Master in

Natural Resources for

Tropical Rural Development
Water Resources
Evaluation and Management
GW contamination
U2e

Elena Bresci
elena.bresci@unifi.it

- Definitions and concepts

- Mechanism of contamination
- Contamination origin and classification
- Transport processes

DEPARTMENT OF
AGRICULTURAL, FOOD AND
FORESTRY SYSTEMS
GESAAF

(Source: Zaporozec and Miller, 2000 in Groundwater contamination inventory,

IHP-VI, Series on groundwater no.2, UNESCO 2002 )

DEPARTMENT OF
AGRICULTURAL, FOOD AND
FORESTRY SYSTEMS
GESAAF

Groundwater Contamination
Infiltrating water may bring contaminants down to the aquifer.
Water is considered contaminated when it is harmful to human use.
Sources of water contamination:
Agricultural activities
Human wastes
Industrial effluents

DEPARTMENT OF
AGRICULTURAL, FOOD AND
FORESTRY SYSTEMS
GESAAF

Agricultural activities

Herbisides
Pesticides
Fertilizers
Animal wastes
Slaughter houses

Human wastes

Household garbage
Septic tanks
City landfills

Industrial wastes
Heavy metals from industries
Mine wastes
Radioactive wastes

DEPARTMENT OF
AGRICULTURAL, FOOD AND
FORESTRY SYSTEMS
GESAAF

Ground Water Contamination

Contaminated ground water can be

extremely difficult and expensive to
clean up

DEPARTMENT OF
AGRICULTURAL, FOOD AND
FORESTRY SYSTEMS
GESAAF

Chemical constituents in groundwater

Major

Secondary

Minor

Trace

Calcium (Ca)

Potassium (K)

Aluminium (Al)

Molybdenum (Mo)

Magnesium (Mg)

Iron (Fe)

Arsenic (As)

Nickel (Ni)

Sodium (Na)

Manganese (Mn)

Barium (Ba)

Phosphate (PO4)

Bicarbonate (HCO3)

Strontium (Sr)

Cadmium (Cd)

Radium (Ra)

Chloride (Cl)

Boron (B)

Chromium (Cr)

Selenium (Se)

Sulfate (SO4)

Fluoride (F)

Cobalt (Co)

Silver (Ag)

Silica (SiO2)

Carbonate (CO3)

Copper (Cu)

Uranium (U)

Nitrate (NO3)

Lead (Pb)

Zinc (Zn)

Mercury (Hg)

Sulfide (H2S)

DEPARTMENT OF
AGRICULTURAL, FOOD AND
FORESTRY SYSTEMS
GESAAF

Classification of GW contamination sources

Classification by
Way of release

Discharge sources; transport sources;

Origin

Domestic; agriculture;

Chemical type

Heavy metals; hydrocarbons; pesticides;

Location

Above ground surface; below surface;

Character

Point; diffuse

Potential sources of groundwater

contamination listed by the character of
discharge
(Adapted from: U.S. EPA, 1989)

(Source: Zaporozec and Miller, 2000 in Groundwater

contamination inventory, IHP-VI, Series on
groundwater no.2, UNESCO 2002 )

Summary of groundwater
contamination sources by origin

(Source: Zaporozec and Miller, 2000 in Groundwater

contamination inventory, IHP-VI, Series on
groundwater no.2, UNESCO 2002 )

DEPARTMENT OF
AGRICULTURAL, FOOD AND
FORESTRY SYSTEMS
GESAAF

Contamination Sources

Natural

Sedimentary rocks and soils

Human influenced
Agricultural
Industrial

Saltwater encroachment
Residential
Atmospheric sources

Over-exploitation
Lake eutrophication

Lake acidification

Accidents

DEPARTMENT OF
AGRICULTURAL, FOOD AND
FORESTRY SYSTEMS
GESAAF

Mechanism of contamination
The contaminant introduced into the soil-rock-groundwater system is able to spread within
the system only if a transport mechanism is available, for example, a flowing liquid.
As soon as the contaminant reaches the subsurface water in the unsaturated or saturated
zone, various processes determine its fate:

physical: advection, dispersion, evaporation, filtration;

geochemical: acid-base reactions, adsorption; ion exchange, oxidation-reduction,
precipitation-dissolution;
biochemical: transpiration, bacterial respiration, decay, and cell synthesis

