Subsurface Flow and Transport Modeling Research ...Subsurface Flow and Transport Modeling Research:...
Transcript of Subsurface Flow and Transport Modeling Research ...Subsurface Flow and Transport Modeling Research:...
Subsurface Flow and TransportModeling Research: Incorporating
Biologically Mediated Processes
Annual NABIR PI MeetingWarrenton, Virginia
Steve Yabusaki
Yilin Fang
Phil Long
Pacific Northwest National LaboratoryPacific Northwest National Laboratory
April 19, 2005
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Predicting Coupled Process Behavior inPredicting Coupled Process Behavior inField-Scale SystemsField-Scale Systems
Recent Workshops“Integrating Numerical Models of Reactive Flow and Transport into FundamentalGeoscience Research,” DOE-BES, June 2003
“A Science-Based Case for Large-Scale Simulation,” DOE-SC, June 2003
“Conceptual Model Development for Subsurface Reactive Transport Modeling,”Multiagency Working Group on Subsurface Reactive Solute Transport, April 2004
Reliable prediction of field scale behavior is a scientific challengeMany field-scale issues are difficult to address at the lab scale
Many processes and properties are difficult to monitor in the field
Reactive transport models integrate fundamental earth science research andfocus on complex natural environments where individual time and space-dependent processes are linked
Need for multidisciplinary research teams dedicated to developing aquantitatively mechanistic understanding of behaviors at a particular field siteto address the range of scales and multiple interacting processes
Build field-scale process models on a framework of understanding fromfundamental experiments and characterization studies at complementarylength scales in the field
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Conceptual Model: Old RifleConceptual Model: Old RifleBiostimulationBiostimulation Experiments Experiments
Bulk of uranium and sulfate in the aquifer originated asleachate from mill tailings
Uranium transported as U(VI) with the bulk adsorbed tothe sediments under background geochemical conditions
Acetate stimulates the growth of microbial populations thatremove aqueous U(VI) from solution via homogeneousreduction reactions that form uraninite
Initial bioreduction of aqueous U(VI) is 75 to 85 percentefficient and is attributed to iron reducing bacteria that useFe(III) minerals as a terminal electron acceptor
Once bioavailable iron is depleted, the iron reducingbacteria are succeeded by sulfate reducing bacteria,which are less efficient at U(VI) removal from groundwater
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How do spatial and temporal variations inHow do spatial and temporal variations inhydrogeology and chemistry affect uraniumhydrogeology and chemistry affect uranium
behavior?behavior?Heterogeneous materials
Permeability
Iron and uranium
Depth-dependent U(VI) and DOHighest DO and U(VI) near the water table
IssuesOxygen diffusion through water table
Background utilization of DO
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How do seasonal and episodic hydrologicHow do seasonal and episodic hydrologicevents affect uranium behavior?events affect uranium behavior?
Seasonal and event-driven changes
Velocity field
Oxidation of zonesaffected by water tablefluctuations
Issues
Rapid oxidation of zonesaffected by water tablefluctuations
Highest Uconcentrationsbypassing treatmentzones
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What controls the post-amendmentWhat controls the post-amendmenturanium behavior?uranium behavior?
Residual enzymatic reductive capacity of biomass
Uranium surface complexation
Fe(II) adsorption / desorption
Mineral precipitation and dissolution [Fe(III)oxides/hydroxides, uraninite, FeS(am), siderite, calcite]
Coprecipitation
Alteration in surface reactivity
Alteration of access to reactive surfaces
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Goal and ObjectivesGoal and Objectives
Goal
Systematic and quantitatively predictiveunderstanding of the mechanistic contribution byindividual subsurface processes to the observeduranium behavior at the Old Rifle UMTRA field site.
