Sie sind auf Seite 1von 19

Journal of Contaminant Hydrology 93 (2007) 130 148

www.elsevier.com/locate/jconhyd

Modelling geochemical and microbial consumption of dissolved


oxygen after backfilling a high level radiactive waste repository
Changbing Yang a,1 , Javier Samper a,, Jorge Molinero b , Mercedes Bonilla a
a
E.T.S. de Ingenieros de Caminos, Canales y Puertos, Universidad de La Corua, Campus de Elvia s/n. 15192 La Corua, Spain
b
Escola Politcnica Superior, Universidad de Santiago de Compostela, 27002 Lugo, Spain
Received 27 April 2006; received in revised form 7 December 2006
Available online 24 January 2007

Abstract

Dissolved oxygen (DO) left in the voids of buffer and backfill materials of a deep geological high level radioactive waste
(HLW) repository could cause canister corrosion. Available data from laboratory and in situ experiments indicate that microbes
play a substantial role in controlling redox conditions near a HLW repository. This paper presents the application of a coupled
hydro-bio-geochemical model to evaluate geochemical and microbial consumption of DO in bentonite porewater after backfilling
of a HLW repository designed according to the Swedish reference concept. In addition to geochemical reactions, the model
accounts for dissolved organic carbon (DOC) respiration and methane oxidation. Parameters for microbial processes were derived
from calibration of the REX in situ experiment carried out at the sp underground laboratory. The role of geochemical and
microbial processes in consuming DO is evaluated for several scenarios. Numerical results show that both geochemical and
microbial processes are relevant for DO consumption. However, the time needed to consume the DO trapped in the bentonite buffer
decreases dramatically from several hundreds of years when only geochemical processes are considered to a few weeks when both
geochemical reactions and microbially-mediated DOC respiration and methane oxidation are taken into account simultaneously.
2007 Elsevier B.V. All rights reserved.

Keywords: Hydrobiogeochemical model; Microbial processes; Reactive transport; HLW repository; Oxygen consumption; DOC respiration;
Methane oxidation; BIOCORE; CORE

1. Introduction Nuclear Waste Management Company (SKB) where


various in situ experiments have been carried out in
Underground facilities are being operated by several fractured granites. Some experiments such as the REX
countries around the world for performing research and experiment aimed at evaluating the stability of redox
providing demonstration of the safety of a deep conditions in engineered barriers and the surrounding
geological high level radioactive waste (HLW) reposi- rock. Redox conditions in deep hard rock environments
tory. The sp Hard Rock Laboratory (HRL) is one of are usually stable with redox potentials between 0.1
such facilities launched and operated by the Swedish and 0.4 V (Haveman et al., 1998). Construction of the
repository will alter natural redox conditions. Initial
Corresponding author.
redox conditions in a saturated HLW repository are ex-
E-mail address: jsamper@udc.es (J. Samper). pected to be determined by the presence of trapped
1
Now at Department of Geological Sciences Indiana University atmospheric O2 in the pores of the buffer material. Even
Bloomington Indiana. trace amounts of O2 can lead to an oxidizing redox
0169-7722/$ - see front matter 2007 Elsevier B.V. All rights reserved.
doi:10.1016/j.jconhyd.2007.01.008
C. Yang et al. / Journal of Contaminant Hydrology 93 (2007) 130148 131

potential (King et al., 2001). Oxygen could be The bentonite buffer material is an integral compo-
detrimental for copper canisters. Cu corrosion by O2 nent of the Swedish KBS-3 concept for a HLW reposi-
has been studied in detail by Vzquez et al. (1994) and tory because it provides mechanical and chemical
King et al. (1995). The predominant reaction pathway stability, hydraulic isolation, and radionuclide sorption
involves the reduction of O2 to OH ions via four se- and retardation (Arcos et al., 2003). Geochemical
quential 1-electron transfer steps, according to the over- stability of the bentonite buffer is essential for repository
all irreversible reaction: performance. LOT experiments were launched by SKB
in order to evaluate the response of bentonite buffer to
O2 2H2 O 4e 4OH geochemical processes induced by a thermal pulse, ce-
which is catalyzed by different Cu surface states. ment and geochemical variability around the repository
Puigdomenech and Taxen (2000) performed a detailed (Arcos et al., 2003). Experiments are carried out at
thermodynamic review for copper, focusing on the vertical boreholes exposed to repository conditions for 1,
implications for canister corrosion in a HLW repository. 5 and 20 years. Each test borehole contains a central
They concluded that dissolved oxygen (DO) and sulphide heater inside a copper tube surrounded by compacted
in groundwater are the most damaging components for MX-80 bentonite cylindrical blocks. Heaters simulate
copper corrosion. DO will react with copper to produce the thermal power from decay of spent nuclear fuel. A
either Cu2O(cr) or Cu+ depending on pH. predictive reactive transport model for some special
Evaluating the consumption of the remaining O2 is cases of the LOT experiment was presented by Arcos
important for the performance assessment of a HLW et al. (2003). Model results indicate that cation exchange
repository (Wersin et al., 1994; Johnson et al., 1996; and calcite dissolution/precipitation are key processes
King et al., 2001). Wersin et al. (1994) used a model to for the chemical performance of the bentonite.
predict the evolution of oxygen in the near-field of a Here we present the application of a coupled hydro-
repository in Swedish granites taking into account oxy- biogeochemical model to evaluate geochemical and
gen diffusion and oxidation of pyrite and dissolved Fe microbial consumption of DO trapped in the bentonite
(II). They estimated that the time required for O2 con- buffer after backfilling a potential HLW repository in a
centration to decrease to 1% of its initial value ranges crystalline formation similar to that at the sp site.
from 7 to 290 years. Similar estimates were derived by The model is solved with BIOCORE2D , a general
Johnson et al. (1996) for Canadian granites. None of purpose code developed by Zhang (2001) and later
these studies considered the role of microbial processes improved by Yang (2006). Bentonite data for our
in consuming DO. model are taken from the model of Arcos et al. (2003).
Numerous studies have been conducted on microbial First, we describe the REX experiment from which
activity related to nuclear waste disposal (McKinley and estimates of microbial parameters are derived. Then,
Grogan, 1991; McKinley et al., 1997; Wang and Francisb, microbial processes and parameters are described. Six
2005). Living microorganisms have been found in back- scenarios are simulated, the results of which allow the
fill materials, natural analogues, low-level radioactive evaluation of the role of biotic and abiotic processes in
wastes, and candidate sites for HLW disposal (Barnhart consuming DO.
et al., 1979; Amy et al., 1992; Pedersen, 1999, 2000a,b;
Wang and Papenguth, 2001; Jolley et al., 2003; Liu and 2. REX experiment
Neretnieks, 2004). Microbes catalyze redox reactions
in the repository environment, play a significant role in The REX project (Redox Experiment in Detailed
buffering redox conditions, may be beneficial to restore Scale) was carried out by SKB, JNC and ANDRA at
prevailing reducing conditions in short periods of time the sp HRL from 1998 to 2001 with the main
(Pedersen, 1999) and immobilize radionuclides (Have- objective of investigating in situ DO depletion after a
man and Pedersen, 2002). Available data from in situ controlled oxidizing perturbation (Puigdomenech
experiments conducted by SKB at the sp site such as et al., 2000). Specific aims of the project included:
the Redox zone and REX experiments indicate that 1) assessing the capacity of the host rock to buffer redox
microorganisms play a substantial role in consuming DO conditions against an oxidizing disturbance; 2) deter-
and controlling redox conditions (Bateman et al., 1998; mining the kinetics of oxygen uptake; and 3) developing
Kotelnikova and Pedersen, 1998; Rivas-Prez and quantitative descriptions of these processes that could
Banwart, 1998; Kotelnikova and Pedersen, 1999; Puig- be used in performance assessment of repository redox
domenech et al., 2000, 2001; Trotignon et al., 2002; stability for the post-closure phase (Puigdomenech
Samper et al., 2003; Molinero et al., 2004). et al., 2000).
132 C. Yang et al. / Journal of Contaminant Hydrology 93 (2007) 130148

