Reactive Transport & Biodegradation Model (Part I)
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1 Projet no.: (STREP) SEDBARCAH SEDiment BioBARriers for Chlorinated Aliphati Hydroarbons in ground water reahing surfae water Reative Transport & Biodegradation Model (Part I) Harald Kalka Short Leture at the Meeting Wageningen, January 006 Start date of projet: 01/01/005 Lead ontrator for Work Pakage 5 (Modeling): Duration: years UIT GmbH Dresden
2 Reative Transport and CAH-Biodegradation Model SEDBARCAH 1 Basi Equations Transport Phenomena 3 Enzyme Kinetis 4 Model Parameters 5 Software Presentation / Examples H. Kalka, UIT Gmbh Dresden, Germany Wageningen / January 006
3 Main Proesses Advetion Dispersion Sorption Enzyme Kinetis Population Dynamis Wageningen / January Thermodynamis CO- Equilibrium ph, ORP Transport Biodegradation Geohemistry Multi-Layer Model (Compartment Model) redutive dehlorination obi oxidation PhreeqC Mass & Charge onservation
4 Multi-Layer Model (Compartments) Layer A Layer B Layer C inflow F(t) Transport & Reations along a flow line 1 Model for Tasks Column Experiments Field-Sale Appliations Zenne Site Bath Reations (only kinetis) Pelhrimov Site Wageningen / January
5 Basi Equation (ADR) multi-speies model i CAH s, Cl -, DOC, O, CO... R t i v i x D L x i Φ bio ( i, j ) sorption advetion dispersion biodegradation Set of Partial Differential Equations (PDE) PCE TCE TCE DCE Wageningen / January
6 Operator Splitting t Φ Φ Φ adv Φ disp Φ bio n n1 n 1/ 3 n / 3 n 3/ 3 ~ Φ ~ Φ ~ Φ adv disp bio ( ( ( n, t) n 1/ 3 n / 3, t), t) FD method m intermediate steps k intermediate steps t / m t / k Runge-Kutta for ODE Wageningen / January
7 Cell size & Time step Layer A Layer B Layer C N A ells N B ells N C ells Vpore onst εaa x A εba x B... x L L N L L flow: pore veloity: V Q t Q vl ε A L pore x t onst L t V Q pore AεL x Q L onst Wageningen / January
8 Wageningen / January Analytial Solution x D x v t L λ 4Dt w) x(v erf D w) x(v exp 4Dt w) x(v erf D w) x(v exp t) (x, 0 λ D 4 v w π x ) t ( exp x erf 0 t, x for 0 0 t 0, x for 0 x 0, t for 0 0 > > >
9 Numerial Test N 40 ells v 9.8 mm/h t.56 h L 1 m 0 mm onentration [mm],1,0 1,9 1,8 1,7 α L 5 mm α L 50 mm 1,6 1,5 λ 0 λ 0 1,4 1,3 1, 1,1 1,0 0,9 α L 50 mm 0,8 0,7 λ 5 h -1 0,6 0,5 0,4 0,3 0, 0,1 0, Model versus Analytial Solution time [h] Wageningen / January
10 Degradation Pathways PCE Cl - TCE Cl - redutive dehlorination (erobi) DCE Cl - CO Cl - VC Cl - obi oxidation CO Cl - CO ETH Wageningen / January
11 Eletron Transfer e-donor e-aeptor DCE VC Cl - Mirobe e - ½CH O ½ CO O Mirobe H O 4e - ½DCE CO Cl - redutive dehlorination obi oxidation Wageningen / January
12 Eletron Balane CHCl CH O HO CO 4H 4e CHCl H e CHCl CH Cl DCE Corg H O VC CO H Cl erobi obi CHCl CHCl 4H O CO 10H 8e Cl O 4H 4e H O DCE O CO H Cl Wageningen / January
13 Biodegradation ODE (part I) d [PCE] Λ d [TCE] Λ P d [DCE] Λ d [VC] d [ETH] Λ Λ P T T T D D V V E Λ Λ Λ Λ T D D V V E E C Λ Λ D C V C d [CAH] abbreviations: Λ Λ Λ Λ P T D C Λ Λ T D V C ( Λ Λ ) Λ Λ V E D V are E C V C Λ V E Wageningen / January
14 Biodegradation ODE (part II) d [Cl d [C org d [O ] d [CO ] ] Λ y Corg Λ Λ D C Λ V C 5 Λ D C Λ V C 3 ] yco Λ Λ Λ E C for CH O as C org y Corg y CO stoihiometri oeffiients CO ΗCO HCO 3 - d [H ] d [Cl ] ( CO equilibiurm ) PhreeqC Wageningen / January
15 Population Dynamis biomass populations dx dx Y Y Λ Λ k k d d X X stationarity yield oeffiient death rate dx 0 Wageningen / January
16 Environmental Fators Temperature (ARRHENIUS behavior) ph miroorgs prefer ph ORP Moisture Content but: prodution of org. aids, HCl ( erobi / obi ) Nutrients C:N:P 10:10:1 Inhibiting or Toxi Compounds Wageningen / January
