity),
10 times We examined two competing hypothesesregarding source
3420 KENT ET AL.' MODELING THE INFLUENCE OF VARIABLE pH
set to 0 while the pH was kept at 5.3 for 2 years,after which 0 100 200 300 400
time the original pH gradient and Zn concentrationwere im- Distance downgradient, meters
posedat the boundaryonceagain.The same2-yearpulsewas Figure 8. Resultsof the Zn-pulsesimulations: Zn concentra-
repeatedbetween40 and 42 years.For the Zn-pulse simula- tionsandpH values(solidcontourlines)after(a) 31 and(b) 41
tion, 2-year-longpulseswith 20-/•M Zn were introducedall years.
KENT ET AL.: MODELING THE INFLUENCE OF VARIABLE pH 3421
underscorethe pitfalls in usingmodel calibrationto elucidate 0 lOO 200 300 400 500 600
processescontrollingthe transport of reactive contaminants
discussedby Brusseau[1998] and Brusseauand Srivastava Distance downgradient, meters
[1999].
Figure 9. Simulationof the transportof Zn followingsource
5.6. Influence of Source Cessation on Fate of Zn cessation,basedon assumptions aboutevolutionof groundwa-
Contamination ter pH describedin the text. Sourcecessationwas assumedto
begin after 59 years of sewagedisposal.
Sewage disposal onto the beds shown in Figure 1 was
stoppedin December 1995 upon completionof a new treat-
ment plant [LeBlancet al., 1999].As discussed in the previous
section,flushingof the sewage-contaminated zone with ambi- dient (Figure9a). At 59 yearsthe upgradientboundarycondi-
ent groundwatershouldlead to decreasingpH values.A sim- tionswere changedby settingthe Zn concentrationequal to 0
ulation was performed to illustrate qualitativelythe effect of and the H2CO3/HCO•- concentrationratio to yield a pH of 5.3.
acidification of Zn-contaminated sediments as a result of The simulationresultsshow large increasesin Zn concen-
source cessation. trationsin the Zn-contaminatedregion(Figures9b-9d). The
The simulationwasconductedalonga two-dimensional ver- highestZn concentrationsobservedin the simulationresults
tical crosssectionthat extendsto 600 m, which is approxi- are 25-30 /aM (Figure 9c), i.e., greaterthan 10 times those
mately the distancebetween the disposalbeds and Ashumet prior to sourcecessation.This phenomenon,generallyreferred
Pond (Figure 1). The nature of the downgradientboundary to as the "snowploweffect," has been observedin laboratory
was not changed,and thus no attempt was made to describe column,experiments[Starr and Parlange,1979; Selim et al.,
the influence of the pond on the flow field. The base-case 1992;Hinz and Selim,1994].
parameters(Table 2) and one-site SCM were used in the Increases in Zn concentrations observed in the simulations
simulation.For the first59 years,2/aM Zn wasinput alongthe resultfrom desorptionin responseto decreasesin pH. Greater
upgradientboundaryin the presenceof the imposedpH gra- increasesin dissolvedZn concentrationsare observeddeeper
3422 KENT ET AL.: MODELING THE INFLUENCE OF VARIABLE pH
4.5 5.0 5.5 6.0 6.5 A region with elevatedconcentrationsof dissolvedZn was
pH observed within a sewageplume in a sandand gravelaquifer.
