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UMWELTLEISTUNGEN UIT Nov 2007
Biodegradation of CAHs in River Sediments
The European Project1
The Model2
3 Model Parameters
4 Model vs. Reality
5 Results & Conclusions
SEDB
ARCA
HHarald Kalka, UIT GmbH Dresden
XVIII. Sächsisches Altlastenkolloquium, Dresden
UMWELTLEISTUNGEN UIT Nov 2007
EU Projekt: SEDBARCAH (2005-2007)
VITO (Mol, B) W. Dejonghe *)K. Hamonts, L. Diels
sampling, microbiologybatch and column tests
KUL (Leuven, B) J. Dyck, D. Springael microbiology
WU (Wageningen, NL) M. Sturme, H. Smidt microbiology
Aquatest (Prague, CZ) J. Kuklik, P. Kozubek sampling, analytics
GSF (München, D) T. Kuhn, R. Meckenstock isotope fractionation
AUA (Jena, D) J. Perner, L. Eckart data interpretation, guidelines
C&E (Chemnitz, D) T. Lange, A. Rieger, A. Forbrig batch and column tests
UIT (Dresden, D) H. Kalka, H. Märten modeling, monitoring
*) project manager
UMWELTLEISTUNGEN UIT Nov 2007
Sediment Biobarriers for CAHs
Reductive Dechlorination
CAHs
biodegradation in the sediment
River
Aquifer
UMWELTLEISTUNGEN UIT Nov 2007
Two CAH-Sites
Belá River
B
Zenne River
CZDC
E / V
C
PCE / TCE
UMWELTLEISTUNGEN UIT Nov 2007
Site Specific Data
Zenne Site
Batch Tests
Column Tests
Sampling VITO / C&
E
Model Simulation
UMWELTLEISTUNGEN UIT Nov 2007
Batch tests
Column tests
Field sites
kinetic data
transport data
Modeling Strategy1
Mod
el fo
r 3 T
asks
Dynamical Modeling Guidelines
UMWELTLEISTUNGEN UIT Nov 2007
SEDBARCAH
The Model
UMWELTLEISTUNGEN UIT Nov 2007
The CAH-Model for Column and Batch Testsin
flow
= F(
t)
Layer A Layer B Layer C
Reactive 1D-Transport
Bulk Water
Sediment (Pore Water)Batch Test(Kinetics only)
UMWELTLEISTUNGEN UIT Nov 2007
Degradation Pathways
2CO2
Cl-
aerobicoxidation
ETH
Cl-
Cl-
Cl-2CO2 + 2Cl-
2CO2 + Cl-
VC
reductive dechlorination
(anaerobic)TCE
DCE
PCE
UMWELTLEISTUNGEN UIT Nov 2007
Electron Transfer
DCE
Microbe
e-Do
nor
e-Ac
cept
or VC + Cl-
½ CH2O ½ CO2
2e-
O2
Microbe
2H2O
½ DCE CO2 + Cl-
4 e-
reductive dechlorination aerobic oxidation
UMWELTLEISTUNGEN UIT Nov 2007
Biodegradation – Part I
anaTPdt
]PCE[d
anaDT
anaTPdt
]TCE[d
aerCD
anaVD
anaDTdt
]DCE[d
aerCV
anaEV
anaVDdt
]VC[d
aerCE
anaEVdt
]ETH[d
aerCV
anaEVdt
]CAH[d
anaEV
anaVD
anaDT
anaTP
ana
areCE
aerCV
aerCD
aer
abbreviations:
UMWELTLEISTUNGEN UIT Nov 2007
Biodegradation – Part II
aerCV
aerCD
ana 2dt
]Cl[d
anaCorg
org ydt
]C[d
aerCE
aerCV2
5aerCD
2 32dt
]O[d
aerana2CO
2 2ydt
]CO[d
)mequilibiurCO(dt
]Cl[ddt
]H[d2
for CH2O as Corg
21
Corgy
21
2COy
stoichiometric coefficients
HCO3-
CO3-2
CO2
PhreeqC
UMWELTLEISTUNGEN UIT Nov 2007
population dynamics
Basic Idea
Factorization
)t(Xrate
enzymekinetics
PCE
TCE
DCE
VC
ETH
UMWELTLEISTUNGEN UIT Nov 2007
MICHAELIS-MENTEN 1913
PEESSE k
k
k
]S[K]S[v
dt]P[d
S
max
steady state
+ +
E S ES E P
UMWELTLEISTUNGEN UIT Nov 2007
Enzyme Kinetics – Inhibition
+
E
H
EH
+
E
2S
ESS
+
E
S ESG