The REX project included laboratory studies using tunnel entrance) at a site having the oldest and most
minerals, rock samples, groundwaters and microbes saline groundwaters of the sp underground laboratory
from the sp site. This part of the project included: ([Cl] = 0.4 M aprox.). Prior to each O2 injection, the
the Replica experiment performed at CEA, France recirculation system was filled with O2-free groundwater
(Trotignon et al., 2002); batch and flow-through column from the adjacent borehole KA2862A. O2 injection
experiments (University of Bradford, UK); and micro- pulses started by replacing part of the borehole water by
bial investigations (DBL-Goteborg University). The groundwater samples that had been previously saturated
framework for microbial investigations was named the with either air or O2(g). The procedure was performed at
MICROBE-REX project (Kotelnikova and Pedersen, a hydrostatic pressure of 35 bar. The reaction chamber
1998, 1999). The REX project included also a set of was made of gold-plated stainless steel. Tubing connec-
in situ experiments consisting on the injection and tions and valves were stainless steel. The tubing material
monitoring of non-reactive tracers and DO. Both reactive was PEEK (PolyEtherEtherKetone). A gear pump was
and conservative species were injected into a borehole used to circulate groundwater from the reaction chamber
intersecting a fracture surface which was hydraulically to the measuring electrodes. All the equipment was
isolated by packing a borehole section (Fig. 1). Exper- sterilized before its emplacement inside the borehole to
iments were performed in a closed re-circulating system prevent microbial contamination. A total of 11 O2 injec-
placed in borehole KA2861A. The circulation loop had a tion tests were performed during the REX in situ experi-
total volume of about 1 L. The REX niche is located ment (Puigdomenech et al., 2001). Temperature varied
380 m below ground surface (aprox. at 2860 m from the between 13 and 16 C during most of the experiments.

Fig. 1. Setup of the REX in situ experiment (top) and time evolution of measured and computed dissolved oxygen (bottom).
C. Yang et al. / Journal of Contaminant Hydrology 93 (2007) 130148 133

pH increased from 7.2 at the beginning up to 10 at the position at sp underground laboratory. At present,
end of tests. In general, oxygen was consumed in a nevertheless, such information is not available. It is
few days. worth noting, however, that the key parameter for
The results of the REX project allow quantifying the modeling purposes is yield coefficient, which relates the
oxygen reduction capacity of the granitic bedrock at rate of DOC consumption to microbial growth the rate.
sp (Puigdomenech et al., 2000, 2001). In addition, it Therefore, uncertainties in DOC composition are lumped
can be concluded from them that aerobic respiration of into the yield coefficient of DOC, a parameter usually
DOC is an efficient process for DO consumption in calibrated from laboratory or in situ experiments.
groundwaters (Kotelnikova and Pedersen, 1998). Aerobic heterotrophic bacteria are expected to play
a relevant role in the post-closure stage of a HLW
3. Microbial models repository. Aerobic heterotrophs, probably of the bacte-
rial group Pseudomonas, use DOC as a substrate and DO
Different microbial groups contribute to oxygen as an electron acceptor. In our model, acetate and formate
reduction at the sp site. The following main groups respiration are lumped into a single process denoted
of microorganisms were isolated in oxidizing waters of by DOC respiration which is assumed to proceed ac-
the REX experiment (Kotelnikova and Pedersen, 1999): cording to:
aerobic heterotrophs (15%); methane oxidizers (14%);
heterotrophs
hydrogen oxidizers (14%); and sulphate reducers (14%). CH2 O O2 Y HCO
3 H Biomass
Main electron donors available for microbes in sp deep
groundwaters are dissolved organic carbon (DOC) and Kotelnikova and Pedersen (1999) measured concentra-
CH4 (Puigdomenech et al., 2000, 2001). Although dis- tions of organic electron donors in groundwaters of the
solved H2, HS and Fe(II) could also contribute to O2 spo site at the REX experiment and reported values from
uptake, they have concentrations and reducing capacities 3.8 to 34 M for acetate, from 5 to 52 M for formate and
smaller than those of DOC and CH4. Aerobic respiration from 240 to 292 M for total DOC. Pedersen (2000a)
of organic matter and methane oxidation are the micro- analyzed DOC concentrations at different depths within
bially-driven processes most likely responsible for the sp site and found that DOC varies from 170 M at
oxygen depletion at the REX experiment (Yang et al., 400 m depth to 1500 M at 68 m below the ground
2005). surface. The total number of aerobic and microaerophilic
heterotrophs counted in the REX groundwater after O2
3.1. DOC respiration pulses was 5.4 104 cells/mL (Kotelnikova and Pedersen,
1999). This counting does not include attached micro-
Groundwater DOC consists of high molecular weight organisms which may be more abundant than dissolved-
(HMW) molecules, namely humic and fulvic acids, and suspended microorganisms. Trotignon et al. (2002)
low molecular weight (LMW) compounds such as reported that the amount of heterotrophic aerobes can
aliphatic hydrocarbons, substituted alcohols and organic be up to 1.7 105 cells/cm2 counted in biofilms of the
acids (Atlas and Bartha, 1987). The LMW fraction is laboratory Replica experiment.
recycled by microorganisms and partly derived from
microbial activity transformation of deep kerogens 3.2. Methane oxidation
(Murphy et al., 1992; Aravena et al., 1993). DOC is a
complex mixture of compounds derived from biotic and The REX project revealed that methane-oxidizing
abiotic reactions which can be consumed or produced bacteria are common in the sp HRL tunnel (Kotelni-
by microorganisms. One of its compounds is glucose, kova and Pedersen, 1999). CH4 and H2 have been
which is an easily respirable substrate, but it is not com- detected in all investigated boreholes in sp with con-
monly found in groundwaters. Acetate is a key inter- centrations which exceed the half-saturation constants of
mediate product in anaerobic metabolism of organic competent microorganisms able to oxidize these sub-
matter both in marine and groundwater environments. strates. This indicates that concentrations of these com-
Formate is also a very important intermediate product in pounds are large enough to support significant microbial
anaerobic reactions. Formate may be present as a tran- growth. Measured concentrations of dissolved methane
sient molecule in metabolic pathways. in sp groundwater range from 0.9 up to 980 M.
Modeling DOC respiration by heterotrophic micro- Active methanotrophic bacteria have been found in sp
organisms requires knowing the composition of DOC. groundwater. In fact a new species, named Methylomo-
There are ongoing projects to determine DOC com- nas Scandinavica, was isolated from sp groundwaters
134 C. Yang et al. / Journal of Contaminant Hydrology 93 (2007) 130148

and characterized for the first time (Kalyuznaya et al., Kinetic parameters of DOC respiration have been
1999). Physiological characterization of M. scandina- reported by several researchers (Qu and Bhattacharya,
vica revealed that this species grows in the range of 5 1996, Kotelnikova and Pedersen, 1999). Vogelaar et al.
30 C and pH = 59, attaining optimal growth at 17 C (2003) reported growth and decay kinetic parameters of
and pH = 6.87.8. It was also found that it is a halophilic mesophilic (30 C) aerobic biomass which were
species which is able to grow in a wide range of sa- determined in continuous and batch experiments from
linities. This species is clearly adapted to the environ- measured oxygen uptake rates. Biomass was cultivated
mental conditions prevailing at the sp site. on a single soluble substrate (acetate) in a mineral
Methanotrophic bacteria are relevant microbial spe- medium. The specific growth rate was 11.52 2.64 d 1.
cies for the consumption of oxygen. Microbially-driven The biomass decay constant was 0.96 d 1. Biomass
methane oxidation is assumed to proceed according to: yield coefficient takes a value of 0.5 g biomass/g of
acetate. A Pseudomonas half-saturation constant for
CH4 2O2 Y HCO3 H H2 O Biomass acetate of 7.2 mg/L (125 M) is reported by Qu and
Bhattacharya (1996). These Monod-kinetic parameters
which is catalyzed by M. scandinavica. have been taken as a first guess for our numerical model.
Half-saturation constants of M. scandinavica are
3.3. Microbial rate laws and parameters 32.5 M for methane and 1.5 M for oxygen
(Kalyuznaya et al., 1999). For other Monod-kinetic
The growth rate of heterotrophic and methanotrophic parameters we relied on microbial parameters of meth-
bacteria, rg, is assumed to follow a dual Monod-kinetic ane oxidizers reported by Pedersen (1991), Smith et al.
law: (1997) and Arcangeli and Arvin (1999). Such values
were used to assign a priori values of microbial model
Csub Cea parameters (see Table 1).
rg l C b 1
Ksub Csub Kea Cea
3.4. Calibration of REX microbial model
where Cb, Csub and Cea are concentrations of biomass,
substrate, and electron acceptor, respectively, is spe- DOC respiration and methane oxidation use DO as
cific growth rate, K( ) denotes half-saturation constants, an electron acceptor and therefore compete to consume
and subindexes sub and ea refer to substrates (DOC for it. The consumption rate of DO depends on the values of
heterotrophs and CH4 for methanotrophs) and electron microbial kinetic parameters in Eqs. (1)(4). Therefore,
acceptor (oxygen), respectively. numerical simulation of microbial consumption of DO
The rate of substrate consumption, rsub, is related to trapped in the voids of the repository requires knowing
that of microbial growth, rg, through: appropriate microbial kinetic parameters.
A 1-D microbial reactive transport model of the REX
1 in situ experiment which accounts for DOC respiration
rsub rg 2
Ysub

