∂c ∂c 2

∂c
= - v + D x 2 − kc ± S d
∂t ∂x ∂x
for 0 < t ≤ t 0 ,
C0   (U − w)x   x − wt   (U + w)x   x + wt 
C(x,t ) = exp erfc  + exp erfc 
2   2D   2 Dt   2D   2 Dt 

for t > t 0 ,
  (U − w)x    x − wt   x − w(t − t ) 
exp  erfc  − erfc 0
 
C0   2D    2 Dt   2 D(t − t 0 )  
C(x,t) =  
2   (U + w)x    x + wt   x + w(t − t )
+exp   erfc   − erfc  0

  2D    2 Dt   2 D(t − t 0 ) 

where w = U 1+ 4kD
2 U 1
1 Introduction

Lesson objectives:
To understand conceptually the steps in modeling:
1. Define the problem
2. Conceptualization of system--determine what
is known, define system
3. Selection or development of mathematical
description (model)--important to understand
assumptions, data requirements and model
limitations
4. Model calibration--parameter adjustment
5. Evaluation of model results--do they make
sense??
2
Modeling objectives

•Increase understanding--which phenomena are

important, may provide insight into fundamental
behavior

•Predict effects of mitigation, remediation efforts

•Estimate exposure => health & environmental risk

•Model Identification

3
Modeling Protocol

4
 Modeling Protocol
Developing conceptual models

1. Establish the PURPOSE of the model.

Determine what questions are to be answered.
Defines what equations need to be selected and solved.
Determines what type of data is necessary.

2. Define the problem: contaminant(s), location

Define the “evaluative environment”
• Source: steady? Plant discharge, leaking tank, old spill?
• Relevant phases: what media (air, water, soil) are
affected? Properties of media important
• Model boundaries: scale? Soil grains -> globe

5
Example: someone has dumped their houseboat waste into Lake
Powell. Health officials are concerned about immediate and future
effects on human health. Define the evaluative environment.
air
soil
water
sediment

What characteristics of environment could be important?

Air water soil/sediment

P, T, wind velocity density grain density
(depends on altitude) mixing, stratification organic matter
Mixing, stratification T (P) permeability
Aerosol-deposition rates surface tension porosity
flow
pH
ionic strength
redox potential
particulate matter
6
Develop a CONCEPTUAL MODEL of the system.

Must gather and integrate field data.

i.e. Need to determine the type of aquifer, its units, and
boundaries.
Often includes the conceptual water budget.
It is important to visit the field site during this step!

7
 Select proper GOVERNING EQUATIONS and
COMPUTER CODE

Need equations and code to model your specific site.

Should verify equations and code against known analytical
solutions
or to modeling problems in similar settings.

DESIGN the model

Convert conceptual model to the form necessary for the

equations and code.
Includes descritization in time and space.
Must set boundary and initial conditions.
Must select initial parameters to be used in model.

8
 CALIBRATE the model

• Compare model to experimental data (calibration data set)

• Calibrate model based on calibration data set--model
coefficients, rate constants initially chosen from lab studies
or literature--tune within a range of observed or reported
values, using some mathematically defined criteria (e.g.
minimizing sum of squared errors)

• Performance criteria--how much error is acceptable? For

both calibration and verification-can be tight or loose; define
before calibration or verification

9
 Verify the Model
Once you have a model you must measure (collect data) to
verify the model(known as model validation).
All Models must be verified and validated.

Model Verification

Model verification refers to the process of removing computational

or conceptual errors from a model. This process is an attempt to
make the model internally consistent, and is usually performed by
the developers of the model before it is accessible to the general
public. Even after a model is in use, model users may occasional find
errors or inconsistencies. If this information is communicated to the
developers, they can improve later versions of the model.

10
 VALIDATE the model

See if the model can simulate a second set of field data correctly
(validation data set.)
Must specify the purpose of model and conditions and range in
which it is valid (all have limitations)

Use the model to PREDICT

Use the calibrated model to determine how it responds to future

events.
Must estimate future conditions.

11
Sensitivity and uncertainty analysis
• Determine how the model responds to uncertainty in
parameter values.
• May need to do for different stress periods.
• Can be a lot of uncertainty in values for future conditions.
• Determine SENSITIVITY to future parameter uncertainty
• sensitivity: which input parameters make the most
difference in the model output
• uncertainty: which input parameters should we know
more precisely to make the model more precise?

Both are important

change in parameter
sensitivity often defined as :
change in output

12
 Sensitivity analysis
Definitions vary. In most studies, sensitivity analysis is the
study of model properties through - not necessarily realistically
sized - changes in the input variables and the analysis of its
effect on model outputs. The questions addressed are for
instance:

· whether or not some output is affected at all by some

input

· continuity, differentiability, monotonic increase or
decrease of the model's response to input variation

Most of the variation of outputs is generally caused by a

small number of inputs.

13
Uncertainty
In this context: imperfect knowledge regarding aspects of a model.
Uncertainty regarding model variables is usually specified by a
probability distribution or by a sample of measured values (an
empirical probability distribution); sometimes it is specified by a set
of possible values. We adhere to the probabilistic concept of
uncertainty, and we use variances as measure of uncertainty.

