Fate and Transport of

Contaminants

CHAPTER 4
By N Abdullah
Learning objectives

1. To explain contaminant release via air emission

2. To determine the transport of contaminants in the
subsurface
3. To describe the fate of contaminants in the subsurface
Example: Fate of Pesticides in the
environment.
CONTAMINANT RELEASE

Liquid- runoff, discharge to surface water, leachate

to ground water
Solid- in air (fugitive dust), in water (suspended
solid)
Gas- stack emission, particulate emission
AIR EMISSIONS

Types of Air Emissions

Point: Landfill vent or incinerator stack (g hr-1)
Line: Dust from road and/or vehicle (g hr-1 m-1)
Area: Lagoon or construction site (g hr-1 m-2)
Volume: Building with open windows (g hr-1 m-3)
Puff: Volatile emissions from an accidental spill,
instantaneous (g/ total release)
AIR EMISSIONS
Volatilization
Transfer of a chemical substance from a liquid to a
gaseous phase.
Predominant source at most uncontrolled hazardous
waste sites.
function (temp, Pv , dC).
measured using Fick's Law. (J=D dc/dcx)
AIR EMISSIONS
Particulate Emissions
From waste treatment operations, incinerator
Fugative emission-
from materials handling and surface areas (eg. Roadways,
open waste piles, landfills etc).
Concern at inactive hazardous waste site
Controlled by 2 Parameters- wind (erodes and transport)
and disturbance of the soil
The Soil Conservation Service has a graphical method for
predicting annual average wind and erosion and resulting
soil loss.
Transportable and suspendible amount is that portion of the total
soil loss represented by particles 100 m diameter or smaller.
Inhalable size 10 m in diameter or smaller.
AIR EMISSIONS
Particulate Emissions
The greatest source of fugitive dust is remediation involving soil
handling.
E = k(0.0032) (U/5)1.3
(M/2)1.4
Where,
E = emission factor, k = particle size multiplier,
U = mean wind speed (mil/h) and M = material moisture content
(%)
The emission factor, E, may be multiplied by the tons of material
handled to achieve an estimate of total emissions.
 AIR EMISSIONS
Example:
Given: A site to be remediated has the following soil characteristics:
The average particle size < 15m, k = 0.48
The mean wind speed in the worst season in the Spring is 22 mph
The moisture content is only 60% can be raised to 85% by judicious
spraying. Over spraying is not a good idea as a hw leachate may be
formed.
The soil that needs to be moved occupies a vol. of 346' x 123' x 56' of which
1000 tons can be move per day.
The average soil density is 75 lb/ft3
Find: Estimate 1) the particulate emissions on a daily basis 2) the
particulate emissions on a total site basis.
 AIR EMISSIONS
Solution: Particulate Emission per Day
From p. 156 (La Grega) for particle size < 15 m, k= 0.48

E = k(0.0032) = 0.48(0.0032) = 0.001536 x 6.86/190.4

E = 5.53 x 10-5 lb of particulate/ton of soil moved

Daily emissions = Daily tons of soil moved x E

Daily emissions = 1000 tons/day x 5.53 x 10-5 lb

Daily emissions = 0.055 lbs of particulates / day

 AIR EMISSIONS
Solution: Emissions for Entire Site
Total tonnage = 346' x 123' x 56' x 75 lb/ft3 x 1 ton/2000lbs
Total tonnage = 89,372 tons
Total emissions = Total tons of soil moved x E
Total emissions = 89,372 tons/day x 5.53 x 10-5 lb
Total emissions = 4.94 lbs of particulates / total site
b) Water contaminant;
Surface & ground Water Contamination
Sources of Groundwater Pollution
 WATER RELEASES
Controlled releases
Virtually every industrial
and commercial facility
generates a wastewater and
it not possible to clean the
water to 100% standards.
Surface water (streams,
rivers and lakes)
Not groundwater
Uncontrolled release
Landfill leachate
(groundwater).
2. TRANSPORT OF CONTAMINANTS IN
THE SUBSURFACE