where Ysub is the yield coefficient. The consumption rate Table 1


of electron acceptor, rea, is related to the rate of microbial Ranges of reported of kinetic parameters for methane oxidizers
growth, rg, through: Parameter Range Value Reference

fea Specific growth rate, Maximum 12.9 Pedersen (1991)


rea rg 3 (d 1) Average 1.5 Arcangeli and
Ysub Arvin (1999)
Minimum 0.215 Kotelnikova and
where fea is the proportionality coefficient between the Pedersen (1999)
rates of consumption of substrate and electron acceptor Decay constant Maximum 0.96 Pedersen (1991)
which in our model is taken equal to 1 for both microbial k (d 1) Average 0.25 Arcangeli and
processes. Arvin (1999)
Microbial decay is assumed to obey the following Minimum 0.085 Arcangeli and
Arvin (1999)
first-order kinetic law: Yield coefficient, Maximum 0.57 Arcangeli and
Y(g biomass /g CH4) Arvin (1999)
rdecay k VCb 4
Average 0.39 Harrison (1973)
Minimum 0.07 Broholm et al. (1992)
where k is the decay constant.
C. Yang et al. / Journal of Contaminant Hydrology 93 (2007) 130148 135

and methane oxidation has been constructed. The model Table 3


has been used to calibrate microbial kinetic parameters Geochemical and microbial components and processes considered in
the hydrobiogeochemical model
from measured oxygen data. Prior estimates of microbial
parameters were derived from published microbial pa- Components Ca2+, Cl, Fe2+, H2O, H+, HCO3 , K+, Mg2+, Na+,
O2(aq),SiO2(aq), SO2 4 , CH4, DOC
rameters. Fig. 1 shows a comparison of computed and Aqueous Ca(H 3 SiO 4 ) 2(aq) , CaCl+ , CaCl 2(aq) , CaCO 3(aq) ,
measured time evolutions of DO at the REX chamber. It complexes CaH2SiO4(aq), CaH3SiO+4, CaHCO+3, CaOH+,
can be seen that computed O2 concentrations match CaSO4(aq), CO2(aq), CO2 +
3 , Fe(OH)2(aq), Fe(OH)2 ,

well the trend of measured O2 data. Calibrated values of
3+ +
Fe(OH)3(aq), Fe(OH)4 , Fe , FeCl , FeCl2(aq), FeCl2 4 ,

microbial parameters are within the range of reported FeCO3(aq), FeCO3+, FeHCO+3, FeOH2+, FeSO4(aq),
H2(aq), H2SiO2 4
4 , H4(H2SiO4)4 , H6(H2SiO4)4 ,
2
values (see Table 2). HCl(aq), HS, HSiO3 , HSO4 , KCl(aq), KHSO4(aq),
Sensitivity runs were performed to evaluate model KOH(aq), KSO4 , Mg(H3SiO4)2(aq), MgCl+, MgCO3(aq),
uncertainties caused by microbial kinetic parameters. MgH2SiO4(aq), MgH3SiO+4, MgHCO+3, MgSO4(aq),
Model results show that the time evolution of oxygen NaCl(aq), NaCO3 , NaHCO3(aq), NaHSiO3(aq),
computed in the REX chamber is sensitive to most NaOH(aq), NaSO4 , OH
Minerals Calcite, siderite, anhydrite, Fe(OH)3(s), quartz,
microbial parameters. However, DO is most sensitive to chlorite, pyrite
the specific growth rate constant of heterotrophic bacteria. Microbes Methylomonas, heterotrophs
Stoichiometric coefficients and equilibrium constant are taken from
4. Simulation of oxygen consumption EQ3/6, Wolery, 1979).

4.1. Coupled hydrobiogeochemical model ment. Groundwater flow in granite will be negligible in
areas with a low fracture density. Therefore, diffusion
The consumption of O2 trapped in the voids of a will be the main solute transport mechanism in both
potential HLW repository has been evaluated using a bentonite and granite. Parameters for the bentonite are
multicomponent microbial reactive transport model taken from those of the model of the LOT experiment
which accounts for 14 primary species, more than 50 (Arcos et al., 2003). Parameters for granite are taken
aqueous complexes, 7 minerals and 2 microbial pro- from Samper et al. (2003). Effective diffusion coeffi-
cesses (see Table 3). Stoichiometric coefficients and cients for granite and bentonite are 1.27 10 12 and
equilibrium constant for aqueous complexes were taken 5 10 10 m2/s, respectively. Porosities are equal to 0.004
from EQ3/6 database (Wolery, 1979). Model domain is for granite and 0.33 for bentonite.
1D axisymmetric (Fig. 2) and includes two material Both inner and outer boundaries are assumed imper-
zones: the bentonite buffer made of compacted MX-80 vious. Granitic water is assumed to be initially under
bentonite (0.05 m b r b 0.4 m) and the sp granite reducing conditions and containing dissolved organic
formation (0.4 m b r b 10 m). The domain is discretized matter. Its chemical composition was taken equal from
using 301 1D finite elements, 60 of which are in ben- values measured at borehole KA2861A (Puigdomenech
tonite and the remaining 241 elements are in granite. et al., 2000, 2001). The initial chemical composition of
Bentonite is assumed to be initially saturated because bentonite was taken from the numerical model of the
its saturation will be enhanced during bentonite emplace- LOT experiment (Arcos et al., 2003) except for DO. Its
concentration in bentonite porewater is initially assumed
to be in equilibrium with atmospheric conditions. Initial
Table 2 chemical compositions of granite and bentonite pore-
Calibrated microbial kinetic parameters for DOC respiration and waters adopted in the model are listed in Table 4.
methane oxidation for the model of the REX experiment at the sp site After backfilling, DO in the bentonite will react
Parameter Calibrated value with iron minerals of bentonite and diffuse into gran-
Methane oxidation Specific growth rate 0.215 d 1 itic porewater. In the granite, DO can be consumed by
Decay constant 0.085 d 1 Methylomonas and heterotrophs as well as by abiotic
Yield coefficient 0.41 g Biomass/g CH4 chemical processes. Bentonite porewater is assumed to
Half-saturation methane 32.5 M
be free of biomass and organic matter initially. Initial
Half-saturation oxygen 1.5 M
DOC respiration Specific growth rate 11.52 d 1 concentrations of DOC and CH4 in granite were taken
Decay constant 0.96 d 1 from the REX experiment (Puigdomenech et al., 2000,
Yield coefficient 0.5 g Biomass/g DOC 2001).
Half-saturation DOC 125 M Initial mineral abundances in granite and bentonite
Half-saturation oxygen 1.5 M
are listed in Table 5. Initial porewaters are assumed at
136 C. Yang et al. / Journal of Contaminant Hydrology 93 (2007) 130148

Fig. 2. Scheme of model domain (left, modified from Pers and Konsult, 2004) and 1-D axisymmetric finite element grid (right) for the coupled model
of O2 consumption in the bentonite buffer.

