Mathematical Modeling of

Pollutant Transport in Groundwater

Rajesh Srivastava
Department of Civil Engineering
IIT Kanpur
Outline of the Talk

•Sources
•Processes
•Modelling
•Applications
Sources of GW Pollution

•Irrigation
•Landfills
•Underground Storage tanks
•Industry
Advection
• Mass transport due to the flow of the water
• The direction and rate of transport coincide
with that of the groundwater flow.

Diffusion
• Mixing due to concentration gradients

Dispersion
• Mechanical mixing due to movement of
fluids through the pore space
 Dispersion

Velocity
• Spreading of mass due to
– Velocity differences
within pores Position in Pore

– Path differences due to the

tortuosity of the pore
network.
 Pore Spaces
Stagnant or
Mobile/ Immobile liquid Intra-particle pores
flowing
liquid
Gas

Figure: Courtesy Sylvie Bouffard, Biohydrometallurgy group, Vancouver 12 18

 Brief Chronology

Unsaturated flow equation by Richards (1931)

Coats and Smith (1964) proposed dead-end pores in oil wells
Equilibrium reactive transport theories proposed
Breakthrough curves with pronounced tailings observed
Non-equilibrium models developed
Goltz and Roberts (1986) physical non-equilibrium model
Brusseau et al. (1989) developed MPNE
Slow and Fast Transport model developed by Kartha (2008)
 Experimental Setup
INFLOW A OUTFLOW B
1 1
C/Co

C/Co
0 0
Time Time
Start Start

A B
 Conservation of Liquid Mass
   l  l  
  .   l ul    S l
t
where Sl is source/sink term.

Darcy velocity in unsaturated porous medium ul  K   l  hl
Pl
Hydraulic head based on elevation head z hl  z 
 l gˆ
k   l   l gˆ
Hydraulic conductivity K l  
l
 k
Darcy velocity ul    Pl   l gˆ 
l
Liquid pressure in unsaturated conditions Pl  Pg  Pc
Intrinsic permeability in unsaturated conditions k  klr ksat
 Brooks-Corey and van Genuchten Relations
•Relation between suction pressure, liquid pressure, and liquid saturation
•Relation between relative permeability and liquid saturation

Effective saturation is given as  le    l   r   1   r 

Gas pressure Pg is considered zero, therefore Pl   Pc

B.C. - Model V.G. Model

Suction
Pc  Pb le1   l g 1 
Pc  *   le  1 
 1 
pressure

Relative  3 2 
klr   le  1  (1   le 
  1/   2
Permeability klr   le  
)
• van Genuchten equations
l r 1
 le   
1r  1

 1   1

 


kr   le 1  1   1/
le  
 2
 0.5

0.45

0.4
Water Content

0.35

0.3

0.25

0.2
0.001 0.01 0.1 1 10

Suction (cm)
 1

0.1
Rel. Hyd. Cond.

0.01

0.001

0.0001
0.001 0.01 0.1 1 10
Suction
Transport Model
Reactive advective-dispersive equation
   l  l C 
  .   l ul C    .   l l D*C 

R
t

Here we use multi-process non-equilibrium equations.

MPNE model

Liquid exists in mobile and immobile phase.

Solid in contact with mobile and immobile liquid.
Instantaneous sorption mechanism between liquids and solids.
Rate-limited sorption mechanism between liquids and solids.
 MPNE Equations
 C m 
 l   l   im  Cm   f  l  b Fm K m   .   l ul Cm  
t t
 .   l    l   im  D*Cm    l  Cm  Cim   f b km  1  Fm  l K m Cm  Sm 2    S l C0

Where, Si - concentration of metal in sorbed phase (i.e. solid),

Ki - adsorption coefficient, ki - sorption rate,
α - mass transfer rate between mobile and immobile liquid,
Fi - fraction for instantaneous sorption,
f - fraction of sorption site in contact with mobile liquid.
S m 1 C m S m 2
  l Fm K m  km  1  Fm   l K m C m  S m 2 
t t t
S im 1 C im S im 2
  l Fim K im  kim   1  Fim   l K im C im  Sim 2 
t t t
C im S im 1 S im 2
 l  im   1  f  b   1  f  b   l  C m  Cim 
t t t
 Numerical Solution for Unsaturated Flow