DEPARTMENT OF
AGRICULTURAL, FOOD AND
FORESTRY SYSTEMS
GESAAF

DEPARTMENT OF
AGRICULTURAL, FOOD AND
FORESTRY SYSTEMS
GESAAF

DEPARTMENT OF
AGRICULTURAL, FOOD AND
FORESTRY SYSTEMS
GESAAF

Flow direction can change

DEPARTMENT OF
AGRICULTURAL, FOOD AND
FORESTRY SYSTEMS
GESAAF

DEPARTMENT OF
AGRICULTURAL, FOOD AND
FORESTRY SYSTEMS
GESAAF

Exchange flux in
centimeters per day

(from http://sofia.usgs.gov/publications/sir/2004-5069/)

DEPARTMENT OF
AGRICULTURAL, FOOD AND
FORESTRY SYSTEMS
GESAAF

Transport processes
It is considered the flux of solute into and out a fixed elemental volume within the flow
domain.
Mass balance

chemical or
biochemical
advection
reactions or
hydrodynamic dispersion
radioactive decay
The physical processes controlling the flux into and out of the elemental volume are
- advection
- hydrodynamic dispersion

DEPARTMENT OF
AGRICULTURAL, FOOD AND
FORESTRY SYSTEMS
GESAAF

Loss or gain of solute mass in the elemental volume can occur as a result of chemical or
biochemical reactions or radioactive decay.

DEPARTMENT OF
AGRICULTURAL, FOOD AND
FORESTRY SYSTEMS
GESAAF

Advection

Hydrodynamic
dispersion

It describes the movement of the contaminant with and

at the speed of the moving water. It is attributed to
transport by the flowing water. The rate of transport is
equal to the effective velocity.
Water, and hence the contaminant, may move faster
than the average in some portions of the aquifer and
slower than the average in other portions of the
aquifer.

Dispersion leads to a spreading of concentration fronts as they evolve over time and
enhanced mixing of contaminated water with surrounding uncontaminated water.

Occurs as a result of mechanical mixing and molecular diffusion.

DEPARTMENT OF
AGRICULTURAL, FOOD AND
FORESTRY SYSTEMS
GESAAF

Dispersion
Dispersion is a mixing process.
Qualitatively, it has a similar effect to turbulence in surface-water regimes.
For porous media, the concepts of average linear velocity and longitudinal dispersion
are closely related.
Longitudinal dispersion is the process whereby some of the water molecules and solute
molecules travel more rapidly than the average linear velocity and some travel more
slowly.
The solute therefore spreads out in the direction of flow and declines in concentration.

DEPARTMENT OF
AGRICULTURAL, FOOD AND
FORESTRY SYSTEMS
GESAAF

Dispersion process is related to the tortuosity, branching, and inter-fingering of pore

channels.
The spreading of the solute in the direction of bulk flow is known as longitudinal
dispersion.
Spreading in directions perpendicular to the flow is called transverse dispersion.
Longitudinal dispersion is normally much stronger than transverse dispersion.

DEPARTMENT OF
AGRICULTURAL, FOOD AND
FORESTRY SYSTEMS
GESAAF

Chemical or biochemical reactions or radioactive decay

Radioactive
decay

It results in the transformation of a

radioisotope into one or more daughter products.

It may result in:

Oxidation-reduction
acid-base
precipitation-dissolution complexation
substitution
microbial cell synthesis
reactions

- the transformation of one contaminant into

another more or less dangerous,
-the temporary or long-term mobilization or
immobilization of a contaminant,
-the alteration of the effective velocity of a
contaminant to a value other than the average
velocity of the water.

DEPARTMENT OF
AGRICULTURAL, FOOD AND
FORESTRY SYSTEMS
GESAAF

Non reactive compound

Solute moves in the porous medium but its concentration remains the same.

Reactive compound
Solute concentration is reducing mainly thanks to micro-organisms present in the soil
first layer.