equilibrium with both quartz and calcite. Bentonite m2s for pH = 7 to 3 10 12 mol/m2s for pH = 12. Ac-
porewaters are initially at equilibrium also with anhy- cording to these values, a constant dissolution rate of
drite. While pyrite and chlorite dissolve according to 10 12 mol/m2s was adopted for chlorite in our model.
kinetic laws, calcite, quartz and anhydrite are assumed to Kinetics of pyrite oxidation has been studied extensively
be at local chemical equilibrium. by Williamson and Rimstidt (1994) and Evangelou
Pyrite and chlorite are key inorganic reducers for DO (1998). The kinetic oxidation of pyrite depends on the
which are assumed to dissolve kinetically. Brandt et al. concentrations of both H+ and DO according to
(2003) reported a steady-state dissolution rate for
chlorite at 25 C and pH 5 of 10 13 mol/m2s. They rm rje CO0:52 CH0:11
5
reported dissolution rates ranging from 4 10 13 mol/
where ke is effective kinetic rate constant which is equal
Table 4
to 6.5 10 9 mol/m2/s, and is specific surface area.
Concentrations (M) of initial waters Values of for pyrite and chlorite are listed in Table 5.
Species Initial waters
The numerical model was solved with BIOCORE2D,
a general purpose code developed by Zhang (2001)
Bentonite Granite
based on CORE2D (Xu et al., 1999; Samper et al., 2000)
Ca2+ 1.85 10 2 1.24 10 1 and later improved by Yang (2006). BIOCORE2D solves
Cl 1.26 10 1 3.69 10 1
for groundwater flow, heat and multicomponent solute
Fe2+ 9.67 10 12 9.67 10 6
pH 8.4 7.2 transport in variably saturated porous media with a
HCO3 1.7 10 4 4.6 10 4
K+ 2 10 4 6.73 10 4
Mg2+ 4.43 10 3 1.78 10 3 Table 5
Na+ 2.31 10 1 1.42 10 1 Initial mineral volume fractions in bentonite and granite
Eh 0.73 0.13
Minerals Bentonite Granite
SiO2(aq) 2.49 10 4 7.16 10 5
SO2
4 7.63 10 2 6.56 10 3 Calcite 4.75 10 3 10 2
DOC 2 10 10 2 10 4 Quartz 1.18 10 1 10 1
Heterotrophs (mg/L) 4 10 8 4 Anhydrite 9.12 10 4 0
CH4 10 10 10 4 Fe(OH)3(s) 0 0
Methylomonas (mg/L) 10 8 1 Siderite 0 0
Pyrite 1.11 10 3 (0.33) 10 3 (0.04)
Values for bentonite are taken from the model of the LOT experiment
Chlorite 0 10 1 (0.04)
(Arcos et al., 2003).
Species not considered by Arcos et al. (2003) in their numerical Values within parentheses correspond to specific surface areas for
model of the LOT experiment. Eh in bentonite is different than that in kinetically-controlled mineral phases (m 1). Values for bentonite are
the numerical model of the LOT experiment. taken from the model of the LOT experiment (Arcos et al., 2003).
Table 6
Description of scenarios with their main features and model input parameters
Main features Scenarios

C. Yang et al. / Journal of Contaminant Hydrology 93 (2007) 130148


S1_unreactive S2_ChlG S3_ChlG_PyrG&B S4_ChlG_PyrG&B_MicG_DocG S5_ChlG_PyrG&B_MicG_DocG&B S6_ChlG_PyrG&B_MicG&B_DocG&B
O2 diffusion Yes Yes Yes Yes Yes Yes
Chlorite dissolution in granite No Yes Yes Yes Yes Yes
Chlorite dissolution rate No 10 12 10 12 10 12 10 12 10 12
constant (mol/m2/s)
Pyrite dissolution in bentonite No No Yes Yes Yes Yes
and granite
Pyrite dissolution rate constant No No 6.5 10 9 6.5 10 9 6.5 10 9 6.5 10 9
(mol/m2/s)
Microbial processes in granite No No No Yes Yes Yes
Microbial processes in No No No No No Yes
bentonite
Initial concentration of CH4 in N.a. N.a. N.a. 10 4 10 4 10 4
granite (mol/L)
Initial concentration of CH4 in N.a. N.a. N.a. 0 10 4 10 4
bentonite (mol/L)
Initial concentration of DOC in N.a. N.a. N.a. 2 10 4 2 10 4 2 10 4
granite (mol/L)
Initial concentration of DOC in N.a. N.a. N.a. 0 2 10 4 2 10 4
granite (mol/L)
Time needed to consume 5000 1560 40 a 27 4 19 days
O2 (years) 225 b
Also indicated is the time needed to consume O2 in each scenario. Chl denotes chlorite and Pyr pyrite. While chlorite is only present in granite (ChlG), pyrite is present in both bentonite (B) and granite
(G), PyrG&B. Mic refers to microbial processes which can take place in granite (MicG) or in both granite and bentonite (MicG&B). Doc refers to dissolved organic carbon which initially is present in
granite (DocG) or in granite and bentonite (DocG&B). N.a. = not applicable.
a
Time to consume oxygen computed in scenario S3_ChlG_PyrG&B for specific surface areas of pyrite equal to those listed in Table 5.
b
Time to consume oxygen computed in scenario S3_ChlG_PyrG& for specific surface areas of pyrite equal to 10 times smaller than those listed in Table 5.

137
138 C. Yang et al. / Journal of Contaminant Hydrology 93 (2007) 130148

Fig. 3. Time evolution of DO in the bentonite at a point located at a radial distance of 0.15 m for scenarios 1 to 6 (see Table 6 for details of each scenario).

complete suite of geochemical reactions such as aqueous (d) microbial uptake of DO in granite which contains
complexation, acidbase, redox, adsorption, cation dissolved substrates (DOC and CH4) for microbial
exchange, mineral dissolution/precipitation and gas processes.
dissolution/exsolution (Samper et al., 2006). It considers
the following set of microbial processes: growth, meta- In order to assess the role of biotic and abiotic pro-
bolic competition, decay, metabiosis and endogeneous cesses in oxygen consumption the following six scenarios
respiration. BIOCORE2D has been verified against are simulated:
other codes such as BIOCLOG3D (Engesgaard, 2000,
Kildsgaard and Engesgaard, 2001, Brun and Enges- S1_unreactive. Only diffusion of O2 from the
gaard, 2002) and FEREACT (Tebes-Stevens et al., bentonite to the granite with no chemical reactions.
1998). BIOCORE2D and CORE2D have been used to S2_ChlG. Oxygen diffusion and kinetically-con-
model laboratory and in situ experiments including trolled dissolution of chlorite in granite. One of the
biotransformation of Fe(III) minerals (goethite) into Fe
(II) minerals (pyrite) in the CERBERUS Experiment in
Boom clay (Zhang, 2001; Zhang and Samper, 2001;
Samper et al., 2006), interpretation of the Redox Zone
Experiment in a fracture zone of the sp site (Samper
et al., 2003, Molinero and Samper, 2004; Molinero et al.,
2004; Molinero and Samper, 2006), inverse reactive
transport of laboratory experiments (Dai and Samper,
2004) and coastal aquifers (Dai and Samper, 2006; Dai
et al., 2006) and stochastic cation exchange and reactive
transport in aquifers (Samper and Yang, 2006).

4.2. Scenarios

The coupled hydrobiogeochemical model assumes


that the following biotic and abiotic processes may con-
tribute to the consumption of DO in bentonite porewater
after backfilling:

(a) oxygen diffusion from bentonite into granite Fig. 4. Time evolution of redox potential Eh (top) and pH (bottom) in
(b) chlorite dissolution in granite; bentonite at a point located at a radial distance of 0.15 m for scenarios 3
(c) pyrite oxidization in bentonite and granite; to 6 (see Table 6 for details of each scenario).
C. Yang et al. / Journal of Contaminant Hydrology 93 (2007) 130148 139

products of the dissolution of chlorite, Fe(II), is place also in bentonite. This assumption may seem
oxidized by O2 in granite and hence dissolution of unrealistic according to the research works reported
chlorite consumes O2. This scenario aims at evaluat- by Pedersen (1995, 2002), Motamedi et al. (1996),
ing the role of chlorite dissolution. Pedersen et al. (2000a,b), Masurat and Pedersen
S3_ChlG_PyrG&B. Scenario similar to the previous (2003) and Sellin and Hedin (2004). However, recent
one, but accounting also for kinetic dissolution of observations from partial dismantling of the in situ
pyrite both in bentonite and granite. FEBEX experiment revealed the presence of sulphate
S4_ChlG_PyrG&B_MicG_DocG. Scenario similar to reducing bacteria (SRB) and their effect on the corro-
S3_ChlG_PyrG&B with microbial processes taking sion of metallic sensors embedded in compacted
place only in granite. bentonite blocks. SRB activities were significant in
S5_ChlG_PyrG&B_MicG_DocG&B. Scenario simi- areas with high humidiy and temperatures below
lar to S4_ChlG_PyrG&B_MicG_DocG. and consid- 50 C (Madina and Azkrate, 2004).
ering that concentrations of DOC and methane in
bentonite are equal to those in granite. The following abbreviations are used to denote
S6_ChlG_PyrG&B_MicG&B_DocG&B. Scenario scenarios: Chl for chlorite and Pyr for pyrite. While
similar to S5_ChlG_PyrG&B_MicG_DocG&B and chlorite is only present in granite (ChlG), pyrite is
assuming that the two microbial processes take present in both bentonite (B) and granite (G), PyrG&B.

