Environmental Modeling

Scope
1) Introduction
2) Transport Phenomena
3) Chemical Reaction Kinetics
4) Equilibrium Chemical Modeling
5) Goundwater Contaminants
6) Eutrophication of Lakes
7) Conventional Pollutants in River
8) Toxic Organic Chemicals
9) Modeling Trace Metals
10)Atmospheric Deposition
11)Global Change and Global Cycles
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Introduction

Scope on Environmental Modeling

To gain understanding of the fate and
transport of chemical by quantifying their
reactions, speciation and movement
To determine chemical exposure
concentrations to aquatics organism and/or
humans in the past, present or future,
To predict future conditions under various
loading scenarios or management action
alternatives
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Where do all chemicals go?

Are they with us forever?
How rapidly are they degraded?
Example: the fate, transport and
persistence of chemical in the
environment.
Models for conventional pollutants,
eutrophication, toxic organic chemicals
and metals in surface water.
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Mathematical Models
To determine chemical exposure
concentrations
To assess the effects of chemical
pollutants
For waste load allocations, risk
assessment, or environmental impact
assessments.

Water quality criteria

Aquatic organisms and their uses should not be
affected unacceptably if two conditions are met:
The 4-day average concentration of the toxicants
does not exceed the recommended chronic criterion
more than once every three years on the average
The 1-hour average concentration does not exceed
the recommended acute criterion more than once
every three years on the average.

The models can be developed for frequencyduration relationships of pollutant exposure.

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Environmental models
To predict the future chemical
concentrations under various scenarios or
management action alternatives.
Principle of continuity: matter is neither
created or destroyed in macroscopic
chemical, physical and biological
interaction = mass balance

Mass Balances
Water quality = something inherent or distinctive
about water
Distinctive (quality) parameters = chemical,
physical and biological parameters, mostly in mass
quatitaties or concentration unit (mg, mg L -1, moles
L-1)
The fate of chemicals in aquatic environment:
Reactivity
Rate of their physical transport through the environment

Mathematical model == accounting procedures

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Key elements in a mass balance:

A clearly defined control volume
A knowledge of inputs and outputs that
cross the boundary of the control volume
A knowledge of the transport
characterisitics within the control volume
and accros its boundaries

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Control Volume
The boundaries are clearly define with
respect to their location, so that :
i. the volume is known and
ii. mass fluxes across the boundaries can be
determined
iii. Transport accross the boundaries of the control
volume must be known or estimated.
iv. A knowledge of chemical, biological and
physical reactions that the substance can
undergo within the control volume is needed.
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accumulation

If the system is at steady state = no change in

concentration with respect to time = dC/dt = 0

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Change in storage
The accumulation of mass of water = water balance

Inflows = volumetric inputs of tributaries and

overland flow
Outflows = all discharges from the water body
Direct precipitation = the water that falls directly on
the surface
Evaporation = the volume of the water that leaves
the surface of the water body to the atmosphere
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 If the lake or stream basin is not

sufficiently tight with respect to inputs
and outflows to groudwater, the
piezometric surface of the groundwater
adjacent to the water body must also be
measured:

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Water budget

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Model Calibration and Verification

To perform mathematical model, four
ingredients are necessary:
Field data on chemical and mass discharge
inputs
A mathematical model formulation
Rate constants and equilibrium coefficients for
the mathematical model
Some performance criteria with which to
judge the model
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Requires two sets of field data

For model calibration: compare between
simulation result and field measurements
For model verification: from different
circumstances (a different year or an
alternate site)

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Model Calibration
Statistical comparison between model
results for the state variations (chemical
concentrations) and field measurements.
If errors are acceptable model calibrated.
If error are not acceptable tune the model
(constants and coefficients) obtain
acceptable simulation model calibrated