The mass conservation equation is solved for liquid pressure

Implicit finite-difference method is used

 n 1, s  1

 l  l n1, s 1   l n  
 i , j ,k   S l  i , j ,k
i , j ,k
Residual form of Rli , j ,k 
t
conservation of mass
k  Pl n 1, s 1  Pl n 1, s 1  
equation for liquid
 l   q
b
   l gˆ  Aqi , j ,k  1
p qi , j ,k i , j ,k


q  l   xq i , j ,k  
   

Taylor’s series expansion of residual  dR n 1, s  

 n 1, s 1  n1, s 
   in, j,k1, s   P  n1, s 1
l
equation will lead to the following R R
q  dPl  lqi , j ,k
l i , j ,k l i , j ,k
form  qi , j ,k 

Pl
n1, s 1
 Pl
n1, s 
  Pl 
n 1, s 1 
Pressure values updated at each iteration step
i , j ,k i , j ,k i , j ,k
 Numerical Solution for MPNE Transport

Conservation of mass for metal is solved for concentration in liquid

Implicit finite-difference in time step used for formulations
Residual formulation obtained for concentration in mobile liquid
1
S m 2
n  1
The finite-difference formulation   S m n2  km t (1  Fm )  l K m C m n1 
for sorbed concentration is  1  k m t   

The residual formulation for solute concentration in mobile liquid is:


   S l C 0    l   l   im   f  l  b Fm K m 

C m   C m  
n 1 n
  
  C m n1  C m n1  
i , j ,k   l  d q ulq
 n  1
RCm   q i , j ,k
 Aq   1 
b

 t  q   xq  i , j ,k 
     
 n1 
  n  1 b
 
 
ACim
1

  l  ulq C mq Aqi , j ,k  1   l  C m   n1  l C m  ACim C im  ASim 2 S im 2   i , j ,k
 n  1  n  n  n  n
 
q
 
  n
 S im  k  t  1  F   K C  n  1  
 f  b km   1  Fm   l K m C m     
n1 2 im im l im im



 1  kim t   i , j ,k

 dRC n  
Taylor’s series expansion of the above residual equation RC  n  1
 RCm n
  m
 n
 C m n 1
q  dC m 
m

 
C m
n  1
 C m    C m
n 1
Updated Concentration is n
Verification of the Numerical Model
Inflow qt = 3 cm/d

FLOW
(Compared with
10 cm
VG’s Flow Model
and Kuo et al. (1989)

150 cm
Infiltration Model)

Water Table

ksat 5.905×10-9 cm2

ε 0.45
σr 0.22
α* 0.025 cm
λ 0.394
Δz 1 cm
Δt 100 s
MPNE Transport

30 cm

Input Parameters
ρb 1.360 g.cm-3 α 8.681×10-7 s-1

θ 0.473 km 7.673×10-4 s-1

q 5.914×10-4 cm.s-1 kim 7.673×10-4 s-1

dz 0.34 cm Km 0.429 cm3.g-1

L 30.0 cm Kim 0.416 cm3.g-1

T0 7.672 days (662861 s) f 0.929
Fm 0.5 Fim 0.5
 Concept of Slow and Fast Transport
Movement of liquids is heterogeneous
Liquid flow is conceptualized as slow and fast zones
Multiple sources of non-equilibrium solute interactions occurs between
solids and different liquids 4

I II III
Immobile αim Slow Liquid Fast Liquid
αsf
Liquid Csl and σsl Cfs and σfs
Cim and σim

Kim kim Ksl ksl

IV V VI VII

Rate – Rate-
Instant limited Instant
limited
Sorption Sorption Sorption
Sorption
Site, Site, Site,
Site,
Sim1 Sim2 Ssl1
Ssl2
 Conservation of solute mass
• Solute mass conservation in fast liquid

C fs
 l  fs
t


  .   l u fs C fs    .  fs D*f  l C fs    S fs C 0   l sf C fs  C sl 

• In slow liquid
C sl 
 l   sl  f  b  l Fsl K sl    .  l usl C sl  
t
 S sl C 0   l sf  C sl  C fs    l im  C sl  C im    .   l  sl Dsl* C sl 
 f  b k sl  1  Fsl   l K sl C sl  S sl 2 
Conservation of solute mass….

• Rate of change of instantaneously sorbed solute mass

S sl 1 C sl
  l Fsl K sl
t t

• Rate of change of rate-limited sorbed mass

S sl 2 Similar instantaneous and
 k sl  1  Fsl   l K sl C sl  S sl 2  rate-limited sorption exist
t
for immobile liquid

• Solute mass conservation in immobile liquid

C im
  l  im  (1  f )b  l Fim K im  t
  1  f   b kim  1  Fim   l K im C im  Sim 2 

  l  im  C sl  C im 
 FINITE-DIFFERENCE FORMULATION OF SFT MODEL
The implicit finite-difference form of metal mass conservation in fast moving liquid in a
FD cell is:
 C n  1
 C fsn  
 l fs
fs

t
i , j ,k

q

 l  u fsq C fsnq 1 Aqi , j ,k  1  
b

  
u fsq  C fsn  1  C fsn  1 
 l    fsq dq
q   fsq
 q
 x q
i , j ,k

 i ,j ,k 
 
 Aq  1     S fs C0  l  sf C fsn  1  Csl n  1
b
 i , j ,k

   