14
Sources of uncertainty
Uncertainty exists at the level of inputs and output of the model.
Uncertainty of model formulation also exists. We will assume
that the model is deterministic, and that uncertainties are
solely introduced via the inputs.

Input uncertainty is caused by natural variation (e.g. weather, soil

or water variation) as well as by imperfection of data. Although the
causes of uncertainties may differ, their effect is the same, namely
uncertainty about model outputs. Up to the modeler whether or not
to incorporate natural variation in the model; the choice depends
also on the spatial or temporal scale at which the model is used.

The input uncertainty of different parameters may contain

correlations caused by biological or physical mechanisms, e.g.
correlation between photosynthesis rate during the day or night, or
between weather at two consecutive days. 15
PRESENT RESULTS of model and model design

Probably one of the most important steps.

You may have a great model, but you need to show to others.
Difficult to do for laypersons.

Remember that modeling is an iterative process.

After the above steps are completed, it is important to re-
examine the model,
Find where it is successful and where it is less than satisfactory,
then improve it.

16
This is science and philosophy, like the
scientific method.
It has changed the way science is done and is
the basis of a modern technologically based
approach.

17
 Some Thoughts on Modeling the Environment &
Models used in Environmental Evaluation

Essential skills for successful model development.

1. Identifying the problem variables accurately.

2. Constructing appropriate relations between these variables.

3. Taking measurements judging the size of quantities that are

significant and the limitations for these relationships. Set limits.

18
4. Collecting data, decide how to use them and test your
model before your finalize it. Modify the model with data
and with additional theoretical relationships that you find
through this process.

5. Know and document the limits of the model by estimating

the parameters within the model that cannot be measured or
calculated from data.

6. Limit the use of the model to its functional and appropriate

capabilities excluding the inappropriate use of the model.

19
 Example:Ocean Disposal of Nuclear Waste
It has been suggested that canisters of nuclear waste can safely be driven into the
ocean floor and stored without contaminating large regions of ocean.
Model Proposed by Researcher
Assumptions made by the model
1. The canisters will penetrate the ocean floor to a minimum depth of 50 Meters.
2. No disturbance of the ocean water will be caused by the presence of the
canisters.
3. Canisters will last for over 1,000 years.
4. After 1,000 years, leaching will occur.
5. A diffusion model was constructed to distribute the radioactive leached
isotopes. Taking into consideration exclusively brownian movement and
diffusion aspects of the dispersion in the water.

20
 Questions:

How was the model constructed?

•What are the important variables and parameters?
•What are the relationships?
•What is the mathematical relationship? (an example of a
typical diffusion algorithm)

21
The process of solute movement are commonly described by the advection-
dispersion equation.

∂c/∂t = Dm(∂2c/∂x2) - v ∂c/∂x

Where: ∂c/∂
∂t is the change in concentration with the change in time, and
c is solute concentration
t is time
D is the dispersion coefficient (D = Do+ ev)
where: e is the coefficient of solute dispersivity in soil, and Do is the
molecular diffusion coefficient
v is pore water velocity (given by water flux (q) divided by the volumetric
water constant (theta)
Ref. Modeling Chemical Transport in Soils: Natural and Applied
Contaminants, Hossein Chadiri and Calvin Rose, Lewis Publishers, pg. 147,
1992.
22
Then, the following steps were taken and questions asked:

•Model Verification, Evaluation, Validation, and Limitation:

•Were the assumptions valid?
•Is this an appropriate model?
•If it was not a good model, why and how would you improve it?

23
 Model Type

Deterministic Stochastic

Steady State non-Steady State Steady State non-Steady State

Conservative non-Conservative Conservative non-Conservative

24
 Some model types
Deterministic: a partial differential is solved, numerically or
analytically, for a given set of input values, atmosphere,
stream, lake or aquifer parameters, and boundary conditions.
The resulting output variable has a specific value at a given
place in the system. There is a fixed relationship between input
and output.
Steady state: system does not vary with time. Inputs are constant
and system eventually reaches some equilibrium condition.
a. conservative parameter: material doesn't react or decay.
b. nonconservative: waste undergoes reactions, transformations,
decay.
Dynamic: system changes with time due to changing conditions
or inputs.
a. conservative
b. nonconservative
25
Stochastic: a model for which there is a statistical
uncertainty in the value of the output variables due to
uncertainties in the system parameters, input parameters,
or errors in measurement. Models allow for random
fluctuations. Uses mean and standard deviations of
parameters.

Steady state, conservative and nonconservative

Dynamic, conservative and nonconservative

26
 Model Type

Deterministic Stochastic

Steady State non-Steady State Steady State non-Steady State

Conservative non-Conservative Conservative non-Conservative

27
Contaminant Transport
• Mass Balance
• Advective transport
• Diffusion and
dispersion
• Volatilization
• Adsorption
• Biodegradation
processes
• Chemical Reaction
28
1.2.4 Define fate and transport phenomena

• physical
• basic mass balance, reactor theory
•advection: transport of contaminants due to bulk flow
of water or air
• diffusion: spread of contaminants due to random
molecular motion
• dispersion: spread of contaminants due to mechanical
mixing

Can have transport between phases (aqueous, vapor,

solid), transport within a phase, complete mixing within
a phase (Topics 4 & 5)

• chemical and biological rxns (Topic 2) 29

 Subdivisions of Transport Process
Transport

Mass Balance

Loading Advective Dispersive

physical movement spreading to down gradient Reactions
of contaminants mixing due to turbulence etc.