1. Hydrologic Cycle
2. Ground Water Flow
3. Hydraulic Conductivity of Geologic Materials
4. Flow in the Unsaturated Zone
5. Contaminant Transport Mechanisms
6. Real-World Contaminant Transport
7. Flow and Transport Equations
8. Ground Water Modeling
HYDROLOGIC CYCLE

A continuous circulation of water in the atmosphere, surface

and subsurface.
Waters reaching the saturated zone in the subsurface will flow
from areas of high hydraulic head to low hydraulic head.
If the stratum readily permits this flow it is know as an aquifer
and if it does not, it is an aquitard or confining layer. If the
aquifer is free to move up and down, it is an unconfined
aquifer. The stratum is homogeneous if the properties of the
soil do not vary with location.
An isotropic stratum does not vary with orientation or
direction. An anisotropic stratum has a higher hydraulic
conductivity in the horizontal direction and less in the vertical.
Most soils are anisotropic and heterogeneous, but they are
usually considered homogeneous.
Aquifer Pollutant:
Pollutants classified according to source
Biological (bacteria, viruses)
Industrial/chemical (fuel spills, TCE)
Pollutants classified according to behaviour
Miscible (solutes)
Immiscible
 GROUND WATER FLOW
Darcy's Law
Darcy's Law is the basis of our understanding of subsurface ground water flow:
Q=kiA
Q = flowrate
k = hydraulic conductivity ( k = 1x10-2 cm/sec for medium to fine sand)
i = hydraulic gradient, describes the rate of change in which the head is lost
as water flows through the porous materials:
where, i = (h1 - h2)/ l (hydraulic gradient)
A = cross sectional area of flow (perpendicular to flow direction)
l = sand column length
h1 and h2 = head at location1 and 2, respectively
Darcy's Law is empirical
Rearranging the first equation:
Q/A = ki,
Q/A = specific discharge, Darcy flux, or Darcy velocity,
= ki
Flow is in direction of declining hydraulic head requiring a negative sign. In
differential form:
= -k dh/dl (where dh/dl = hydraulic conductivity)
Darcy Experiment
GROUND WATER FLOW
Hydraulic head
Energy potential
Bernoulli energy equation
Elevation head + pressure head + velocity head
2D-flow (more in slide24)
Equipotential line
Flow lines
Laplace Equation
HYDRAULIC CONDUCTIVITY(k) OF
GEOLOGIC MATERIALS
Impermeable soil such as a tight clay may have a k of 1x10-9 cm/sec;
the most permeable material such as a clean gravel may be 1x10 5
cm/sec.
Two things should be remembered regarding k:
Order of magnitude refinement is appropriate
The value given for a specific material type may be very different
than the k for the entire formation.
Transmissivity (rate of water flow in vertical section of aquifer under
hydraulic gradient), T is the k times the aquifer thickness, t.
T=kt
CONTAMINANT TRANSPORT
MECHANISMS

Contaminants that are dissolved in water are solutes and the

water is the solvent and the combination is the solution. As the
water flows, the contaminants are transported with the water a
process known as advection.
As the water flows around the soil particles, it is mixed, a
process known as mechanical dispersion. The result is
dilution or reduction in the contaminant concentration.
A one time introduction of pollutants is termed a slug and
opposed to a continuous source. If the pollutant is introduced
at a discrete location, it is known as a point source as
opposed to a non-point source.
 CONTAMINANT TRANSPORT
MECHANISMS
The distribution and extent of contaminants migrating in the
subsurface is known as the plume.
Contaminates, particularly the ionic and molecular constituents, will
move from areas of high concentration to areas of low
concentration and this process is termed diffusion.
in formations of medium to high hydraulic conductivity- advective
transport and associated mechanical dispersion dominate the
contaminant transport
In formation of low hydraulic conductivity, including clay liners-
diffusive transport is the controlling mechanism.
REAL-WORLD CONTAMINANT
TRANSPORT