+
G
]S[IK]S[v
1S
max
11 K
]H[1I
2S
max
I]S[K]S[v
22 K
]S[1I
3S
max
I1
]S[K]S[v
33 K
]G[1I
competitive inhibition
self-inhibition(HALDANE)
non-competitive inhibition
UMWELTLEISTUNGEN UIT Nov 2007
Enzyme Kinetics
3 × 4 Parameters
ii1i1ii
iji
K]i[1]i[
K]1i[
K]1i[1K
k
saturation self-inhibition
specific rate
UMWELTLEISTUNGEN UIT Nov 2007
Population Dynamics
)A(A
)A(
XYdt
dX
)B(B
)B(
XYdt
dX
Y = 18 µg/µMΓ = 0.005 day-1
Two
Stra
ins
X0(A) , X0
(B) Initial Condition Free Parameters
UMWELTLEISTUNGEN UIT Nov 2007
SEDBARCAH Computer Program
Online Visualization
User Interface
Output
fast C++ code incl. PhreeqC high flexibility
UMWELTLEISTUNGEN UIT Nov 2007 - 19 -
Example Configurations
1 Layer (40 cells)
without CAH
constinflow
with Xana
A B C
without with CAH without
A B C
t = 0:
A
t = 0:
constinflow
3 Layers
no Xana no Xana
UMWELTLEISTUNGEN UIT Nov 2007
SEDBARCAH
Model Parameters
UMWELTLEISTUNGEN UIT Nov 2007
Main Question
ONE parameter set for all problems
Bela Site
Zenne Site
Columns
Batch Test?
Culture
In-situ
UMWELTLEISTUNGEN UIT Nov 2007
The Kinetic-Parameter Set
modified literature data
ki Ki Ki i
µmol/µg/d µM µM
PCE 0.06 1.6 0
TCE 0.60 1.8 900
DCE 0.07 1.8 750
VC 0.008 5 750
pureculture
batch & column tests
UMWELTLEISTUNGEN UIT Nov 2007
SEDBARCAH
Modell vs. Reality
(about 100 batchand column tests)
UMWELTLEISTUNGEN UIT Nov 2007
Batch Zenne / VC Degradation
0,000
0,005
0,010
0,015
0,020
0,025
0,030
0,035
0,040
0,045
0 2 4 6 8 10 12 14 16 18 20 22 24 26 28 30 32 34 36days
conc
entra
tion
[mM
] R PCE - model TCE - model DCE - model VC - model ETH - model VC_1 - fact VC_2 - fact VC_3 - fact VC - factETH
XFAST
0,000
0,005
0,010
0,015
0,020
0,025
0,030
0,035
0,040
0,045
0 2 4 6 8 10 12 14 16 18 20 22 24 26 28 30 32 34 36days
conc
entra
tion
[mM
] R PCE - model TCE - model DCE - model VC - model ETH - model VC_1 - fact VC_2 - fact VC_3 - fact VC - factETH
XFAST
0,000
0,005
0,010
0,015
0,020
0,025
0,030
0,035
0,040
0,045
0 2 4 6 8 10 12 14 16 18 20 22 24 26 28 30 32 34 36days
conc
entra
tion
[mM
] R PCE - model TCE - model DCE - model VC - model ETH - model VC_1 - fact VC_2 - fact VC_3 - fact VC - factETH
XFAST
0,000
0,005
0,010
0,015
0,020
0,025
0,030
0,035
0,040
0,045
0 2 4 6 8 10 12 14 16 18 20 22 24 26 28 30 32 34 36days
conc
entra
tion
[mM
] R PCE - model TCE - model DCE - model VC - model ETH - model VC_1 - fact VC_2 - fact VC_3 - fact VC - factETH
XFAST
X0 = 3 000 X0 = 2 400
X0 = 1 400 X0 = 700
UMWELTLEISTUNGEN UIT Nov 2007
Batch Zenne / DCE degradation
0,000
0,002
0,004
0,006
0,008
0,010
0,012
0,014
0 2 4 6 8 10 12 14 16 18 20 22 24 26 28 30 32 34 36 38 40 42 44 46 48 50
conc
entra
tion
[mM
] R
DCE - model VC - model ETH - model DCE - fact VC - fact ETH - fact
FAST
0,000
0,002
0,004
0,006
0,008
0,010
0,012
0,014
0 2 4 6 8 10 12 14 16 18 20 22 24 26 28 30 32 34 36 38 40 42 44 46 48 50days
conc
entra
tion
[mM
] R