Fig. 5. Spatial distribution of DO computed after 0.8, 2.1, 5 and 10.5 years for scenarios 2 to 5 (see Table 6 for details of each scenario).
140 C. Yang et al. / Journal of Contaminant Hydrology 93 (2007) 130148

The term Mic refers to microbial processes which can Consumption of DO runs parallel to the decrease of
take place in granite (MicG) or both granite and bentonite redox potential Eh. Fig. 4 shows the time evolution of
(MicG&B). Doc refers to dissolved organic carbon computed Eh and pH in bentonite at a point located
which initially is present in granite (DocG) or in granite at r = 0.15 m. One can see that at early times Eh
and bentonite (DocG&B). Main features and model input remains constant and equal to its initial value of 0.73 V.
parameters for each one of the six scenarios are listed in Then, it decreases dramatically when the concentration of
Table 6. DO decreases. The redox potential in scenario S4_ChlG_
PyrG&B_MicG_DocG decreases after 30 years from
4.3. Results 0.73 V to 0.2 V. Later, it decreases at a smaller rate and
reaches a value of about 0.05 V after 150 years. The time
4.3.1. Oxygen consumption and Eh evolution of pH shows a trend similar to that of Eh. It
Consumption of DO in bentonite porewater is decreases smoothly from its initial value of 8.4 to a quasi
analyzed in terms of the time evolution of DO in the steady value of 7.75.
bentonite at a point located at a radial distance of 0.15 m. Fig. 5 shows the spatial distribution of oxygen
Computed evolutions for scenarios S1_unreactive, computed at different times for scenarios 2, 3, 4, and 5.
S2_ChlG and S3_ChlG_PyrG&B are shown in Fig. 3A. Oxygen diffuses slowly from bentonite into granite and
One can see that the time required for the concentration of reacts with iron minerals. The penetration of the oxygen
DO in bentonite to decrease to a value much lower than its front into granite when microbial processes are con-
initial value is more than 5000 years when only DO sidered (see scenario S4_ChlG_PyrG&B_MicG_DocG)
diffusion is considered (scenario S1_unreactive). Such is much smaller than that computed without microbial
time is 1560 years when only chlorite dissolution is processes. (see scenario S3_ChlG_PyrG&B). Oxygen
allowed (scenario S2_ChlG) and reduces to 40 years penetration depth after 10.5 years is 0.1 m for
when both chlorite and pyrite are considered (scenario S4_ChlG_PyrG&B_MicG_DocG compared to 0.65 m
S3_ChlG_PyrG&B). Clearly, O2 consumption by chlorite for S3_ChlG_PyrG&B.
is much smaller than by pyrite because the kinetic rate of Table 6 summarizes the times needed to consume DO
pyrite depends on the concentration of oxygen (see in bentonite porewater in all 6 scenarios. The analysis of
Eq. (5)). The time for oxygen consumption is very sen- these times indicates that dissolution of chlorite in
sitive to the product of specific surface area times the granite is less efficient than pyrite dissolution in
effective kinetic rate constant of pyrite, e, in Eq.(5). For a consuming DO. Effectiveness of pyrite dissolution in
specific surface area of pyrite 10 times smaller than that in DO depletion depends greatly on pyrite specific surface
S3_ChlG_PyrG&B, the time required to consume DO area. Microbial processes play a major role in O2 con-
increases from 40 to 225 years, other parameters being sumption. The presence of dissolved organic matter in
the same.
The time evolution of oxygen in bentonite computed
in scenarios S4_ChlG_PyrG&B_MicG_DocG, S5_
ChlG_PyrG&B_MicG_DocG&B, and S6_ChlG_
PyrG&B_MicG&B_DocG&B are shown in Fig. 3B. It
can be seen that the time needed to consume O2 in
bentonite is 27 years in S4_ChlG_PyrG&B_MicG_
DocG, 4 years in S5_ChlG_PyrG&B_MicG_DocG&B
and 19 days in S6_ChlG_PyrG&B_MicG&B_DocG&B.
Oxygen is consumed faster in S4_ChlG_PyrG&B_
MicG_DocG than in S3_ChlG_PyrG&B because con-
trary to the latter, the former accounts for microbial
reactions in granite. When bentonite porewater contains
organic matters without microbial growth in bentonite
(S5_ChlG_PyrG&B_MicG_DocG&B), the time need-
ed to consume O2 is much smaller than that in S3_ChlG_
PyrG&B. The time needed to consume oxygen dramat-
ically decreases to less than 3 weeks when microbes are
allowed to grow in bentonite. Therefore, microbial Fig. 6. Spatial distribution of pH computed at different times in
reactions play a relevant role on O2 consumption. scenario S4_ChlG_PyrG&B_MicG_DocG.
C. Yang et al. / Journal of Contaminant Hydrology 93 (2007) 130148 141

bentonite porewater can influence O2 consumption even 4.3.3. Organic matter and microorganisms
if microbial processes take place only in granite. Fig. 7 shows the spatial distribution of CH4, DOC,
heterotrophs, and methanotrophs computed in scenario
4.3.2. Ph S4_ChlG_PyrG&B_MicG_DocG at t = 0, 0.8, 2.1, 5,
Fig. 6 shows the spatial distribution of pH computed and 10.5 years. Initial concentrations of CH4 and DOC in
in scenario S4_ChlG_PyrG&B_MicG_DocG at t = 0, granite are 10 4 and 2 10 4 mol/L, respectively. Their
0.8, 2.1, 5 and 10.5 years. Initial values of pH are 8.4 concentrations in bentonite are zero. Microbial consump-
and 7.2 in bentonite and granite, respectively. One can tion of organic compounds in granite porewaters is fast and
see that pH decreases with time in bentonite while it takes place in a thin band located near the bentonitegranite
increases in granite due to diffusion of OH from interface. DOC and CH4 show diffusive fronts which
bentonite into granite. Although one of the products of propagate with time into granite (Fig. 7A and B). Microbes
microbial growth is H+, it can be concluded that pH in the grow mostly within a 10 cm thick band located near the
granite is not dominated by microbial processes. Instead, granitebentonite interface due to the limitation imposed
pH increases due to calcite dissolution which buffers the by the availability of the electron acceptor (O2) which must
protons released by microbial processes (see Fig. 8E). diffuse from bentonite into granite (Fig. 7C and D).