Objectives
Determine the interplay between microbial and abiotic reactionsgoverning field-scale bioremediation in the context of site-specifichydrologic and geochemical conditions
Determine the impact of biostimulation on the geochemical controls(Eh, carbonate speciation and complexation, pCO2, mineralsolubility, adsorption, pH) governing the mobility and long-term fateof uranium
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ApproachApproach
Build field-scale conceptual process modelsFlow and transport
Biogeochemistry of biostimulation
Uranium surface complexation
Systematically integrate process models into acomprehensive field-scale flow and biogeochemicalreactive transport simulation capability
TEAPs and abiotic consequences of biostimulation affectinguranium mobility
Reoxidation and uranium mobility
Latent capacity for removal of aqueous U(VI)
Evolving surface chemistry (mineral precipitation/dissolution,adsorption/desorption)
PhilosophyStart simple to isolate major behaviors
Systematically add process complexity and detail
Use modeling to gain insight and target knowledge gaps
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2002 Flow Field2002 Flow Field
2002 M-07 Water Level
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7.2
7.4
7.6
7.8
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8.4
Jun-02 Jul-02 Aug-02 Sep-02 Oct-02 Nov-02 Dec-02
Days From Injection
Wat
er T
able
Ele
vatio
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Gradient Direction and Relative Magnitude
N
2002 field experiment
No prior augmentation
Steady flow field
Injection June 22 – Oct 23
Modeling assumptions
1-D domain
Constant velocity anddispersivity based onbromide transport
Bulk tank release ratedistributed uniformly overinjection gallery
Injection averaged oversaturated thickness
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Initial Flow and Transport ModelingInitial Flow and Transport Modeling
10 mM Bromide injected
Breakthrough at monitoringwells
General trends reproduced withconstant velocity anddispersivity
Row 2 has highestconcentrations and maximumvariability missed by averageinjection
Preferential flow paths
Release not uniform or fullymixed
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0 20 40 60 80 100 120 140 160 180 200 220 240 260 280 300
Time (d)
Br
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Model
25d 54d 89d 123d
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Br
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25d 54d 89d 123d
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Time (d)
Br
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Model
25d 54d 89d 123d
Row 1
3.66 m downgradient
Row 3
14.63 m downgradient
Row 2
7.32 m downgradient
M-06 M-11M-01
Old Rifle Test Plot
Monitoring wells Control
Wells Acetate
GW flow
6.1m
16m
24m
Injection Gallery
M-15M-05 M-10
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Biologically Mediated ReactionsBiologically Mediated Reactions
3 energetics-based TEAPreactions
Stoichiometry fromRittman/McCarty 2001
Includes biomass yield
Uranium reduction onlyactive during iron reduction
Dual Monod Rate LawHalf-saturation constantsfrom Wang/Jaffe et al. 2003
Calibrate rate and thresholdconcentration for utilization
( )
( )
acceptorelectronalminterfortcoefficiensaturationhalfK
substrateorganicfortcoefficiensaturationhalfK
acceptorelectronalminterforrateoxidationsubstrateorganic
nutilizatioacceptorelectronalminterfortcoefficienindicator
ionconcentratacceptorelectronalminterC
acetateeiionconcentratsubstrateorganicdissolvedC
acceptorselectronalminterofnumberN
where
sitessorptionfreewithtermlastreplacesTEAPIIIFe
CK
C
CK
CR
Cs
Cs
eAm
eA
eA
C
eA
eAeAs
eA
N
eA CCs
CeAmeA
bio
C
eA
=
=
=
=
=
=
=
++=
,
,
,
,,
,
.,.
