CAH-Modeling & Batch & Column Tests (Part III)
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1 Project no.: (STREP) SEDBARCAH SEDiment BioBARriers for Chlorinated Aliphatic Hydrocarbons in ground water reaching surface water CAH-Modeling & Batch & Column Tests (Part III) Harald Kalka Short Lecture at the Meeting Leuven, January 2007 Start date of project: 01/01/2005 Lead contractor for Work Package 5 (Modeling): Duration: 2 years UIT GmbH Dresden
2 CAH-Modeling SEDBARCAH 1 Basic Idea 2 DCE & VC degradation 3 The Complete Chain 4 Column Tests 5 Conclusions & Outlook January 2007
3 The D13 Puzzle A huge number of experiments. About 30 model parameters Calculations
4 Main Question Does exist ONE parameter set for all problems? Batch Test Zenne Site Culture Bela Site Columns In-situ
5 Basic Idea PCE TCE rate = X(t) λ DCE VC population dynamics enzyme kinetics ETH Factorization Ansatz
6 Enzyme Kinetics specific rate λ i j = K i k [i 1] [i + 1] [i] 1 + Ki 1 Ki+ 1 i [i] K ii saturation self-inhibition 3 4 Parameters
7 Kinetic Parameter Set PCE k i µmol/µg/d 0.06 K i µm 1.6 K ii µm 0 pure culture TCE DCE VC batch & column tests modified literature data
8 Zenne / DCE degradation FAST MID SLOW xslow all data bundled into 4 groups initial population X 0 µg/l pore water fitted parameter 0,014 0,012 0,010 0,008 0,006 0,004 0,002 0,000 0,014 0,012 0,010 0,008 0,006 0,004 0,002 0,000 FAST DCE - model VC - model ETH - model DCE - fact VC - fact ETH - fact MID DCE - model VC - model ETH - model DCE - fact VC - fact ETH - fact
9 Variation of X 0 0,0040 DCE 0,0035 0,0030 0,0025 0,0020 0,0015 0,0010 0,0005 0,0000 FAST MID SLOW XSLOW initial biomass in µg/l
10 CAH-Modeling Population Dynamics Zenne DCE January 2007
11 Bacterial Growth Individual Cell (Cell Growth) Increase in Cellular Mass and Size Populations of Cells Increase in Total Number of Cells X Difficult to Measure Lag Exp Stationary Death t
12 Population Growth for various X 0 dx dt yield = population density [µg/l pore water] R YΩ ΓX 0 X = X(t) Var_FAST Var_MID Var_SLOW Var_XSLOW death rate Zenne DCE
13 CAH-Modeling BATCH TEST VC and DCE degradation January 2007
14 Zenne / VC Degradation 0,045 0,040 XXFAST 0,040 XFAST 0 = X 0 = ,045 0,035 0,035 0,030 0,025 0,020 0,015 0,010 PCE - model TCE - model DCE - model VC - model ETH - model VC_1 - fact VC_2 - fact VC_3 - fact VC - fact ETH 0,030 0,025 0,020 0,015 0,010 PCE - model TCE - model DCE - model VC - model ETH - model VC_1 - fact VC_2 - fact VC_3 - fact VC - fact ETH 0,005 0,005 0,000 0, ,045 0,045 0,040 XXFAST 0,040 XFAST 0 = X 0 = 700 0,035 0,035 0,030 0,025 0,020 0,015 0,010 PCE - model TCE - model DCE - model VC - model ETH - model VC_1 - fact VC_2 - fact VC_3 - fact VC - fact ETH 0,030 0,025 0,020 0,015 0,010 PCE - model TCE - model DCE - model VC - model ETH - model VC_1 - fact VC_2 - fact VC_3 - fact VC - fact ETH 0,005 0,005 0,000 0,
15 Bela Site DCE degradation in sediment MP1 0,012 0,011 0,010 0,009 0,008 0,007 0,006 0,005 0,004 0,003 0,002 0,001 0,000 0,090 0,080 0,070 0,060 0,050 0,040 0,030 0,020 0,010 DCE 1 ppm DCE - model VC - model ETH - model DCE - fact 20 VC - fact DCE - model DCE 10 ppm VC - model ETH - model DCE - fact 12 DCE - fact 20 X 0 = 100 µg/l 0,000 0,280 0,260 0,240 0,220 0,200 0,180 0,160 0,140 0,120 0,100 0,080 0,060 0,040 0,020 0, DCE - model VC - model DCE 50 ppm ETH - model DCE - fact 12 DCE - fact
16 CAH-Modeling BATCH TEST The complete degradation chain January 2007
17 PCE Degradation PCE What is new? strain A TCE DCE 1 2 Strong Adsorption Two Strains VC strain B ETH