DEPARTMENT OF
AGRICULTURAL, FOOD AND
FORESTRY SYSTEMS
GESAAF

Longitudinal and transverse dispersion

longitudinal
dispersion

transverse
dispersion

10-6

10-5

10-4

10-3

10-2

10-1

Aquifer velocity

(from Groundwater Freeze and Cherry, 1979)

DEPARTMENT OF
AGRICULTURAL, FOOD AND
FORESTRY SYSTEMS
GESAAF

Non reactive constituents in homogeneous medium

non reactive dissolved constituent
saturated, homogeneous, isotropic medium
steady state uniform flow
1 D flow

2C
C C
Dl 2 vl
=
l
l
t

where:

l = curvilinear coordinate in the longitudinal flow

vl= effective linear groundwater velocity in the longitudinal direction
Dl = coefficient of hydrodynamic dispersion
C = solute concentration

The effects of chemical reactions, biological transformations, and radioactive decay are not included
in this form of transport equation.

DEPARTMENT OF
AGRICULTURAL, FOOD AND
FORESTRY SYSTEMS
GESAAF

The coefficient of hydrodynamic dispersion may be expressed in terms of two components:

Dl = l ve + D*

dynamic
dispersivity
molecular
diffusion
where:

= dynamic dispersivity: a characteristic property of the porous medium [L]

D*= coefficient of molecular diffusion for the solute in the porous medium [L2/T]
e = effective velocity in the longitudinal direction [L/T]

DEPARTMENT OF
AGRICULTURAL, FOOD AND
FORESTRY SYSTEMS
GESAAF

Example
Non reactive tracer at concentration C0 is continuously introduced into a steady state flow regime at the
upstream end of a column packed with homogenous granular medium.
The tracer input is represented by a step function.

(from Groundwater Freeze and Cherry, 1979)

DEPARTMENT OF
AGRICULTURAL, FOOD AND
FORESTRY SYSTEMS
GESAAF

If it is assumed that the tracer moves through the column with no mechanical dispersion or molecular
diffusion, the tracer front will pass through as a plug flow and will exit from the column as a step
function.

In real situation, mechanical dispersion and molecular diffusion occur and the breakthrough curve
spreads out causing the tracer to begin to appear in the outflow from the column before the arrival of
water traveling at the velocity ve.

(from Groundwater Freeze and Cherry, 1979)

DEPARTMENT OF
AGRICULTURAL, FOOD AND
FORESTRY SYSTEMS
GESAAF

These are instantaneous pictures of the dispersion interface, inside the column, at various time
prior to breakthrough. The tracer front is spreading along the flow path.
The spreading of the profile increases with the travel distance.

Time 2

Time 1

Mechanical dispersion and molecular diffusion cause some of the tracer molecules to move faster
than the average linear velocity of the water and some to move slower.

(from Groundwater Freeze and Cherry, 1979)

DEPARTMENT OF
AGRICULTURAL, FOOD AND
FORESTRY SYSTEMS
GESAAF

The spreading out of the concentration profile is caused by both mechanical dispersion
and molecular diffusion.

(from Groundwater Freeze and Cherry, 1979)

DEPARTMENT OF
AGRICULTURAL, FOOD AND
FORESTRY SYSTEMS
GESAAF

At low velocity

diffusion is the important contributor to the

dispersion

At high velocity

Mechanical mixing is the dominant dispersive process

Laboratory experiments on tracer migration in saturated homogeneous granular

materials have established relations between the influence of diffusion and mechanical
dispersion. The exact shape of the relation between the Peclet number and Dl/D*
depends on the nature of the porous medium and on the fluid used in the experiment.

Pe =

where d = average particle diameter

ve d
D*

DEPARTMENT OF
AGRICULTURAL, FOOD AND
FORESTRY SYSTEMS
GESAAF

Relation between the Peclet number and the ratio of the longitudinal dispersion coefficient and
the coefficient of molecular diffusion in a sand uniform sized grains (after Perkins and Johnston,
1963 in Freeze, 1979).
(from Groundwater Freeze and Cherry, 1979)

DEPARTMENT OF
AGRICULTURAL, FOOD AND
FORESTRY SYSTEMS
GESAAF

The effect of longitudinal dispersion depends on velocity values.