)(
µ
µ
0.125CH3COO- + 0.6FeOOH(s) + 1.155H+ + 0.02NH4+ = 0.02BM_iron + 0.6Fe++ + 0.96H2O + 0.15HCO3
-
0.125CH3COO- + 0.0057H+ + 0.0038NH4+ + 0.1155SO4
-- = 0.0038BM_sulfate + 0.0114H2O + 0.231HCO3- + 0.1155HS-
0.1250CH3COO- + 0.3538H2O + 0.0113NH4+ + 0.775UO2
++ = 0.0113BM_iron + 0.855H+ + 0.1938HCO3- + 0.775UO2(s)
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Sulfate / Sulfide BehaviorSulfate / Sulfide Behavior
3-4 mM/L sulfide generation
Typical field aqueoussulfide measurement 3uM/L
Implies sulfide associatedwith sediment
2003 AVS: equivalent to~15 mM/L, 5 mM/L, 4mM/L, 1.5 mM/L
Acid Volatile Sulfide (AVS)
Distance of Collected Sediment Core from Injection Gallery
-20 -10 0 10 20 30
0.0
0.5
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2.5
Depth-13' BLS
Depth-15' BLS
Depth-17' BLS
Upgradient Downgradient
P-11Upgradient corecollected at -14.75ftfrom gallery.No AVS detected
P-12
P-13P-14
P-15
uM
/g
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Insights: Need for additional Fe++Insights: Need for additional Fe++
FeS formation on surfaceinferred
Need 3-4 mM/L Fe++ toreact sulfide
Maximum aqueous Fe++measurement is 196 uM/L
Additional Fe++ wouldhave to be associated withsolid phases
Fe++ adsorption
Consistent with otherinvestigators
Multilevel sampling cell endsJanuary 2004
B-02 M-03 M-08 M-13
GroundwaterFlow Direction
Injection Gallery
Aquifer top
Aquifer bottom
PNC-CAT x-ray microprobe
Blackened sediment
Fe and Sulfur
No XRD for sulfide minerals
evidence for FeS(am)
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Expansion of the BiogeochemicalExpansion of the BiogeochemicalReaction NetworkReaction Network
42 total reactions
Aqueous
Ca++, Fe++, K+, Mg++, Na+, H+, NH4+, Cl-, CO3
-, HS-, SO4--
Mineral
CaCO3, FeOOH, FeCO3, FeS, UO2
Sorption
Fe++
Biologically-mediated (by acetate)
Fe(III), U(VI), sulfate TEAPs
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AcetateAcetate
Acetate injected for 123 days
In Row 1, acetate concentrationsdiminish significantly after 40days
Decrease in sulfate
Decrease in Fe++
Model: acetate peak diminisheswith travel distance
Acetate concentrations arespatially and temporally variable
Multiple peaks with later arrivalsin Row 1
Highest concentration in Row 2
Row 3 has much lower acetatethan predicted
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time (d)
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te (
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time (d)
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25d 54d 89d 123d
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time (d)
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25d 54d 89d 123d
Row 1
Row 2
Row 3
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Uranium Uranium BioreductionBioreduction
Initial aqueous U(VI)spatially variable
Initial timing ofaqueous U(VI)removal reproducedby model
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time (d)
U(V
I) u
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Iron Iron BioreductionBioreduction, Dissolution, and Sorption, Dissolution, and Sorption
Initial Fe++ increasefollowed by decreaseafter onset of sulfatereduction
Model predictscumulative peak whichis not obvious in welldata
Effect is observed in2004 experiment
Issues
Fe++ adsorption
Fe++ production may bemuch higher
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time (d)
Fe
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Model
25d 54d 89d 123d
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Sulfate Sulfate BioreductionBioreduction
Sulfate reduction beginsafter 40 days of ironreduction
Rapid and completeutilization of acetate
Sulfate reduction limitedby acetate supply
3 - 4 mM sulfate removedunderestimated by model
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Uranium Experiments on Rifle SedimentsUranium Experiments on Rifle Sediments
Rifle Aquifer Background Sample(RABS)
Sediment sample collectedDecember 2004
10 gallons of < 2 mm prepared
Experiments
Grand Junction
Princeton (Jaffe)
Issues
High background U
Break off point between labile andnonlabile
Kinetics
530504Elapsed time, h
1.120.208Labile U(VI), ug/g
4.2565.15Surface area, m2/g
