Biodegradation of CAHs in River Sediments

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