Because mechanical dispersion is weaker in the longitudinal direction, the transverse dispersion
coefficient remains diffusion-controlled until the flow velocity is quite high.
(from Groundwater Freeze and Cherry, 1979)

DEPARTMENT OF
AGRICULTURAL, FOOD AND
FORESTRY SYSTEMS
GESAAF

One of the characteristic features of the dispersive process is that it causes the
spreading of the solute.
If its possible it is in both the directions: longitudinal and transverse.

Example 1
Dispersion in a sand box of a non reactive tracer introduced CONTINUOUSLY in a 2D
dimensional horizontal flow field.

The mass of the tracer is changing and it occupies an increasing volume of porous medium.
(from Groundwater Freeze and Cherry, 1979)

DEPARTMENT OF
AGRICULTURAL, FOOD AND
FORESTRY SYSTEMS
GESAAF

Example 2
Dispersion in a sand box of a non reactive tracer introduced as an INSTANTANEOUS point source
in a 2D dimensional horizontal flow field.

The tracer zone develops with an elliptic form as the tracer is transported though the porous
medium. The total mass of the tracer does not change, but the mass occupies an increasing
volume of porous medium.
(from Groundwater Freeze and Cherry, 1979)

DEPARTMENT OF
AGRICULTURAL, FOOD AND
FORESTRY SYSTEMS
GESAAF

The process of mechanical dispersion is directionally dependent even though the porous
medium is isotropic. This occurs is the process of mechanical dispersion to be anisotropic.

DEPARTMENT OF
AGRICULTURAL, FOOD AND
FORESTRY SYSTEMS
GESAAF

Effect of density on migration of contaminant solution in uniform flow

field
The transport equation is based on the assumption that there is no significant density
difference between the contaminant or tracer fluid and groundwater in the flow
domain.
Slightly more dense

Spreading in a shallow zone to the

water table.

Larger density contrast

The plume move downward into the

groundwater flow system.

Much larger density contrast

The plume move much more

downward into the
groundwater flow system.

(from Groundwater Freeze and Cherry, 1979)

DEPARTMENT OF
AGRICULTURAL, FOOD AND
FORESTRY SYSTEMS
GESAAF

Prediction of contaminant migration patterns requires accurate knowledge of the

density of the contaminant solution as well as that of the groundwater.

Boundary conditions of the

flow motion

Homogeneous layer

The presence of a thin higher

conductivity layer causes the
contaminant to move through
the flow system within this
layer
The contaminant moves over
the first lens and under the
other one. To reach the
discharge area, it passes the
second lens near the end of its
flow path.
A higher conductivity bed is
discontinuous in the central
part. This originates a great
distortion in the migration
pattern. The contaminated
zone spreads out in the central
part and extends to the water
table zone.
(from Groundwater Freeze and Cherry, 1979)

DEPARTMENT OF
AGRICULTURAL, FOOD AND
FORESTRY SYSTEMS
GESAAF

Prediction of contaminant migration patterns requires accurate knowledge of

stratigraphy of the system.
Lack of such information could result in inadequate monitoring and protection of the
groundwater flow system.

DEPARTMENT OF
AGRICULTURAL, FOOD AND
FORESTRY SYSTEMS
GESAAF

References
Cosgrove, W. J.; Rijsbergman, F. R., 2000. World Water Vision. Making Water Everybodys Business.
Earthscan Publ., London, UK.
Freeze, R.A.; Cherry, J.A. 1979. Groundwater. Englewood Cliffs, NJ: Prentice-Hall, 604 p.

Lindsey R.K., Franzini J.B., Freyberg D.L., Tchobanoglous G., 1993. Water resources engineering, McGrawHill)
UNESCO, 1992. Groundwater. UNESCO, Paris, France, Environ. and Development Briefs No. 2,
14 pp.
UNESCO, 2002. Groundwater contamination inventory. A methodological guide. Ed. By A. Zaporozec, IHP-VI,
SERIES ON GROUNDWATER NO.2