TRANSPORT AND FATE OF

CONTAMINANTS IN THE
SUBSURFACE

IMPORTANT PROCESSES AFFECTING

THE FATE AND TRANSPORT OF
ORGANIC COMPOUNDS IN THE
SUBSURFACE

1
 INTRODUCTION

• Contaminant transport & fate refers to the physical,

chemical, and biological processes that impact the
movement of the contaminants from point A to point B
and how these contaminants may be altered while they
are transported.
• Physical processes move mass from point to point
• Chemical and biological processes redistribute mass
among different phases and chemical forms
2
 INTRODUCTION
• The environmental fate and transport of a
contaminant is controlled by the compound’s
physical and chemical properties and the nature
of the subsurface media through which the
compound is migrating.
• Non-aqueous phase liquid (NAPL): Immiscible
with water -Less dense than water (LNAPL)
e.g. petroleum products; Denser than water
(DNAPL) e.g. chlorinated solvents
• NAPL plumes, whether mobile or residual, tend
to act as a continuing source of groundwater
contamination. 3
 INTRODUCTION
Processes that affect fate and transport of
contaminants dissolved in groundwater:-
• Non-destructive: Result only in the
reduction of a contaminant’s concentration
but not of the total contaminant mass in the
system (e.g., advection and dispersion,
sorption, volatilization, etc.)
• Destructive: that result in degradation of
contaminants (e.g. biodegradation and
abiotic degradation mechanisms)
4
 Summary of the processes that affect fate
and transport of contaminants
dissolved in groundwater
• Advection and dispersion: Reduces solute
concentration.
• Sorption: Transfers contaminant from
aqueous to solid phase
• Volatilization: Transfers contaminant from
aqueous to gaseous phase
• Degradation: Chemical and biological
destruction of the pollutant.
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6
 CHEMICAL KINETICS
• Many environmental fate processes, such as the
degradation of pollutant chemicals, are not usefully
modeled as equilibrium chemistry problems because the
rate of the reaction is more important to quantify than the
final composition of the system.
• Even though it may be known that at equilibrium a
certain chemical will be fully degraded, it is crucial to
know whether degradation will take seconds, years, or
perhaps centuries.

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 CHEMICAL KINETICS
• The rate at which the concentration of reacting molecules
changes with time is described by first-order kinetics,

where C is the concentration of the parent compound

[M/L3], t is the time [T], and k is the rate constant [T-1].
• On integration from time =0 to t, the equation becomes;

where Ct is the concentration of the parent compound at

some time t [M/L3],C0 is the initial concentration of the
parent compound [M/L3], k is the rate constant [T-1],and t
8
is the time [T].
 CHEMICAL KINETICS
• Half-life (t1/2),which represents the amount of time
it takes for the parent compound to decay to half
its initial concentration can be derived as;

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1-D partial differential equation
describing solute transport in the
saturated zone

10
 ADVECTION
• The bulk motion of fluid is common throughout the
environment;
• The transport of solutes by the bulk movement of ground
water is known as advective motion, described
mathematically by the direction and the magnitude of its
velocity.
• If a chemical is introduced into flowing air or water, the
chemical is transported at the same velocity as the fluid .

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 ADVECTION

Advection is the most important process driving

dissolved contaminant migration in the subsurface.

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 ADVECTION
The linear groundwater velocity in the direction
parallel to groundwater flow caused by advection
is given by:

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 HYDRODYNAMIC DISPERSION
The process whereby a contaminant plume
spreads out in directions that are longitudinal
and transverse to the direction of plume migration.
Mechanical Dispersion is mixing that occurs as a
result of local variations in velocity around some mean
velocity of flow caused by heterogeneity of the porous
aquifer medium.

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Longitudinal dispersion and transverse (Horizontal and Vertical)
HYDRODYNAMIC DISPERSION
Physical processes causing mechanical dispersion
at the microscopic scale

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 HYDRODYNAMIC DISPERSION
Molecular Diffusion occurs when concentration gradients
cause solutes to migrate from zones of higher concentration
to zones of lower concentration, even in the absence of
groundwater flow.
• Fick’s First law of diffusive flux under steady-state
conditions:-

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 HYDRODYNAMIC DISPERSION
Molecular Diffusion:
For systems where the dissolved contaminant
concentrations are changing with time, Fick’s
Second Law must be applied.

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 HYDRODYNAMIC DISPERSION

Equation of Hydrodynamic Dispersion

Hydrodynamic dispersion, D, has two
components, mechanical dispersion and
molecular diffusion.

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HYDRODYNAMIC DISPERSION
1-D Advection-Dispersion Equation:
obtained by adding hydrodynamic
dispersion.