The implicit finite-difference form of metal mass conservation in slow moving liquid in a
FD cell is:
 C n  1
 C sl n  
 l sl  f l b Fsl K sl
sl

t
i , j ,k

     
 l  u slq C slnq 1 Aqi , j ,k   S slC 0   l sf C sln  1  C fsn  1   l im C sln  1  C imn  1
q
 i , j ,k

   C sl n  1  C sl n  1  
f  b ksl   1  Fsl   l K sl C sl
 n  1  n  1
 Ssl 2   i , j , k  l   d q u slq  q A 
i , j ,k

q   x q  qi , j ,k 
   

The implicit finite-difference form of metal mass conservation in immobile liquid in a FD

cell is:

 C n  1  n
 C im   1 f   k
l   im   1  f  b Fim Kim 
im

t
b im
 1  Fim   l K imC im

 n  1  n  1
 Sim   n 1
2    l im C sl
 n  1
 C im  
Formulations continued….

Residual equations are formed for the finite-difference equations

for conservation of metal mass in fast and slow moving liquids.

Residual equations expanded using Taylor’s series approximation.

dRC nfs 1,s 

RC nfs 1,s  1  RC nfs   n  1, s 
 C fsn  1,s  1
dC fs

dRC nsl 1,s 

RC nsl 1,s  1  RC nsl   n  1, s 
 C sl n  1,s  1 
dC sl

The linear system of equations is solved

Update concentration terms:

C fsn  1,s  1  C fsn  1,s    C fsn  1,s  1

C sl n  1,s  1  C sl n  1, s    C sl n  1,s  1

Numerical Model Validation…..
Verification and Evaluation (Brusseau et. al.,
1989)
Bulk density 1.36 g.cm-3
Porosity 0.473
Inflow rate 5.11 cm.d-1
Dispersivity 0.34 cm
Column height 30.0 cm
Immobile saturation 0.071
Sorption coefficient Ksl 0.429 cm3.g-1
Sorption coefficient Kim 0.416 cm3.g-1
Sorption rate 0.663 d-1
Mass transfer rate αim 0.075 d-1
Instantaneous sorption fraction 0.50
Pulse duration 7.67 d
Brusseau, M.L., Jessup, R.E., Rao, P.S.C.: Modeling the transport of solutes….. Water Resources
Research 25 (9), 1971 – 1988 (1989)
REMEDIATION OF GROUNDWATER POLLUTION
DUE TO CHROMIUM IN NAURIA KHERA AREA OF
KANPUR

Central Pollution Control Board Lucknow

National Geophysical Research Institute Hyderabad
Industrial Toxicology Research Centre Lucknow
Indian Institute of Technology Kanpur
 N R

0
2 6 .4 5 5

2 6 .4 5 N a u r iy a k h e r a
~ 5 km2

al
C an
2 6 .4 4 5

2 6 .4 4

Pan R oad
du
R iv
er R a il
2 6 .4 3 5

N G R I / C P C B / IT R C / IIT -K
0
8 0 .2 5 5 8 0 .2 6 8 0 .2 6 5 8 0 .2 7

Location map of Nauriyakhera IDA, Kanpur, U.P.

CGWB Observations in Kanpur 1994-2000

• Cr 6+ found in groundwater generally exceed > 0.11 mg/l

(Permissible Limit is 0.05 mg/l)

• Cr 6+ observed in Industrial areas in depth range of 15 – 40 m >10 mg/l

• Nauriakhera (Panki Thermal Power Plant Area) Cr 6+

14 m - 8.0 mg/l
15 m – 0.31 mg/l
35 m – 7.0 mg/l
40 m – 0.68 mg/l

• Used Chromite ore (Sodium Bichromate) dumped in pits and low lying areas
cause of Cr pollution

• Persistence in the phreatic zone up to 40 m depth despite presence of thick clay

zones
 N R
10 4
32 31 11
0
2 6 .4 5 5 9

3128
5
2 7 6 18
13
1 14
2 5 1 62 3 5 1
2 6 .4 5 24 26
N a
1 9 22 202 1 1 7
u r iy a k h e r a

al
C an
2 6 .4 4 5
28

30

27
2 6 .4 4

Pan R oad
du
R iv
er R a il
2 6 .4 3 5 O b s e r v a tio n W e ll

N G R I / C P C B / IT R C / IIT -K
0
8 0 .2 5 5 8 0 .2 6 8 0 .2 6 5 8 0 .2 7

Observation Wells in Nauriyakhera IDA, Kanpur, U.P.