18 Bela Site PCE degradation in sediment MP1 X 0 = µg/l 0,018 0,016 0,014 0,012 0,010 0,008 0,006 0,004 0,002 0,000 0,060 0,055 0,050 0,045 0,040 0,035 0,030 0,025 0,020 0,015 0,010 0,005 0,000 0,120 0,110 0,100 0,090 0,080 0,070 0,060 0,050 0,040 0,030 0,020 0,010 0,000 PCE 1 ppm 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 PCE 10 ppm 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 PCE 50 ppm 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
19 Ignoring Adsorption 0,18 0,16 PCE 220 µm Mass Balance Violation? mass [µmol] R 0,14 0,12 0,10 0,08 0,06 0,04 0,02 0, PCE - model TCE - model DCE - model VC - model ETH - model ETH_bulk VC_bulk DCE_bulk TCE_bulk PCE_bulk
20 Mass Balance for PCE Degradation m i = const PCE adsorbed mass [µmol] R mass [µmol] R ads pore dissolved CAH_ads CAH_pore CAH_bulk PCE 220 µm CAH_ads ETH_bulk VC_bulk PCE 220 µm DCE_bulk TCE_bulk PCE_bulk ETH_pore VC_pore DCE_pore TCE_pore PCE_pore
21 Autoclaved Sediment A: B: 100 X 0 in µg/l groundwater 1 10 HW surface water SW 0,10 0,09 0,08 0,07 0,06 0,05 0,04 0,03 0,02 0,01 0,00 DCE 10 ppm DCE - model HW DCE - model SW DCE - fact HW DCE - fact SW ,009 0,008 0,007 0,006 0,005 0,004 0,003 0,002 0,001 0,000 PCE 1 ppm / HW PCE - model TCE - model DCE - model VC - model PCE - fact TCE - fact DCE - fact ,009 PCE - model 0,008 PCE 1 ppm / SW TCE - model DCE - model 0,007 VC - model PCE - fact 0,006 TCE - fact 0,005 DCE - fact 0,004 0,003 0,002 0,001 0,
22 Bela / Aquifer Material 0,26 0,24 0,22 0,20 0,18 0,16 0,14 0,12 0,10 0,08 0,06 0,04 0,02 0,00 0,26 0,24 0,22 0,20 0,18 0,16 0,14 0,12 0,10 0,08 0,06 0,04 0,02 0,00 HW2 / HW3 PCE - model 0,20 X 0 = TCE - model X 0 = DCE - model PCE - HW3 12 TCE - HW3 12 DCE - HW3 12 PCE - HW2 20 TCE - HW2 20 DCE - HW PCE - model HW3 - CS 0,16 X 0 = TCE - model X 0 = 700 DCE - model PCE - fact TCE - fact DCE - fact ,22 0,18 0,16 0,14 0,12 0,10 0,08 0,06 0,04 0,02 0,00 0,10 0,08 0,06 0,04 0,02 0,00 HW4 / HW4-N PCE - model TCE - model DCE - model PCE - HW4 20 TCE - HW4 20 DCE - HW4 20 PCE - H4N 20 TCE - H4N 20 DCE - H4N ,18 HW4 - BI PCE - model TCE - model 0,14 DCE - model PCE - fact 0,12 TCE - fact DCE - fact
23 Bela / Aquifer Material 0,26 0,24 0,22 0,20 0,18 0,16 0,14 0,12 0,10 0,08 0,06 0,04 0,02 0,00 with adsorption PCE model: HW2 / HW3 model: HW4 / HW4-N without adsorption X 0 (aquifer) << X 0 (sediment)
24 CAH-Modeling COLUMN TEST Overview January 2007
25 Geometry and Material Parameters parameter symbol unit Zenne Bela column length L cm cell length x cm cell number N = L/ x inner diameter d cm cross section A = πd 2 /4 cm porosity ε m 3 /m cell volume V cm pore volume V pore = ε V cm flow rate Q ml/d time step (advect.) t = V pore /Q h time step (kinetic) t kin h sediment density ρ dry g/cm dispersivity α cm org. matter content f OC g/g
26 Zenne / Sediment Columns 0,024 0,022 0,020 0,018 0,016 0,014 0,012 0,010 0,008 0,006 0,004 0,002 0,000 DCE - model VC - model ETH - model ETH - fact VC - fact DCE - fact Port 135 mm Port 135 mm Q = 15 ml/d Q = 30 ml/d
27 Zenne / Sediment Columns concentration [mm] 0,032 0,028 0,024 0,020 0,016 0,012 0,008 0,004 0,000 Profile Oct 2006 / Oct 06 ETH 0,0 0,1 0,2 0,3 0,4 0,5 0,6 0,7 0,8 0,9 1,0 1,1 distance [m] distance [m] DCE - model VC - model ETH - model DCE - fact VC - fact ETH - fact mass balance? Profile
28 Bela / Sediment Columns 0,030 0,027 Sediment Port 500 / port mm 500 mm 0,024 0,021 0,018 0,015 0,012 0,009 0,006 0,003 0,000 PCE - model TCE - model DCE - model VC - model ETH - model PCE - fact TCE - fact DCE - fact VC - fact ETH - fact steady state
29 Bela / Sediment Columns concentration [mm] 0,030 0,027 0,024 0,021 0,018 0,015 0,012 0,009 0,006 0,003 0,000 Profile after / after ,00 0,05 0,10 0,15 0,20 0,25 0,30 0,35 0,40 0,45 0,50 0,55 distance [m] distance [m] DCE - model VC - model ETH - model ETH - fact VC - fact DCE - fact Profile