17 Enzyme Kinetis (part I) transition rates Λ Λ biomass i j i j X f i j (CAH) f temperature dependene (C org ) f 3 (T) f 4 (ph) F X fi j(cah) f (O) f3(t) f4(ph) ph dependene inh MICHAELIS-MENTEN and HALDANE f () [] K [] F inh K inh K inh [O non-ompetitive inhibition ] Wageningen / January
18 MICHAELIS-MENTEN Kinetis E S k k ES k E P steady state E S ES E P d[p] v K max S [S] [S] v max d[p]/ ½v max K S k k k [ E0 ] [E] [ES] vmax k[e0] K S [S] Wageningen / January
19 Enzyme Inhibition E H EH ompetitive inhibition v K I [S] [S] I 1 [H] K max 1 S 1 1 E S ESS self-inhibition (HALDANE) v K [S] I 1 [S] K max S [S]I E S G ESG non-ompetitive inhibition v K [S] 1 I [G] I 1 max 3 S [S] 3 K3 Wageningen / January
20 Enzyme Kinetis (part II) k i v (i) max / X CAH speies f i j K I i i k i[i] [i] [i] / K H i many kineti parameters! I i ompetitive inhibition 1 j i [j] K inh ij assumption: self-inhibition (HALDANE) K inh ij K j Wageningen / January
21 Software (1st version 0.40) User Interfae fast C ode inl. PhreeqC high flexibility Online Visualization Data Interpretation Wageningen / January
22 High Flexibility number of layers (ompartments) number of ells per layer number of hemial elements (PhreeqC) number of inflow ompositions unlimited unlimited unlimited unlimited Clearly arranged Input / Output struture Stop-and-Go (alulation with interrupts) Open for future extensions Wageningen / January
23 Input Data (part I) time-step wih t h ell number Ν end time T h ell length x m ross setion area A m porosity ε number of layers N L dispersity α L m inflow solution inp.sol bulk density ρ b g/m 3 Global Data org. arbon ontentent biomass for t0 f o X µg/l Data for eah Layer biomass for t0 initial solution fot t0 X µg/l file: ell.sol Wageningen / January
24 Input Data (part II) temperature temp C ph-value ORP PCE TCE CAH s is-dce VC ETH C org (dissolved organi arbon) ph pe mm mm mm mm mm mm Aqueous Solution Data DIC (dissolved inorgani arbon) mm Cl mm DO (dissolved oxygen) mm file: ell.sol other anions: S(VI), S(-II), N(V),... mm file: inp.sol other ations: Ca, Mg, Na, N(-III),... mm Wageningen / January
25 Input Data (part III) obi erobi max. speifi dehlor. rate half-veloity oeffiient HALDANE oeffiint max. speifi oxid. rate half-veloity oeffiient HALDANE oeffiint O inhibition K inh k i K i K Hi k i K i K Hi µm µmol/µg/d µmol/µg/d µmol/µg/d µmol/µg/d µmol/µg/d µmol/µg/d PCE TCE TCE DCE DCE VC VC ETH DCE CO VC CO ETH CO C org half-veloity oeffiient K Corg µm Population Dynamis yield Y, Y µg/µmol 7 Kineti Parameters death rate k d, k d d 1 Wageningen / January
26 Example Calulations A B C D E F pure advetion advetion dispersion biodegradation with onstant inflow biodegradation with time-dependent inflow biodegradation with population dynamis... other examples Software Presentation Wageningen / January
27 Kineti Parameter Set (Example) erobi k i µmol/mgp/d K i µm K Hi µm λ k i X/ K i d -1 PCE TCE TCE DCE DCE VC VC ETH X mgp/l 30 Y mgp/µm Cl k death d data: Yu & Semprini 004 Data in literature varies strongly! Wageningen / January
28 Demo (3 Example Configurations) onst inflow onst inflow t 0: t 0: 1 Layer (40 ells) A without CAH 3 Layers A B C without with CAH without A B C no X with X no X Wageningen / January
29 Open Questions e - donor C org : CH O, CH 4 or other? fration of DOC? population dynamis: stationarity? obi oxidation? role of other oxidants (NO3 et.)?... and many other questions Wageningen / January
30 WP5 - Next Steps PC-Program end version D11 Model / Software desription Feb month UIT Simulation Column Tests Simulation Zenne & Pelhrimov sites WP1, WP, WP3 ode updating 3 month Statistial Modelling (AUA) WP6 Guidlines Wageningen / January
31 More Info: SEDBARCAH projet Deliverable D11 End of presentation. Wageningen / January
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