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definitions
Mathematical model= a quantitative formulation of
chemical, physical and biological processes that simulates
the system
State variable = the dependent variable that is being
modeled (usually a chemical concentration)
Model parameter= coefficients in the model that are used
to formulate the mass balance equation (rate constants,
equilibrium constants, stoichiometric ratios, etc.)
Model inputs = forcing functions or constants required to
run the model (e.g. Flowrate, input chemical
concentrations, temperature, sunlight)
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 Calibration = a statistically acceptable comparison

between model results and field measurements,
adjustment of model parameters is allowed within
the range of experimentally determined values
reported in the literature.
Verification = a suitably acceptable comparison
between model results and a second (independent)
set of field data for another year or at an alternate
site; model parameter are fixed and no further
adjustment is allowed after the calibration step
Simulation= use the model with any input data set
(even hypothetical input) and not requiring
calibration or verification with field data.
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 Validation = scientific acceptance that

(1) the model includes all major and salient
process,
(2) the processes are formulated correctly, and
(3) the model suitably describes observed
phenomena for the use intended

Robustness = utility of the model established

after repeated applications under different
circumstances and at different sites
Post audit = a comparison of model prediction
to future field measurement at that time

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 Sensitivity analysis = determination of the

effect of a small change in model
parameter on the results (state variable),
either by numerical simulation or
mathematical techniques
Uncertainty analysis = determination of
the uncertainty (standard deviation) of the
state variable expected value (mean) due
to uncertainty in model parameters,
inputs, or initial state via stochastic
modeling techniques.
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Criterion for acceptance

Example: the prediction of dissolve oxygen concentration in the
stream should be within + 0.5 mg L-1 in at least 90% of the
observations.
Statistical goodness fit using chi-square or Kolmogorov-Smirnov
tests.
Paired t-test of model results and field measurement at the same
time
Linear regression of paired data for model prediction and field
observation at the same time
A comparison of model results to field observation and their
standard deviation
Parameter estimation techniques such as nonlinier curve-fitting
regression
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Environmental Modeling and

Ecotoxicology
The role of human in the chemical cycles:
The antopogenic energy flow per unit area > 10 times
photosynthesis
Organic chemicals produced by industry = 150 kg capita-1
year-1 or 40 g m-2 year-1.

Impacted domain:
Oceans
Stratosphere
Deep groundwater aquifiers

1000-1500 new chemical manufactured each year

60,000 chemical in daily use, mostly organic chemicals
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Predicting rates of reaction and

partitioning
Four parameters for prediction rate constants for many
compounds:
Octanol/water partition coefficients
Henrys law constant
Dissociation constant
Sorption spectrum

Reactions:
Hydrolisis
Photodegradation
Volatilization
Sorption
bioconcentration
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Heavy metal pollutants

Pervasive and a greater problem than organic
chemical based on their persistence.
Water quality criteria can be violated by natural
condition, such as Ra-226 and Ba in drinking
water, and cope in clod-water fisheries.
Human acitivities elevate metal concentration:
Hg, Pb, Cd, Cu and Zn in surface waters,
As and Se from agricultural soils
Phosphate, nitrate and ammonium from agricultural
runoff
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Trace elements pollutants

Enrichment in the atmosphere or
hydrosphere
Its chemical speciation
Its biochemical cycling

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Atmospheric transport
Open ocean and lakes are more affected by
pollution impacts through tropospheric than
through riverine transport
Atmophile elements = their mass transport to the
sea is greater from the atmosphere than from
transport by streams.
Example = Cd, Hg, As, Se, Cu, Zn, Sn and Pb.
Atmophile elements=
Volatile or low boiling points
Methylated Hd, As, Se, Sn or Pb.
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Lithophile
Transported by stream= Al, Ti, Mn, Co, Cr,
V and Ni.

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 Volatiles = H2O, CO2, HCl, SO2 from

volcanos
Gigantic acid-base reaction with bases of
the rocks (silicates, carbonates, oxides)
Produce a stationary situation: 20.9% O 2,
0.03% CO2, 79.1% N2, ocean pH ~8.

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