Mechanisms that influence and change idealized flow

predictions.
Fractured Media Flow. Flow will occur in the fractures
which behave like pipes as opposed to the bulk media.
Heterogeneity: If the formation is not homogenous, the
contaminant may transport a great deal more quickly
through a highly conductive lens.
Nonaqueous Phase Liquid (NAPL): Immiscible organic
liquid compounds exist as a separate liquid phase in the
subsurface. Low water solubility. Sinker (DNAPL) and
floater (LNAPL).
FLOW AND TRANSPORT EQUATIONS

1.) Laplace equation for isotropic flow in two dimensions:

2h/ x2 + 2h/ y2 = 0
May be solved by finite elements and finite difference mathematical
methods.
2.) Flow nets (graphical method).
Flow nets. Flow nets are 2-D graphical representations of hydraulic
head conditions in the subsurface.
Lines of equal total hydraulic head are know as equipotential lines
and the potential energy at any point on one of these lines is the same.
Flow lines are perpendicular to the equipotential and represent the
average path a particle of water takes as it flows in the subsurface.
Flow nets give a feel for the flow patterns and are alternate
methodology, independent verification, to other methods.
rapid method to calculate hydraulic head and (2D) flow condition in the
subsurface.
FLOW AND TRANSPORT EQUATIONS

2) Flow nets
Fundamental properties of flow nets:
The head difference between any pair of adjacent equipotentials
is the same as any other pair.
Flow lines intersect equipotentials at right angles.
Figures enclosed by adjacent pairs of equipotentials and flow
lines are essentially square.
The spacing of equipotentials is inversely proportional to the
hydraulic gradient and to the Darcy velocity.
Every flow channel transmits the same quantity of seepage.
The impervious boundary is a flow line; the free water boundary
is an equipotential.
FLOW AND TRANSPORT EQUATIONS
Where;
q = k h nf /nd nf = number of flow channels
nd = number of equipotential drops
2) Flow nets i = (h/nd )/ l I = hydraulic gradient
L = distance between 2 equipotential
FLOW AND TRANSPORT EQUATIONS

3) Finite Difference Method

A 2-D grid is constructed in which each nodal point is modeled to represent
the average head for the area enclosed by the square.
Use i, j notation.
head at a particular node, hi, j , is the average head at the four surrounding
nodes.
Boundaries conditions must be established either as constant head or no-
flow boundaries.
Numerical head values are assigned.
The heads are recalculated using the finite difference equation using the
trial and error relaxation technique until a specified tolerance is achieved.
GROUND WATER MODELLING

Once the model is created, "what-if" scenarios may be easily

evaluated.
Most models are mathematical, although analog, electrical etc.
are possible. Once the numerical model is selected, it must be
digitized so that the data can be fed into a computer.
Calibration or adjusting the model by comparing the model data
to real data comes next.
Once calibrated, the model can be used to:
Guide the placement of monitoring wells.
Predict contaminant concentrations.
Assess remedial alternatives.
Predict residual contaminants
3. FATE OF CONTAMINANTS IN THE
SUBSURFACE

Three processes
1.Retardation Processes
2.Attenuation Processes
3.Mobility Enhancement
1. RETARDATION PROCESS

It refers to processes that impede the transport of

contaminants by removing or immobilizing them from a
free state.
The contaminants are NOT transformed and the
process is reversible.
RETARDATION PROCESS
Sorption association of dissolved or
gaseous contaminant with a solid material
Adsorption surface process
Absorption internal process
Leads to retardation of the contaminant
front
Desorption reverse of either sorption
process
Soil Grain Sorption
Linear Sorption Isotherm
Sorption linearly
related to
aqueous
concentration. kd
S
1

Partition coefficient
is Kd

Kd is related to Kow 0
0 C
Partitioning to Solid Phase

Octanol water partition coeff. [A]octanol

kow =
[A]water
Distribution coeff. [A]solid
kd =
[A]aqueous

Fraction in aqueous phase 1

fw =
1
1 + - 1 kd
n
RETARDATION PROCESS

Linear Sorption Model.