Fig. 7. Spatial distribution of: A) CH4, B) DOC, C) Heterotrophs, and D) Methylomonas computed at different times for scenario
S4_ChlG_PyrG&B_MicG_DocG.
142 C. Yang et al. / Journal of Contaminant Hydrology 93 (2007) 130148

4.3.4. Mineral dissolution and precipitation bentonite and also within a thin band of 0.1 m in granite.
Fig. 8 shows the spatial distribution of pyrite, Since the dissolution rate of pyrite depends on oxygen
chlorite, Fe(OH)3(s), and anhydrite at 0.8, 2.1, 5, and concentration, pyrite dissolution is fast under oxidizing
10.5 years computed in scenario S4_ChlG_PyrG&- conditions while it slows down when DO is consumed.
B_MicG_DocG. One can see that pyrite dissolves in One can see in Fig. 5D that the penetration of the DO

Fig. 8. Spatial distribution of cumulative mineral dissolution/precipitation of: A) pyrite, B) chlorite, C) Fe(OH)3(s), D) anhydrite, and E) calcite
computed at different times for scenario S4_ChlG_PyrG&B_MicG_DocG (positive values for precipitation and negative for dissolution).
C. Yang et al. / Journal of Contaminant Hydrology 93 (2007) 130148 143

front into granite after 10.5 years is only 0.1 m. Beyond because the concentration of dissolved iron is much
that point, oxygen concentration is extremely small and larger in granite than in bentonite. As expected, the
therefore pyrite does not dissolve. largest amount of precipitation of Fe(OH)3(s) occurs
Fig. 8B shows the spatial distribution of cumulative where the fronts of H+ (see Fig. 6) and dissolved iron
amount of chlorite dissolution after 0.8, 2.1, 5 and (Fig. 9D) overlap.
10.5 years. As expected, the cumulative amount of The concentration of SO42 in bentonite and granite
chlorite dissolution is uniform in the granite because the porewaters is controlled by the solubility of anhydrite.
model assumes a constant chlorite dissolution rate. The Fig. 8D shows the spatial distribution of cumulative
saturation index of chlorite remains negative during all amount of anhydrite precipitation computed in scenario
the simulation. S4_ChlG_PyrG&B_MicG_DocG. One can see that
The spatial distribution of cumulative amount of Fe anhydrite precipitates mostly in granite due to SO42
(OH)3(s) precipitation after 0.8, 2.1, 5.0 and 10.5 years is diffusion from bentonite into granite where its concen-
shown in Fig. 8C. One can see that precipitation of Fe tration is much larger than in granite (see Fig. 9C) and its
(OH)3(s) occurs only after 5 years and takes place in both reaction with dissolved Ca2+ (see Fig. 9A).
bentonite and granite. The amount of Fe(OH)3(s) Microbial processes produce HCO3 and H+. The in-
precipitation in granite is larger than that in bentonite crease in HCO3 concentration leads to calcite precipitation.

Fig. 9. Spatial distribution of computed dissolved concentrations of: A) Ca2+, B) HCO3 , C) SO2
4 and D) total iron in scenario
S4_ChlG_PyrG&B_MicG_DocG.
144 C. Yang et al. / Journal of Contaminant Hydrology 93 (2007) 130148

Fig. 10. Sensitivity of computed redox potential (top) and DO concentrations (bottom) in bentonite to an increase in initial DOC concentration in
granite by a factor of 5 compared to the reference run.

On the contrary, the release of protons by microbial pro- (Fig. 9A). It should be noticed that the rate of anhydrite
cesses favors calcite dissolution. Fig. 8E shows the spatial precipitation exceeds greatly that of calcite dissolution
distribution of cumulative amoun of dissolution of calcite (see Fig. 8D and E). Therefore, dissolved Ca2+ released
computed in S4_ChlG_PyrG&B_MicG_DocG. Calcite by calcite dissolution precipitates as anhydrite.
dissolves mainly in granite near the bentonitegranite The spatial distribution of computed HCO3 concentra-
interface. tions shows that HCO3 diffuses from granite into bentonite
(Fig. 9B). One can see that peaks of HCO3 coincide with
4.3.5. Dissolved chemical species those of calcite dissolution and microbial growth.
Concentrations of dissolved Ca2+ in granite pore- Although HCO3 concentration increases due to calcite
water decrease with time due to anhydrite precipitation dissolution and microbial processes, siderite does not
C. Yang et al. / Journal of Contaminant Hydrology 93 (2007) 130148 145

precipitate because dissolved iron concentrations are too decrease significantly. The spatial distribution of com-
low both in granite and bentonite porewaters (see Fig. 9D). puted biomass concentrations (see Fig. 7C and D)
Initial concentration of SO42 in bentonite is larger confirms clearly that microbial growth is large until 0.8
than in granite. Therefore, SO42 diffuses from bentonite years. After that time, bacterial concentrations attain
into granite where it precipitates as anhydrite (Fig. 9C). quasi steady values.
Computed concentration of dissolved iron is much Another source of uncertainty in our model comes
larger in granite than in bentonite where it remains al- from the fact that our model assumes that all microbial
ways low because the iron released by pyrite dissolution species are mobile. While this assumption is valid for
precipitates as Fe(OH)3(s) (Fig. 9D). Dissolved iron most methanotrophic bacteria, some heterotrophic bacte-
concentrations in granite near the bentonitegranite ria could be present as biofilms attached to mineral
interface decrease due to Fe(OH)3(s) precipitation. Far surfaces. Our computer code BIOCORE2D can handle
from such interface, however, concentration of dissolved attachment/detachment of bacteria, biofilm development
iron increases due to chlorite dissolution. and nutrient diffusion through biofilms. Modeling bac-
terial biofilms, however, requires additional parameters
4.4. Model uncertainties for which at present there is no sufficient data. The
analysis of the role of attached bacteria requires further
Sensitivity runs have been performed to evaluate research.
model prediction uncertainties caused by uncertainties in
model parameters and initial conditions. Sensitivities 5. Discussion and conclusions
have been evaluated for scenario S4_ChlG_PyrG&B_
MicG_DocG by changing the following parameters one- Once DO is consumed, computed values of pH and
at-a-time: 1) specific growth rate of Methylomonas, 2) Eh attain the following approximate values: pH = 7.75
specific growth rate of heterotrophs, 3) yield coefficient and Eh = 0.05 V (see Fig. 4). These values of Eh and pH
of CH4, 4) yield coefficient of DOC, 5) initial DOC in are at the boundary of the stability field of native Cu in a
granite and 6) effective diffusion coefficient. Computed thermodynamic Cu stability diagram (see Fig. 11). This
DO concentrations and redox potential in the bentonite diagram corresponds to a total Cu concentration of
buffer are most sensitive to the initial DOC concentration 1 mol/kg at 25 C (Puigdomenech and Taxen, 2000). It
(see Fig. 10). An increase of initial DOC concentration by can be seen that after DO consumption, computed Eh
a factor of 5 reduces the time required to consume DO and pH are at the boundary of the stability field of native
from 27 to 17 years. The increase in DOC reduces also Cu, Cu(cr), and oxidized copper (Cu2O). Therefore, it
the time needed to lower redox potential from its initial can be concluded that computed pH and Eh conditions
value of 0.73 V to a value of 0.2 V. Computed Eh values
after 40 years, however, are the same regardless the initial
DOC. Computed DO and Eh are much less sensitive to a
change in effective diffusion coefficients of bentonite and
granite, De. An increase of De of both materials by a
factor of 2 does not lead to a significant change in the
time evolution of DO (not shown here). On the other
hand, computed results lack sensitivity to changes in the
rest of microbial parameters.
These results differ from those of the microbial
reactive transport model of the Redox Zone experiment
of Samper et al. (2003) and Molinero et al. (2004). They
found concentrations of redox-sensitive species in the
Redox Zone to be sensitive to most microbial para-
meters. Here, on the contrary, oxygen concentrations and
Eh are much more sensitive to initial concentrations of
substrates than to microbial parameters because micro-
bial growth is limited by the availability of both electron Fig. 11. Thermodynamic Cu stability diagram computed for a total Cu
concentration of 1 mmol/kg at 25 C (modified from Puigdomenech
acceptor and substrates. Microbial growth rates are large and Taxen, 2000). It can be seen that computed Eh/pH conditions
as long as concentrations of both DO and substrates are correspond to the boundary of the stability field of native Copper
large. Once either of the two is depleted, growth rates (Cucr) and the oxidized copper (Cu2O).
146 C. Yang et al. / Journal of Contaminant Hydrology 93 (2007) 130148