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 SORPTION
 SORPTION is the process whereby dissolved
contaminants partition from the groundwater and
adhere to the particles comprising the aquifer
matrix.
 Many organic contaminants, including chlorinated
solvents and BTEX (benzene, toluene,
ethylbenzene, and xylenes), are removed from
solution by sorption onto the aquifer matrix.
 Sorption of dissolved contaminants onto the
aquifer matrix results in slowing (retardation) of
the contaminant relative to the average advective
groundwater flow velocity and a reduction in
dissolved BTEX concentrations in ground water.
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 SORPTION
• Mechanisms of sorption: London-van der Waals forces,
Coulomb forces, hydrogen bonding, ligand exchange,
chemisorption (covalent bonding between chemical and
aquifer matrix), dipole-dipole forces, dipole induced
dipole forces, and hydrophobic forces.
• Hydrophobic bonding: important factor controlling the
fate of many organic pollutants in soils
• Hydrophobic (low water solubility) contaminant
molecules tends to partition from the groundwater and
sorb to the aquifer matrix.
• Two components of an aquifer have the greatest effect
on sorption: organic matter and clay minerals. In most
aquifers, the organic fraction tends to control the
sorption of organic contaminants. 21
 SORPTION
Sorption Models and Isotherms

Langmuir Sorption Model: The Langmuir model is

appropriate for highly specific sorption mechanisms
where there are a limited number of sorption sites.

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 SORPTION
Sorption Models and Isotherms
Freundlich Sorption Model: the number of sorption sites is
large (assumed infinite) relative to the number of contaminant
molecules.

The value of n in this equation is a chemical-specific quantity

that is determined experimentally
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 SORPTION
Sorption Models and Isotherms
linear sorption isotherm: Special form of the Freundlich
isotherm that occurs when the value of n is 1. The linear
isotherm is valid for a dissolved species that is present at a
concentration less than one half of its solubility.

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 SORPTION
Sorption Models and Isotherms
Coefficient of Retardation: The coefficient of
retardation, R, is used to estimate the retarded contaminant
velocity.

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 SORPTION
Sorption Models and Isotherms

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 SORPTION
Sorption Models and Isotherms
Characteristic adsorption isotherm shapes

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 SORPTION
Example: Trichloroethylene retention by peat
material (linear Isotherm sorption model)

40

30
q (mg/kg)

20

10

Observed
Linear sorption model ( r2= 0.8542)

0
0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6
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Ce (mg/L)
 SORPTION
Example: Trichloroethylene retention by peat
material (Freundlich Isotherm sorption model)

50

40

30
q (mg/kg)

20

10
Observed
Freundlich sorption isotherm model (r2 = 0.9400)

0
0.0 0.5 1.0 1.5 2.0 2.5 3.0 29
Ce (mg/L)
 DESTRUCTIVE ATTENUATION
MECHANISMS - BIOLOGICAL
• Many anthropogenic organic compounds, including
certain chlorinated solvents, can be degraded by
both biological and abiotic mechanisms.
• Biodegradation is mediated by indigenous
microorganisms
• Biodegradation ultimately transforms dissolved
contaminants into byproducts such as carbon
dioxide, chloride, methane, and water.

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 DESTRUCTIVE ATTENUATION
MECHANISMS - BIOLOGICAL
• Biodegradation of organic compounds dissolved
in groundwater results in a reduction in
contaminant concentration (and mass) and slowing
of the contaminant front relative to the average
advective ground-water flow velocity.
• Microorganisms indigenous to the subsurface
environment can degrade a variety of organic
compounds, including components of gasoline,
kerosene, diesel, jet fuel, chlorinated ethenes,
chlorinated ethanes, chlorobenzenes, and many
other compounds

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 DESTRUCTIVE ATTENUATION
MECHANISMS - BIOLOGICAL
Biodegradation of organic compounds in
groundwater occurs via three mechanisms:
1. Use of the organic compound as the primary
growth substrate;
2. Use of the organic compound as an electron
acceptor; and
3. Cometabolism.

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DESTRUCTIVE ATTENUATION
MECHANISMS - BIOLOGICAL

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 BIODEGRADATION OF ORGANIC
COMPOUNDS VIA USE AS A PRIMARY
GROWTH SUBSTRATE
• The contaminant is used as primary growth
substrates (electron donor) for microbial
metabolism.
1. Aerobic Biodegradation of Primary
Substrates
2. Anaerobic Biodegradation of Primary
Substrates

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 Aerobic Biodegradation of
Primary Substrates
• Biodegradation of organic compounds is often an
aerobic process that occurs when indigenous
populations of microorganisms are supplied with
the oxygen and nutrients necessary to utilize
organic carbon as an energy source.
• The biodegradation of fuel hydrocarbons occurs
rapidly under aerobic conditions

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 Aerobic Biodegradation of
Primary Substrates
• Some pollutants, especially the highly oxidized
chlorinated hydrocarbons (i.e., those containing
more chlorine substituents), are biologically
recalcitrant under aerobic conditions.
• Some of the less chlorinated ethenes and ethanes
such as DCE, VC, and 1,2-DCA, and many of the
chlorinated benzenes can be utilized as primary
substrates and oxidized under aerobic conditions.