DCE - model VC - model ETH - model DCE - fact VC - fact ETH - fact
MID
UMWELTLEISTUNGEN UIT Nov 2007
Bela Site
PCE degradationin sediment MP1
X0 = 2 000 µg/L
0,000
0,002
0,004
0,006
0,008
0,010
0,012
0,014
0,016
0,018
0 2 4 6 8 10 12 14 16 18 20 22 24 26 28 30days
conc
entra
tion
[mM
] R
PCE - model TCE - model DCE - model VC - model DCE - fact 12 TCE - fact 12 PCE - fact 12 DCE - fact 20 TCE - fact 20 PCE - fact 20
PCE 1 ppm
0,0000,0050,0100,0150,0200,0250,0300,0350,0400,0450,0500,0550,060
0 2 4 6 8 10 12 14 16 18 20 22 24 26 28 30 32 34 36 38 40 42 44 46 48 50days
conc
entra
tion
[mM
] R
PCE - model TCE - model DCE - model VC - model DCE - fact 12 TCE - fact 12 PCE - fact 12 DCE - fact 20 TCE - fact 20 PCE - fact 20
PCE 10 ppm
0,0000,0100,0200,0300,0400,0500,0600,0700,0800,0900,1000,1100,120
0 2 4 6 8 10 12 14 16 18 20 22 24 26 28 30 32 34 36 38 40 42 44 46 48 50days
conc
entra
tion
[mM
] R PCE - model TCE - model DCE - model VC - model DCE - fact 12 TCE - fact 12 PCE - fact 12 DCE - fact 20 TCE - fact 20 PCE - fact 20
PCE 50 ppm
UMWELTLEISTUNGEN UIT Nov 2007
Strong Adsorption 1
PCE vs. DCE Degradation
stra
in “A
”
What is new ?
PCE
TCE
DCE
VC
ETH
strain “B”Two Strains 2
UMWELTLEISTUNGEN UIT Nov 2007
PCE/TCE Adsorption
Mass BalanceViolation ??
0,00
0,02
0,04
0,06
0,08
0,10
0,12
0,14
0,16
0,18
0 2 4 6 8 10 12 14 16 18 20 22 24 26 28 30 32 34 36 38 40 42 44 46 48 50days
conc
entra
tion
[mM
] R
PCE - model TCE - model DCE - model VC - model ETH - model
PCE 220 µM
02468
1012141618202224
0 3 6 9 12 15 18 21 24 27 30 33 36 39 42 45 48
days
mas
s [µ
mol
] R
ETH_bulk VC_bulk DCE_bulk TCE_bulk PCE_bulk
UMWELTLEISTUNGEN UIT Nov 2007
Mass Balance for PCE Degradation
02468
1012141618202224
0 3 6 9 12 15 18 21 24 27 30 33 36 39 42 45 48
daysm
ass
[µm
ol] R
CAH_ads CAH_pore CAH_bulk
PCE 220 µM
02468
1012141618202224
0 3 6 9 12 15 18 21 24 27 30 33 36 39 42 45 48
days
mas
s [µ
mol
] R
CAH_ads ETH_bulk VC_bulk DCE_bulk TCE_bulk PCE_bulk ETH_pore VC_pore DCE_pore TCE_pore PCE_pore
PCE 220 µM
constmi
PCE adsorbeddissolved
ads
pore
UMWELTLEISTUNGEN UIT Nov 2007
SEDBARCAH
Population Dynamics
UMWELTLEISTUNGEN UIT Nov 2007
Population Growth for various X0
XYdtdX
yield
death rate
0
400
800
1200
1600
2000
2400
2800
3200
3600
4000
0 4 8 12 16 20 24 28 32 36 40 44 48days
popu
latio
n de
nsity
[µg/
L po
re w
ater
] R
Var_FAST
Var_MID
Var_SLOW
Var_XSLOW
X = X(t)
Zenne
UMWELTLEISTUNGEN UIT Nov 2007
1 strain
Number of Cells per gram dry Soil [cfu/g]
Bacteria cell
Xm
1ndrycell
cell
1 .. 3 µm
ncell 5 10∙ 5 cfu / g
biomass per Literpore water [µg/L]
UMWELTLEISTUNGEN UIT Nov 2007
“Environmental Microbiology” is extraordinary complex (no pure cultures like in lab)
Conclusions
1
2
3
ONE kinetic dataset for ALL batch and column tests(only X0 acts as free parameter)
Population dynamics is strongly time-dependent; 2 bacterial strains for complete CAH degradation