S = K dC
For saturated conditions and non-polar organics.
Kd can be related to organic content:
Kd = Koc foc
A reasonable estimate is forthcoming if the
following conditions are met:
Minimum: Greater than 0.1%; few tenths of a percent;
1% (different sources);
Maximum: 20%
RETARDATION PROCESS

Example (Sorption):
Given: A phenol underground storage tank is leaking such that the
immediate surrounding ground water contains 7.3 mg/l of phenol. The
soil contains 2.5% organic matter, a fact ascertained by analyzing the
soil.
Find: Assuming a linear sorption model, what is the concentration of phenol
sorbed in to the soil? Calculate the sorbed concentration, S.
1.) Kd
From App. B, p.1113, Koc for phenol = 14.2 ml/g Note units.
Kd = Kocfoc units p.187 = 14.2 ml/g x (.025)
Kd = .355 ml/g
2.) S
S = KdC units p.187 = .355 ml/g x 7.3 mg/l
S= 2.59 mg/kg
RETARDATION PROCESS

Ion Exchange
Ion exchange involves the sorption of ions in solution onto
oppositely charged, discrete sites on the surface of a soil
particle. Ion exchange applies to metals while sorption
applies to organics, in general.
The capacity of a soil to retain and exchange cations is
quantified as the cation exchange capacity
Clay has a much higher cation exchange capacity than
other inorganic particles because of its extremely large
surface area that contains many negative sites.
Cations are replaced in the following order:
Na+ < Li+ < K+ < Rb+ < Cs+ < Mg++ < Ca++ < Ba++ <
Cu++ < Al+++ < Fe+++ < Th++++
RETARDATION PROCESS

Precipitation
Precipitation occurs when the concentration of a
solution exceeds the solubility of that compound and
any excess solute changes to a solid and falls out of the
solution.
Reversible.
Particularly applicable to heavy metals.
2. ATTENUATION
PROCESSES
It refers to 2 processes:
irreversible removal
transformation
Chemical Oxidation-Reduction. Redox involves
the gain or loss of electrons.
Biological Oxidation-Reduction
Hydrolysis. Chemical substances reacting with
water molecules.
Volatilization. The conversion of volatile chemical
constituents in ground water to vapor; the vapor
ending up in the atmosphere.
Abiotic Fate Processes
Oxidation-Reduction N O 2 N H 2

Hydrolysis
6e-
Elimination

n itro b e n z e n e a n a lin e

2e- -
C H 3C H 2C l C H 3C H 3 + Cl

c h lo ro e th a n e e th a n e + c h lo rid e
Cl H Cl H
Cl C C H C C
Cl H Cl H
 Volatilization
Transfer of contaminant from aqueous phase, NAPL, or
sorbed phase directly to gas phase
Equilibrium partitioning similar to octanol-water
partitioning
Partitioning equation known as Henrys Law
Hc is the relationship between partial pressure and
aqueous concentration of component
Pc
Hc =
[C]aq

20% Oxygen (0.2 atm partial pressure) => 8 mg/L DO

3. MOBILITY ENHANCEMENT

Opposite of retardation and attenuation i.e. the contaminant is

sped along.
Cosolvation. The presence of bulk solvents promotes
increased interaction between a solute and the solvent that
would not occur in water and can dramatically increase the
mobility of contaminants.
Ionization. Increased solubility
Dissolution. Dissolving of chemical substances such as a
leachate.
Complexation. Also chelation is the formation of a coordinate
bond between a metal ion and an anion know as a ligand.