after depletion of trapped oxygen are in the region where References


copper corrosion is prevented.
The presence of DO left in the voids of bentonite Amy, P.S., Haldeman, D.L., Ringelberg, D., Hall, D.H., Russell, C.,
1992. Comparison of identification systems for classification of
buffer after repository closure could affect canister
bacteria isolated from water and endolithic habitats within the
corrosion and migration of radionuclides eventually deep subsurface. Applied and Environmental Microbiology 58,
released from a damaged canister. Evaluating how O2 is 33673373.
consumed is therefore important for safety analyses. A Arcangeli, J.P., Arvin, E., 1999. Modelling the growth of a
coupled hydrobiogeochemical model has been used to methanotrophic biofilm: estimation of parameters and variability.
Biodegradation 10, 177191.
evaluate O2 consumption by geochemical and microbial
Arcos, D., Bruno, J., Karnland, O., 2003. Geochemical model of the
processes. granite-bentonite-groundwater interaction at sp HRL (LOT
Calibrated parameters from the REX experiment have experiment). Applied Clay Science 23, 219228.
been used for the numerical model of repository con- Aravena, R., Evans, M.L., Cherry, J.A., 1993. Stable isotopes of
ditions. Kinetics of oxygen consumption depends on the oxygen and nitrogen in source identification of nitrate from septic
systems. Ground Water 31, 180186.
coupling between diffusion and oxidation of accessory
Atlas, R., Bartha, R., 1987. Evolution and structure of microbial
minerals in bentonite, and diffusion, mineral oxidation and communities, Microbial Ecology: fundamentals and applications,
microbial processes in granite. Such complex couplings 2nd ed. Addison Wesley Publishing.
have been evaluated with a coupled hydro-bio-geochem- Bateman, K., West, J.M., Aoki, K., Yoshida, H., Coombs, P., Gillespie,
ical reactive transport model for 6 possible scenarios. M.R., Henney, P., Reeder, S., Milodowski, A.E., 1998. Laboratory
examination of microbial effects upon redox in a geological
Numerical results lead to the following major conclusions:
disposal site for radioactive waste. In: McKinley, I.G., McCombie,
C. (Eds.), Scientific Basis for Nuclear Waste Management XXI.
Dissolution of chlorite in granite is much less effec- Mat. Res. Soc. Symp. Proc., vol. 506, pp. 10191020. Pittsburgh,
tive than pyrite dissolution in consuming DO. Penn.
Pyrite dissolution in bentonite is important. The time Barnhart, B.J., Campbell, E.W., Hardin, J.M., Martinez, E., Caldwell,
D.E., Hallett, R., 1979. Potential Microbial Impact on Transuranic
required to consume O2 by pyrite dissolution ranges
Wastes Under Conditions Expected in the Waste Isolation Pilot
from 40 to 225 years depending on the value of the Plant (WIPP). LA-7788-PF. Los Alamos National Laboratory,
specific surface area of pyrite. New Mexico.
Microbial processes play a major role in O2 con- Brandt, F., Bosbach, D., Krawczyk-Brsch, E., Arnold, T., Bernhard,
sumption. They are more effective than geochemical G., 2003. Chlorite dissolution in the acid pH-range: a combined
microscopic and macroscopic approach. Geochimica et Cosmo-
processes in consuming DO. The time required to
chimica Acta 67 (8), 14511461.
deplete the initial DO depends strongly on the initial Broholm, K., Christensen, T.H., Jensen, B.K., 1992. Modeling TCE
concentration of substrates. On the contrary, it is not degradation by a mixed culture of methane-oxidizing bacteria.
sensitive to microbial parameters. Water Research 26, 11771185.
The presence of dissolved organic matter in bentonite Brun, A., Engesgaard, P., 2002. Modeling of transport and
biogeochemical processes in pollution plumes: literature review
porewater can influence O2 consumption even if
and model development. Journal of Hydrology 256, 211227.
microbial processes only take place in granite. The Dai, Z., Samper, J., 2004. Inverse problem of multicomponent re-
time needed to consume O2 decreases from 27 years active chemical transport in porous media: formulation and ap-
without organic matters in the bentonite to 4 years. plications. Water Resources Research 40, W07407. doi:10.1029/
DO is consumed in less than a month if microbial 2004WR003248.
Dai, Z., Samper, J., 2006. Inverse modeling of water flow and
reactions can proceed in bentonite.
multicomponent reactive transport in coastal aquifer systems.
Journal of Hydrology 327 (34), 447461.
Acknowledgements Dai, Z., Samper, J., Ritzi, R., 2006. Identifying geochemical processes
by inverse modeling of multicomponent reactive transport in
This work has been funded by the Swedish Nuclear Aquia aquifer. Geosphere 4 (4), 210219.
Engesgaard, P., 2000. Model for biological clogging in 3D, Brief
Fuel and Waste Management Company (SKB). Thanks
user's manual and guide. Department of Hydrodynamics and
are given to Professor Karsten Pedersen and Dr. Ignasi Water Resources, Danish Technology University, Denmark.
Puigdomenech for their constructive comments and Evangelou, V.P., 1998. Environmental soil and water chemistry:
guidance on microbial processes and to the University Principles and Application. John Wiley and Sons, Inc., New York.
of La Corua for the research scholarship awarded to the Harrison, D.E.F., 1973. Studies on the affinity of methanol- and
methane-utilising bacteria for their carbon substrates. Journal of
first author. We thank the two anonymous reviewers and
Applied Bacteriology 36, 301308.
the Editor-in-charge for comments, suggestions and Haveman, S.A., Pedersen, K., 2002. Microbially-mediated redox
recommendations which contributed to improve the processes in natural analogues for radioactive waste. Journal of
paper. Contaminant Hydrology 55, 161174.
C. Yang et al. / Journal of Contaminant Hydrology 93 (2007) 130148 147