30 Two-Strain Model Population Dynamics dx dt dx dt (A) (B) = = YΩ YΩ A B ΓX ΓX (A) (B) batch columns Y = 18 µg/µm Y = 10 µg/µm Γ = day -1
31 CAH-Modeling CALCULATING CFU s January 2007
32 Number of Cells per gram dry Soil [cfu/g] n cell = 1 m cell ε ρ dry X biomass per Liter pore water [µg/l] Bacteria cell µm mcell = 1.2 g / cm 2.5 µm = 3 10 µ g
33 Microbial Diversity Model X = 0.01 µg/l 1 cfu / g X = µg/l cfu / g 1 strain subsurface species culturable: cells/g (total: cells/g)
34 Model Results: CFU/g post 26 bottom post 25 top Zenne DCE VC ETH aquifer sediment Bela initial population autoclaved SW autoclaved HW PCE TCE DCE aquifer HW4 aquifer HW2 sediment
35 CAH-Modeling PROGRAM CAPABILITIES January 2007
36 Between-the-Discipline Model Advection Dispersion Sorption Enzyme Kinetics Population Dynamics Thermodynamics CO 2 -Equilibrium ph, ORP Transport Biodegradation Geochemistry Multi-Layer Model (Compartment Model) reductive dechlorination aerobic oxidation PhreeqC Mass & Charge conservation
37 Two Options of the CAH-Model Layer A Layer B Layer C inflow = F(t) Reactive 1D-Transport Bulk Water Batch Test (Kinetics only) Sediment (Pore Water)
38 Dynamical-Model Capabilities Population Dynamics D12 D13 X Now used Enzyme Kinetics Anaerobic Pathway Aerobic Pathway T-Dependence ph-dependence Nutrient Limitation X X Transport O2-competition Advection + Dispersion Time-Dependent Inflow Multi-Layer Heterogeneous Populations X Finally used PHREEQC Complete Analyses Open CO2-System Phase Equilibrium Ion-Exchange Total Program Capability
39 CAH-Modeling MODEL LIMITATION Upper Bound for X January 2007
40 Complete Degradation Chain (Symbiosis) DOC Fermentation CAH Numerical Model Lactat Acetat Reductive Dechlorination Cl - CO 2
41 Problem Solving (provisional) to prevent unlimited population growth to simulate limited e-donor supply extra parameter X max unaesthetic!... line 5345 line 5346 Source Code if ( x > xmax ) x = xmax line 5348 line
42 CAH-Modeling SUMMARY and Conclusions January 2007
43 Conclusions Part I 1 Environmental Microbiology is highly complex (more than pure culture media) 2 Our approach is only a first step towards a Quanitative Microbiology 3 ONE kinetic dataset exist for batch/column tests from Zenne and Bela sites (but not unique due to unknown X 0 )
44 Batch Reaction Data Zenne site Bela site Initial Bulk Water Initial Pore Water Adsorption Sediment Water Bacteria Strain A Bacteria Strain B Batch Test PCE TCE DCE VC ETH PCE TCE DCE VC f_oc rho porosity m_sed V_bulk X_0 X_max X_0 X_max µm µm µm µm µm µm µm µm µm % g/cm³ m³/m³ g ml µg/l µg/l µg/l µg/l DCE_FAST 3,6 8 1,5 3,6 8 0,7 1,62 0, DCE_MID 3,6 8 1,5 3,6 8 0,7 1,62 0, DCE_SLOW 3,6 8 1,5 3,6 8 0,7 1,62 0, , DCE_XSLOW 3,6 8 1,5 3,6 8 0,7 1,62 0, , VC_XFAST ,7 1,62 0, VC_ FAST ,7 1,62 0, VC_MID ,7 1,62 0, VC_LOW ,7 1,62 0, DCE_1 10,3 5 1,3 1,23 0, DCE_10 103,2 5 1,3 1,23 0, DCE_ ,3 1,23 0, PCE_ ,3 1,23 0, PCE_10 60,3 3 1,3 1,23 0, PCE_ ,3 1,23 0, DCE_HW 103 0,4 1,23 0, DCE_SW 103 0,4 1,23 0, PCE_HW 12 0,4 1,23 0, PCE_SW 12 0,4 1,23 0, , HW ,14 0, , HW3_CS ,14 0, , HW ,3 1,14 0, , HW4_BI ,3 1,14 0, ,
45 Conclusions Part II 4 Population is time-dependent (non-constant); at least two strains for complete CAH-degradation 5 Deduced CFU s are in accord with other estimations OUTLOOK - Future Model Extensions: Symbiosis of fermentative and respirative bacteria Calculation of δ 13 C data (for isotopic analysis)
46 Modeling in WP5 1 Model for 3 Tasks Batch tests kinetic data Column tests transport data Field sites Statistical Modeling Dynamical Modeling Guidelines WP6
47 SEDBARCAH Computer Program User Interface fast C++ code incl. PhreeqC high flexibility Output Online Visualization
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