< 2< 3Particle size, mm
RABSNABS
Set of batch equilibriumadsorption experiments
RABS+AGW-3
10-8 to 10-5 M/L U(VI)
Comparison of experimentalresults with Naturita surfacecomplexation model
RABS appears to be moresorptive
Adsorption of lower U(VI)concentrations sensitive tolabile U(VI)
Solid to
Solution
TIC pCO2 pH
ADS-1 25 g/L 8.25 mg/L 0.10% 7.62
ADS-2 820 108.35 2.39 7.33
ADS-3 125 92.7 2.23 7.28
ADS-4 125 100.2 3.62 7.06
ADS-5 250 238.4 22.8 6.52
ADS-6 125 100.8 5.23 6.90
ADS-7 250 213.6 20.8 6.52
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Uranium Surface Uranium Surface ComplexationComplexation Modeling Modeling
Generalized composite surface complexation model
Preliminary fit of formation constants for 2 surface reactions, 3 sitetypes
1.92 µM/m2 site density (bidentate)
23 aqueous uranium complexation reactions
Includes Ca-UO2-CO3 ternary complexes
U(VI) Surface Reaction Log Kf
SSOH + UO22+
= SSOUO2+ + H
+ 12.28
SOH + UO22+ = SOUO2
+ + H+ 6.95
WOH + UO22+ = WOUO2
+ + H+ 2.74
SSOH + UO22+
+ H2O = SSOUOOH + 2 H+ 0.033
SOH + UO22+
+ H2O = SOUOOH + 2 H+ -2.12
SOH + UO22+ + H2O = SOUOOH + 2 H + -5.01
Total site concentration of 1.92 _moles/m 2
SSOH denoting very strong binding sites: 0.01% of total sites
SOH denoting strong binding sites: 0.1% of total sites WOH denoting weak binding sites: 99.89% of total sites
-0.50
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-8.5 -8.0 -7.5 -7.0 -6.5 -6.0 -5.5 -5.0 -4.5
Log Dissolved U(VI) (moles/L)
Lo
g K
d (
mL
/g)
ADS-1
ADS-2
ADS-3
ADS-4
ADS-5
ADS-6
ADS-7
model ADS-1
model ADS-2
model ADS-3
model ADS-4
model ADS-5
model ADS-6
model ADS-7
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Dissolved Oxygen Stratification:Dissolved Oxygen Stratification:Framework for 2-D Reactive TransportFramework for 2-D Reactive Transport
~20 cm layer of higher DO near watertable
Transported in from upgradient conditions
Diffusion through water table
OO22 influent with GW influent with GW
+ O+ O22 diffusion at WT diffusion at WT
+ O+ O22 microbial TEAP microbial TEAP
Flow
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Next StepsNext Steps
2-D simulations to investigate depth-dependent issuesIncorporate new information on permeability distribution in the verticalIncorporate new information from geophysics
Refine uranium surface complexation modelAssess labile uranium and adsorption kineticsConsider other combinations of uranium surface complexation reactionsand site types in calibrationIdentify additional experiments for model refinement
Incorporate new process models into comprehensive reactive transportsimulator
Datasets2003 and 2004 field experimentsLaboratory experiments
Impacts of biostimulation on iron chemistrydissolution of uranium-bearing Fe(III) mineralsgeneration of Fe(II) and effect of adsorbed Fe(II) on bioavailability of Fe(III)mineralseffect of precipitation and dissolution on the accessibility of Fe(III) and U(IV)mineral surfaces to aqueous components
Post-amendment uranium mobilityconditions for residual capacity to remove U(VI) from groundwaterconditions where ambient geochemistry is being re-established
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AcknowledgmentsAcknowledgments
University of Massachusetts
University of Tennessee
Dick Dayvault and Stan Morrison, SM StollerCorporation
This research was funded by the Natural andAccelerated Bioremediation Research (NABIR)Program, Biological and Environmental Research(BER), Office of Science, U.S. Department ofEnergy. Pacific Northwest National Laboratory isoperated by Battelle for the United StatesDepartment of Energy under Contract DE-AC06-76RLO 1830.
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Backup SlidesBackup Slides
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AGW-3
in air at 0.8547 atmpH 7.79pCO2 0.06%
Adsorption ExperimentsAdsorption Experiments
0.5
1.0
1.5
2.0
0 50 100 150 200 250 300
Experiments with AGW-3Approach based on Davis et al 2004
Assess applicability of GC-SCM approach
Compare with Naturita results
Adsorption Kinetics
25 g/L
1 uM/L U(VI) added
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Depth-Dependent TransportDepth-Dependent Transport