Haveman, S.A., Pedersen, K., Routsalainen, P., 1998. Geomicrobial sp hard rock laboratory (Sweden). Nuclear Technology 48 (2),
investigations of groundwaters from Olkiluoto, Hstholmen, 151165.
Kivetty and Romuvaara, Finland. POSIVA Technical Report Murphy, E.M., Schramke, J.A., Fredrickson, J.K., Bledsoe, H.W.,
8909. Francis, A.J., Sklarew, D.S., Linehan, J.C., 1992. The influence
Johnson, L.H., Leneveu, D.M., King, F., Shoesmith, D.W., Kolr, of microbial activity and sedimentary organic carbon on the iso-
M., Oscarson, D.W., Sunder, S., Onofrei, C., Crosthwaite, J.L., tope geochemistry of the Middendorf aquifer. Water Resources
1996. The disposal of Canada's nuclear fuel waste: a study of Research 28 (3), 723740.
postclosure safety of in-room emplacement of used CANDU fuel Motamedi, M., Karnland, O., Pedersen, K., 1996. Survival of sulfate
in copper containers in permeable plutonic rock: volume 2: vault reducing bacteria at different water activities in compacted
model. AECL-11494-2, COG-96-552-2. Atomic Energy of Canada bentonite. FEMS Microbiology Letters 141, 8387.
Limited Report. Pedersen, A.R., 1991. Growth kinetic of a methane-oxidizing biofilm.
Jolley, D.M., Ehrhorn, T.F., Horn, J., 2003. Microbial impacts to the M.Sc. thesis Department of Environmental Science and Engineer-
near-field environment geochemistry: a model for estimating ing. Technical University of Denmark.
microbial communities in repository drifts in Yucca Mountain. Pedersen, K., 1995. Microbiological investigations. In: Banwart, S.
Journal of Contaminant Hydrology 6263, 535575. (Ed.), The Redox Experiment in Block Scale. SKB Technical
Kalyuznaya, M.G., Khmelenina, V.N., Kotelnikova, S., Pedersen, K., Report 13467. Stockholm, Sweden.
Trotsenko, Y.A., 1999. Methylomonas scandinavica: a new Pedersen, K., 1999. Subterranean microorganisms and radioactive
methanotropic psychrotrophic bacterium isolated from deep waste disposal in Sweden. Engineering Geology 52, 163176.
igneous rock ground water of Sweden. Systematic and Applied Pedersen, K., 2000a. Microbial processes in radioactive waste
Microbiology 22, 565572. disposal. Technical Report SKB-TR-0004. Stockholm, Sweden.
Kildsgaard, J., Engesgaard, P., 2001. Numerical analysis of biological Pedersen, K., 2000b. Exploration of deep intraterrestrial microbial life:
clogging in two-dimensional sand box experiments. Journal of current perspectives. FEMS Microbiology Letters 185, 916.
Contaminant Hydrology 50, 261285. Pedersen, K., 2002. Microbial processes in the disposal of high
King, F., Quinn, M.J., Litke, C.D., 1995. Oxygen reduction on copper level radioactive waste 500 m underground in Fennoscandian
in neutral NaCl solution. Journal of Electroanalytical Chemistry shield rocks. In: Keith-Roach, M.J., Livens, F.R. (Eds.), Interac-
385, 4555. tions of microorganisms with radionuclides. Elsevier, Amster-
King, F., Ahonen, L., Taxn, C., Vuorinen, U., Werme, L., 2001. dam, pp. 279311.
Copper corrosion under expected conditions in a deep geologic Pedersen, K., Motamedi, M., Karnland, O., Sandn, T., 2000a.
repository. SKB Technical Report, TR-0123, Stockholm, Swe- Cultivability of microorganisms introduced into a compacted
den. SKB Technical Reports are provided free of charge. Those bentonite clay buffer under high level radioactive waste repository
dated after 2000 can be downloaded at www.skb.se. conditions. Engineering Geology 58, 149161.
Kotelnikova, S., Pedersen, K., 1998. Microbial oxygen consumption Pedersen, K., Motamedi, M., Karnland, O., Sandn, T., 2000b. Mixing
in sp tunnel environments. SKB Technical report, PR-HRL- and sulphate reducing activity of bacteria in swelling compacted
9811, Stockholm, Sweden. bentonite clay at high level radioactive waste repository condi-
Kotelnikova, S., Pedersen, K., 1999. The microbe REX Project: tions. Journal of Applied Microbiology 89, 10381047.
microbial O2 consumption in the sp tunnel. SKB Technical Puigdomenech, I., Taxen, C., 2000. Thermodynamic data for copper.
Report, TR-9917, Stockholm, Sweden. Implications for the corrosion of copper under repository con-
Liu, J., Neretnieks, I., 2004. Coupled transport/reaction modeling of ditions. SKB Technical Report TR 0013, Stockholm, Sweden.
copper canister corrosion aided by microbial processes. Radio- Puigdomenech, I., Kotelnikova, S., Pedersen, K., Tullborg, E.L., 2000.
chimica Acta 92, 849854. In-Situ determination of O2 uptake by geologic media: field data
Madina, V., Azkrate, I., 2004. FEBEX Project post-mortem analysis: for the redox experiment in detailed scale. SKB Technical Report,
corrosion study. ENRESA Technical Publication 08/2004. Madrid. IPR-0023, Stockholm, Sweden.
Spain. (available at www.enresa.es). Puigdomenech, I., Ambrosi, J.P., Eisenlohr, L., Lartigue, J.E.,
Masurat, P.A., Pedersen, K., 2003. Microbial sulphide production in Banwart, S.A., Bateman, K., Milodowski, A.E., West, J.M.,
compacted bentonite at the commencement of long-term disposal of 2001. O2 depletion in granitic media: The REX project. SKB
high-level radioactive waste. Scientific Basis for Nuclear Waste Man- Technical Report, TR-0105, Stockholm, Sweden.
agement XXVII. pp. 805810. Kalmar; Sweden; 1519 June 2003. Qu, M.B., Bhattacharya, S.K., 1996. Degradation and toxic effects of
McKinley, I.G., Grogan, H.A., 1991. Consideration of microbiology in acrylic acid on anaerobic systems. ASCE Journal of Environmental
modelling the near-field of a L/ILW repository. Experientia 47 (6), Engineering 122 (8), 749756.
573577. Rivas-Prez, J., Banwart, S., 1998. Redox experiment in detailed scale
McKinley, I.G., Hagenlocher, I., Alexander, W.R., Schwyn, B., 1997. (REX). Task 5.1. Laboratory investigations. SKB Technical
Microbiology in nuclear waste disposal: interfaces and reaction Report, PR-HRL-9815, Stockholm, Sweden.
fronts. FEMS Microbiology Reviews 20 (3), 545556. Samper, J., Yang, C., 2006. Stochastic analysis of transport and
Molinero, J., Samper, J., 2004. Groundwater flow and solute transport multicomponent competitive monovalent cation exchange in
in fracture zones: an improved model for a large-scale field aquifers. Geosphere 2, 102112 (April).
experiment at sp (Sweden). Journal of Hydraulic Research 42, Samper, J., Juncosa, R., Delgado, J., Montenegro, L., 2000. CORE2D:
157172 2004, Extra Issue. A code for non-isothermal water flow and reactive solute transport.
Molinero, J., Samper, J., 2006. Modeling of reactive solute transport Users manual version 2. ENRESA Technical Publication 06/2000.
in fracture zones of granitic bedrocks. Journal of Contaminant Samper, J., Molinero, J., Yang, C., Zhang, G., 2003. Redox Zone II.
Hydrology 82, 293318. coupled modeling of groundwater flow, solute transport, chemical
Molinero, J., Samper, J., Yang, C., Zhang, G., 2004. Biogeochemical reactions and microbial proceses in the sp Island. SKB
reactive transport model of the Redox zone experiment of the Technical Report, TR-0316, Stockholm, Sweden.
148 C. Yang et al. / Journal of Contaminant Hydrology 93 (2007) 130148

Samper, J., Zhang, G., Montenegro, L., 2006. Coupled microbial and Wang, Y.F., Papenguth, H.W., 2001. Kinetic modeling of microbially-
geochemical reactive transport models in porous media: formula- driven redox chemistry of radionuclides in subsurface environ-
tion and application to synthetic and in-situ experiments. Journal of ments: coupling transport, microbial metabolism and geochemis-
Iberian Geology 32 (2), 211217. try. Journal of Contaminant Hydrology 47 (24), 297309.
Sellin, P., Hedin, A., 2004. Interim process report for the safety assessment Wersin, P., Spahiu, K., Bruno, J., 1994. Time evolution of dissolved
SR-Can. SKB Technical Report, R-0433, Stockholm, Sweden. oxygen and redox conditions in a HLW repository. SKB Technical
Smith, L.H., Kitanidis, P.K., McCarty, P.L., 1997. Numerical modeling report TR-9402, Stockholm, Sweden.
and uncertainties in rate coefficients for methane utilization and Williamson, M.A., Rimstidt, J.D., 1994. The kinetics and electro-
TCE cometabolism by a methane-oxidizing mixed culture. Bio- chemical rate-determining step of aqueous pyrite oxidation. Geo-
technology and Bioengineering 53 (3), 320331. chimica et Cosmochimica Acta 58, 54435454.
Tebes-Stevens, C., Valocchi, A.J., van Briesen, J.M., Rittmann, B.E., Wolery, T.J., 1979. Calculation of chemical equilibrium between
1998. Multicomponent transport with coupled geochemical and aqueous solution and minerals: the EQ3/6 software package.
microbiological reactions: model description and example simula- Report UCRL-52658. Lawrence Livermore National Laboratory,
tions. Journal of Hydrology 209, 826. Livermore CA, U.S.A.
Trotignon, L., Michaud, V., Lartugye, J.E., Ambrosi, J.P., Eisenlohr, L., Yang, C., 2006. Conceptual and numerical coupled Thermal-Hydro-
Griffault, L., combarieu, M.D., Daumas, S., 2002. Laboratory Bio-Geochemical Models for three-dimensional porous and
simulation of an oxidizing perturbation in a deep granite environ- fractured media. Ph. D. Dissertation, University of La Corua,
ment. Geochimica et Cosmochimica Acta 66 (14), 25832601. Spain, 400 pp.
Vzquez, M.V., de Snchez, S.R., Calvo, E.J., Schiffrin, D.J., 1994. The Yang, C., Samper, J., Molinero, J., Bonilla, M., 2005. Modeling
electrochemical reduction of oxygen on polycrystalline copper in microbially-mediated consumption of oxygen trapped in voids of a
borax buffer. Journal of Electroanalytical Chemistry 374, 189197. potential repository after backfilling at sp site. VII Jornadas de
Vogelaar, J.C.T., Klapwijk, B., Temmink, H., van Lier, J.B., 2003. Kinetic Zona no Saturada, ZNS'05, pp. 289294. La Corua, Spain.
comparisons of mesophilic and thermophilic aerobic biomass. Journal Zhang, G., 2001. Nonisothermal hydrobiogeochemical models in
of Industrial Microbiology and Biotechnology 30 (2), 8188. porous media. Ph. D. dissertation, University of La Corua, Spain
Wang, Y.F., Francisb, A.J., 2005. Evaluation of microbial activity for 324 pp.
long-term performance assessments of deep geologic nuclear Zhang, G., Samper, J., 2001. Biohydrogeochemistry: a new face of
waste repositories. Journal of Nuclear and Radiochemical Sciences groundwater chemistry. Las Caras del Agua Subterrnea. Inter.
6 (1), 4350. Conf., Barcelona. Ed. IGME, vol. I, pp. 6369.

Das könnte Ihnen auch gefallen