 N R
0 .7 0 .7
0 .0 5 7 0 0
0
2 6 .4 5 5 0 .0 4

1 . 3 10 .044 . 45 7 4
4 .5 7 4
3 . 2 7 4 5 .57 .61 58 7 1 1 . 6 5
0 .8 3 5
0 .5 3 5 3 .7 4 3
0 . 4 8 7 0 0. 4 00 4
2 6 .4 5 0 0 .0 9 6
N au
0 . 00 00. 54. 480 3 0 . 4 7 8
r iy a k h e r a

al
C an
2 6 .4 4 5
0 .0 9

0 .2 5 5
2 6 .4 4

Pan
du
R iv
er March 2005
2 6 .4 3 5

N G R I / C P C B / IT R C / IIT -K
0
8 0 .2 5 5 8 0 .2 6 8 0 .2 6 5 8 0 .2 7

Total Chromium (mg/l) in groundwater - Nauriyakhera IDA, Kanpur

 N R

N a u r iy a k h e r a m g /l

10

al
C an
8

4
T - C r (m g /l)
Pan P ost M on soon
du
R iv 2004
er 2

N G R I / C P C B / IT R C / IIT -K
0

Total Chromium (mg/l) in groundwater -Nauriyakhera IDA, Kanpur

Fence Diagram – Nauriyakhera IDA, Kanpur
Total Chromium Plume from Source after 10 years
Total Chromium Plume from Source after 40 years
 Application to Heap Leaching

• Heap leaching is a simple, low-cost

method of recovering precious
metals from low-grade ores.
• Ore is stacked in heaps over an
impermeable leaching-pad.
• Leach liquid is irrigated at the top
• Liquid reacts with metal and
dissolves it.
• Dissolved metal collected at the
bottom in the leaching pad.
 Why Heap Leaching ?

• Traditional methods of gold extraction viz -

ore sieving, washing, etc. are obsolete and
uneconomical.
• Pyro-metallurgy is highly costly and non-
viable for low-grade ores.
• Leaching is the only process to extract metallic
content from the low-grade ores.
• Among leaching methods – Heap leaching is
most economical
Why we are interested in Heap Leaching?

• Heaps are generally stacked in unsaturated

conditions.
• The dissolution reaction occurs in the presence of
oxygen.
• The flow of liquid and metals inside the heaps are
governed by principles of flow and solute transport
through porous medium
• Solving unsaturated flow equations and reactive
transport equations enables us to model heap
leaching process.
 Mine Pit
ORE PREPARATION

Types of leaching
Sprinklers or wobblers

 Underground in-situ
leaching Heap
 Tank leaching Leach pad
 Heap leaching Recovery Plant

 Pressure leaching
Pregnant solution pond Barren Solution Pond

 Impermeable leach pad

Components of  Liners
a heap  Crushed metal ore
 Irrigation system
 Pregnant solution pond
 Barren solution pond
MPNE Model
Effluent outflow into the leaching pad

Average outflow Cumulative outflow

 The average outflow gradually attains steady state

 Sudden decrease in outflow on stoppage of irrigation
 Rate of recovery reduced after stoppage
MPNE Model

Sensitivity Analyses of MPNE parameters

o Sensitivity Analysis conducted to assess
influence of model input parameter on output.
o Parameters considered are – α, km and kim

Influence of α

Recovery curves
MPNE Model - Sensitivity Analyses.. Influence of km & kim

Higher
recovery
and higher
peaks for
cases
having
Breakthrough Curves Recovery Curves higher
sorption
rates
MPNE Model

Effect of variation in
irrigation

Recovery Curves

Outflow Curves

Higher recovery of metal at

slower irrigation rate
Breakthrough Curves
 Two Dimensional Heap Leaching by SFT method

1.5 m
SFT Parameters

ksl = 4.98×10-6 s-1 0.5 m

(σsl)max = 0.065
αsf = 2.875×10-7 s-1

Grid Spacing 2.5 m

 Horizontal Direction = 1.72 cm
 Vertical Direction = 1.69 cm

Average concentration of
1 N

 C fs  
u f  C sl usl A 
i 
metal in the outflow is C avg 
N
  l
i 1   uA  i 
computed as 
 
SFT Model Sensitivity Analyses of SFT Parameters

Influence of αsf

Breakthrough
curves
αsf has considerable influence in
breakthroughs and recovery of metal after
the irrigation is stopped

Recovery Curves
Thank You !
Questions?