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 Chlorinated Ethenes

Tetrachloroethene Trichloroethene 37
 Aerobic Biodegradation of
Primary Substrates
• During aerobic biodegradation (oxidation) of
chlorinated solvents, the facilitating
microorganism obtains energy and organic carbon
from the degraded solvent.
• Of the chlorinated ethenes, vinyl chloride is the
most susceptible to aerobic biodegradation, and
PCE the least.

38
 Aerobic Biodegradation of
Primary Substrates
• Chlorinated benzenes with up to 4 chlorine atoms
also have been shown to be readily biodegradable
under aerobic conditions
• Fuel hydrocarbons are rapidly biodegraded when
they are utilized as the primary electron donor for
microbial metabolism under aerobic conditions.

39
 Aerobic Biodegradation of Primary
Substrates (Petroleum Hydrocarbons)
• Biodegradation of fuel hydrocarbons occurs
naturally when sufficient oxygen (or other
electron acceptors) and nutrients are available in
the ground water.
• The rate of natural biodegradation is generally
limited by the lack of oxygen or other electron
acceptors rather than by the lack of nutrients such
as nitrogen or phosphorus.

40
 Aerobic Biodegradation of Primary
Substrates (Chlorinated Ethenes)
• Highly chlorinated ethenes (e.g., PCE and TCE)
are not likely to serve as electron donors or
substrates for microbial degradation reactions.
• This is because the highly chlorinated compounds
tend to be much more oxidized than many
compounds present in a natural ground-water
system.

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 Aerobic Biodegradation of Primary
Substrates (Chlorinated Ethanes)
• Of the chlorinated ethanes, only 1,2-dichloroethane
has been shown to be aerobically
mineralized/oxidized.
• The bacteria transform 1,2-DCA to chloroethanol,
which is then mineralized to carbon dioxide.

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 Abiotic Degradation
• Chemical transformations that degrade contaminants
without microbial facilitation; only halogenated
compounds are subject to these mechanisms in the
groundwater environment.
• Dependent on contaminant properties and
groundwater geochemistry.
• Can result in partial or complete degradation of
contaminants.
• Rates typically much slower than for biodegradation.

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 Abiotic Degradation
(Mechanisms)
• Hydrolysis literally means breaking of water.
• Is a substitution reaction in which an organic
molecule reacts with water or a component ion of
water, and a halogen substituent is replaced with a
hydroxyl (OH-) group.
• The hydroxyl substitution typically occurs at the
halogenated carbon leading to production of
alcohols initially.

44
 Abiotic Degradation
(Mechanisms)
• The net result of hydrolysis is that both a pollutant
molecule and a water molecule are split, and the two
water molecule fragments join to the two pollutant
fragments to form new chemicals.
• Using “X” to represent a halogen atom and “R” to
represent the hydrocarbon group, the overall hydrolysis
reaction can be written;

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 Hydrolysis

Dehydrohalogenation
Dehydrohalogenation is an elimination reaction involving
halogenated alkanes in which a halogen is removed from one
carbon atom, followed by the subsequent removal of a
hydrogen atom from an adjacent carbon atom
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47
 COMETABOLISM

• Is defined as the simultaneous degradation of two

compounds, in which the degradation of the second
compound (the secondary substrate) depends on the
presence of the first compound (the primary substrate)
• Cometabolism involves the injection of a dilute solution
of nutrients such as methane and oxygen into the
contaminated groundwater or soil. The microbes that
metabolize these nutrients produce enzymes that react
with the organic contaminant and degrade it to harmless
minerals.
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 BIODEGRADATION OF ORGANIC
COMPOUNDS VIA COMETABOLISM
• The contaminant serves as neither an electron
acceptor nor a primary substrate in a biologically
mediated redox reaction.
• The degradation of the compound is catalyzed by
an enzyme cofactor that is fortuitously produced by
organisms for other purposes.
• Slower process than reductive dechlorination

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 BIODEGRADATION OF ORGANIC
COMPOUNDS VIA COMETABOLISM
• Under aerobic conditions chlorinated ethenes, with the
exception of PCE, are susceptible to cometabolic
degradation
• Aerobic cometabolism of ethenes may be characterized
by a loss of contaminant mass, the presence of
intermediate degradation products (e.g., chlorinated
oxides, aldehydes, ethanols, and epoxides), and the
presence of other products such as chloride, carbon
dioxide, carbon monoxide, and a variety of organic
acids 50