Directly under the sewagedisposalbeds,Zn concentrations up
Figure 10. Vertical profilesof B, Zn, and pH from a multi- to approximately2 t•M were observedup to 15 m below the
level samplerlocatedin one of the disposalbeds (S472;see water table. Downgradientof the disposalbeds,Zn contami-
Figure 1) activeat the time of sampling(in September1995). nation was only observedin a 2- to 4-m-thickregion near the
Approximatealtitudeof water table (WT) is alsoshown. upper boundaryof the sewageplume and exhibiteda sharp
leadingedgeapproximately400 m from the source.Conserva-
tive, nonreactive constituentswere observed greater than
in the aquifer,where higherpH valuesprior to sourcecessa- 5500 m downgradientof the source.Values of pH increased
tion resulted in more extensiveadsorptionof Zn onto the with depth in the aquifer, from approximately5.7 near the
sediments.Between59 years(corresponding to sourcecessa- upper boundaryof the sewage-contaminated zone to greater
tion) and 62 years,in the regionwherethe pH decreasedfrom than 6.6 in the core of the sewageplume.Aqueousspeciation
greater than 6.2 to approximately5.7, a high-concentration of Zn was likely constantover the range of pH and other
core developsin whichZn concentrations greaterthan 15/•M chemicalconditionsobservedin the sewageplume.
are observed(Figure9b). Between62 and 67 yearsthe pH in A reactive transport model incorporatinga semiempirical
this high-concentrationcore remains about 5.7 as it moves surfacecomplexation model(SCM) wasusedto showthat the
downgradient,but Zn concentrationsincreaseto greaterthan observed distribution of Zn contamination in the sewage
25/•M. In additionto desorptionin responseto localdecreases plume resultedfrom pH-dependentadsorptionof Zn on the
in pH values,these high concentrationsresult from the fact aquifer sediments.Parametersfor the SCMs were determined
that the self-sharpening trailing edge of the Zn-contaminated in laboratorybatch experimentswith site-specificsediments.
regionis transportedfasterthan its leadingedge (Figures9b Parametersfor the flow and transportmodel were also ob-
and 9c). Subsequently,Zn concentrations in the high- tained from sourcesindependentof this model. A one-site
concentrationcore decreasebecausealthoughthe tail remains SCM, whichhastwoparameters, accounted well for the influ-
sharp,the leadingedge spreadsout as a result of decreasing ence of pH on Zn adsorptionand transport.A two-siteSCM,
pH valuesout aheadof the advancingZn-contaminatedregion whichhasfour parameters,was alsoable to providean excel-
(Figures9c and 9d). lent estimateof the rate of advancementof the leadingedgeof
The quantitativeaspectsof thesepredictionsare highlyun- the Zn-contaminatedregion. Becausethese SCMs accounted
certain. The predictionsare stronglydependenton the im- for the influenceof variablepH on adsorption,model simula-
posedpH profile at the boundaryand assumedpH buffering tionscouldbe usedto showthat temporalfluctuationsin aqui-
propertiesof the sediments,which are both ad hoc. Measured fer pH valuesunderthe disposalbedswasthe mostlikelycause
pH valuesdirectlyunderthe disposalbedswere not ashigh as of higher Zn concentrationsobservedin the downgradient
thoseimposedin the model calculations(Figure 2). Conse- portionof the Zn-contaminatedregionascomparedwith those
quently,the reservoirof adsorbedZn availablefor mobiliza- at the source.The model alsopredictedlarge increasesin Zn
tion directlyunder the disposalbedsis likely lessthan that in concentrationand mobilityin responseto acidificationof the
the simulations.On the other hand, biodegradationof the Zn-contaminatedregion under the disposalbeds following
particulate organic matter that has accumulatedunder the source cessation.
disposalbedsin the presenceof oxygenmayresultin decreases Simulationof the effectsof spatialand temporalvariability
in pH below 5.3 [Abramset al., 1998], whichwould facilitate of pH on the mobilityof Zn wasachievedmore easilywith the
desorptionof Zn. Furthermore,the rate at which pH changes semiempiricalSCM approachthan would havebeen possible
move throughthe systemdependson the pH-bufferingprop- with modeling approachesbased on distributioncoefficients
erties of the sediments. These uncertainties do not, however, (K• values)or otherempiricaladsorption isothermparameters
call into questionthe main qualitativeaspectsof the predic- (suchasFreundlichor Langmuirisothermparameters).Using
tions.It can be expectedthat dissolvedZn concentrations will these empirical parameterswould require accountingfor the
KENT ET AL.: MODELING THE INFLUENCE OF VARIABLE pH 3423
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