Diffusive
movement from higher
to lower concentration

Point Sources Nonpoint sources

intentional Fugitive emissions Homogeneous Heterogeneous
well defined source unintentional emissions
Single phase Multiple phases
boundary Ill-defined source boundary

30
Sources of Contaminate Loading
• Industrial spills,
discharges and leaks
• Surface impoundments
• Storage tanks and
pipes
• Landfills
• Burial areas and
dumps
• Injection wells 31
Areas of Contamination
• Surface soils
• Subsurface soils
• Shallow ground water
• Deep ground water
• Vapors above water
table
• Drinking water wells
• Receiving
streams/lakes
• Air 32
 Mechanisms of Contamination
Municipal
water well

pond
Leaking
petroleum
tank
Ocean Water table

Infiltration of Leakage from

Fresh hazardous Contaminated
septic tank pesticides and shallow
water fertilizers from Municipal waste site
leakage landfill well
farmlands

Saline Lateral Accidental

Water intrusion of fuel spill
Brine leakage from
saline water ruptured well casing Confining
Unit

Confining
Unit

Abandoned Deep
oil well Aquifer

33
 To upper atmosphere Sun

Wind dispersed contaminants

Volatilization

Precipitation Photochemicals
Sunlight

Volatilization
Landfill
Inflow

Hydrolysis Photolysis
Acid-base equilibria
Biodegradation
Adsorption/
Sewer desorption
Bioaccumulation
Sedimentation

Leachate to Sediment
groundwater Leachate to
groundwater

34
1.2.5 Define the “state” of the system

• Steady or unsteady state

Steady state: no change of mass &/or concentration at
a point with time
dm =0, dC =0
dt dt Opposite is unsteady state,
or Dynamic

m or C

t (at a point)
35
• Equilibrium or nonequilibrium (partitioning between 2 phases)

Chemical equilibrium: net rate of mass transfer between

phases is zero (or rate of forward and backward reaction is 0)
Ratio of concentrations in phases = a specific constant called
the equilibrium partition coefficient = Kij

Concs. change,
Air ratio is constant
CA CA = K at equilibrium CA
Cw AW

Water C Cw
Cw
t
36
 Air
Example: V=100 m3
CA=8 mol O2/m3 CA =20
Given the system is at equilibrium
Water Cw and steady state;
V=100 m3
each phase is well mixed.
Cw=0.4 mol O2/m3

Air CA,out= Air CA,out=

a. b. 6 mol
CA=8 mol 8 mol
CA,in= 8 mol O2/m3 O2/m3 CA,in= 8 mol O2/m3
O2/m3 O2/m3
Water C = Cw,in= 0.1 mol Water C =
Cw,in= 0.4 mol w,out w,out

O2/m3 Cw=0.4 mol3 0.4 mol O2/m3 0.2 mol

O2/m O /m3 (both constant) O2/m3
2
(constant)
All concs. constant
Equilibrium? √ Equilibrium? no--ratio≠20
Steady State? √ Steady State? √
37
 Example (cont.)

c. d.
Both Couts Both Couts
vary but vary and
Both Cins vary Both Cins vary
ratio is ratio ≠ 20
always 20

Equilibrium? √ (note Equilibrium? no

that influent streams do NOT Steady State? no
need to be at equilibrium for
the system to be at equilibrium)
Steady State? no

38
1.3 Developing mathematical models

Mass balance approach (engineering fundamental)--mass cannot

be created or destroyed (except nuclear rxns), but it can be
transferred or transformed

• Define control volume (evaluative environment)

• Define inputs and outputs across and within boundaries =>
mass balance equation (mathematical model)
Accumulation or rate of change of storage = input - output +
reaction (+ generation - consumption)

Inputs Accumulation ↑ Outputs

Decay ↓

Boundary
39
Example (will cover in more depth in Topic 4): closed, steady
state system--no mass flow into or out of system
Total mass in this evaluative environment = sum
Air of mass in each phase
VA, CA
mtotal = CAVA + CwVw + CsVs
Water
Vw, Cw Given Cw, Vi’s--relate CA and Cs to Cw by
Sediment equilibrium partition coefficients
Vs, Cs --Henry’s law Kaw = CA/Cw
--sediment/water partition coeff Κsw = Cs/Cw

⇒ mtotal = KawCwVA + CwVw + ΚswCwVs

= (KawVA + Vw + ΚswVs) Cw

40
We’ll look at 2 good models with sound physical basis

• completely mixed compartment (box) model

Not spatially dependent--concentration is uniform in
each phase

• advection/dispersion models
Changes in concentration with both time and space

41