Remediation of Contaminated Sites

Contaminants – Chemistry and behaviour

Related course material:
Reading n. 01 – Sources and types of groundwater contamination
Reading n. 03 – Water – air equilibrium
Reading n. 04 – MTBE
 CLASSIFICATION OF CONTAMINANTS

Density (for non aqueous phase liquids)

Solubility

Volatility

Chemical nature
Presence of specific elements in the compound
Organic or inorganic compounds
DENSITY
LNAPL: Light non aqueous phase liquids
Examples:

Benzene
Toluene
Ethylbenzene
Source Xylene
(Naphtalene)
LNAPL Vapours
Chloroetylene

Octane
Decane
Groundwater flow Dissolved fraction of NAPL

bedrock
 DENSITY
DNAPL: Dense non aqueous phase liquids
Examples:
TCE
PCE
PCB
Source

DNAPL

Groundwater Dissolved fraction of NAPL

flow

Bedrock
 SOLUBILITY

Solubility refers to the ability of a substance (called solute) to

dissolve in a solvent.

Definition: maximum amount of solute that can dissolve in a

solvent at equilibrium

Depends on:
Temperature
Characteristics of the specific compound

Units of measurement: mg/l; ppm; ppb

Solubility of some
compounds of
environmental
relevance
 EFFECTIVE SOLUBILITY

Si  Xi  Si
e

e
Si = Effective solubility of contaminat (i) (mg/l)
X i = mole fraction of contaminant (i)
Si = solubility of contaminant (i) (mg/l)
 HENRY’S LAW CONSTANT (H or KH)
It is an index of volatilization of a compound dissolved into water.
Used for the assessment of the phase distribution of a
contaminant between water and air.

pair m 3  atm
H H  
Cw mol
where :
pair : partial pressure of the vapour of the compound at temperatur e T;
C w : concentrat ion of the compound in water;

Sometimes it is useful to use a dimensionless H (pair e Cw

both in mol/l)
Compounds with H > 0.05 are considered very volatile
 VAPOUR PRESSURE
It is the pressure of the vapour phase of a compound in equilibrium
with the solid or liquid phase of the compound

Used for the evaluation of the volatility of compounds in separate phase.

B
-
pv  A  e T

Pv = vapour pressure
A, B = constants, dependent on the compound

Raoult’s law for solutions

pa  x a  pa
0 Pa,b = partial vapour pressure of a, b
0
Pb = vapour pressure of the pure compound
pb  x b  pb
0
xa,b= molar fraction
Example of contemporary presence of compounds
with different characteristics
. .
Typical Contamination Gas Foo d Bee

from Service stations

Hexane
Heptane Leaking
Octane Tank... . Tank
. ....
. .. .. ....
.
MTBE . ... .. . .. .. ....
.
. .
.. .. . ........... . . .. .. .
.. . .. .. . .. . . . . .
Vapo r
Floats o
. .
Tetra-ethyl lead .... . ... . ...... .... . .. .. .... . . . . . . . .
.. . .... . ... . . . ..... .. .....LNAP
.. .. .. ... .L........ . .
. . . .. . .
. . . . . .. .. . . ........ .... . .. . .
BTEX . . . . . . . . . ... . . . .

Soluble Plum e
Solub
Ground wate r
Sand Aquife r
Flo w
QUESTION: What are the effects of the different
properties of the compounds present on the migration
of the contamination? .
Gas Foo

Hexane
Heptane Leaking
Octane Tank... . Tank
. ....
. .. .. ....
.
MTBE . ... .. . .. .. ....
.
. .
.. .. . ........... . . .. .. .
.. . .. .. . .. . . . . .
Vapo r
Fl
. .
Tetra-ethyl lead .... . ... . ...... .... . .. .. .... . . . . . . . .
.. . .... . ... . . . ..... .. .....LNAP
.. .. .. ... .L........ . .
. . . .. . .
. . . . . .. .. . . ........ .... . .. . .
BTEX . . . . . . . . . ... . . . .

Soluble Plum e
S
Ground wate r
Sand Aquife r
Flo w
TETRA-ETHYL LEAD (TEL)

It used to be a common
antiknock additive in gasoline
due to its ability to increase the
fuel’s octane rating
It was banned at the end of the
20th century due to: Density 1,65
• Fouling in the catalytic converters Very low water solubility
• Concerns over air pollution and the
accumulative neurotoxicity of lead
• Cases of lead poisoning ascertained
(TEL manifacturing and handling)
 FUEL’S OCTANE RATING

It measures the resistance of fuels to detonation

High Octane rating enables the engine to perform at

higher compression ratios (that might cause detonation)

Definition by comparison with the mixture of iso-octane and

heptane that would have the same anti-knocking capacity as the
fuel under test: the percentage by volume of iso-octane in the
mixture is the octane number of the fuel.

iso-octane
 MTBE (Octane rating = 118)
Liquid

Density 0,74
Solubility = 42 g/l
Henry’s law constant = 0.022
(as a comparison: Benzene H= 0.22)

Question: can MTBE be more volatile than benzene?

Visit the site: www.epa.gov/mtbe/

 ORGANIC COMPOUNDS
VOLATILE ORGANIC COMPOUDS (VOCs)
High Henry’s law constant
High vapour pressure
BTEX
Major constituents of petroleum and related products.
Often used as solvents in chemical processes.

H3C

Benzene Toluene
C6H6 C6H5-CH3
 VOLATILE ORGANIC COMPOUDS (VOCs)
H3C BTEX
H3C

H2C
H3C

o-Xylene Ethyl-benzene
C6H4-(CH3)2 C6H5-C2H5

Source
LNAPL Vapours

Groundwater flow Dissolved fraction of NAPL

bedrock
VOLATILE ORGANIC COMPOUDS (VOCs)

H 3C C
Dimethyl-ketone • Solvent
(acetone) • Used in chemical industry
CH3 (additive in the
production of plastics)

H3C OH Methanol Common laboratory

solvent and used as
antifreeze and in the
production of biodiesel
 ALOGENATED VOCs
Chlorobenzene
C6H5Cl
Cl
Once: Production of pesticides, DDT
Now: Solvent, intermediate in chemical
syntesis (herbicides, rubber)
H H Cl H Cl Cl

Cl C C H Cl C C H Cl C C H

H H H H H H

Chloroethane Dichloroethane Trichloroethane

C2H5Cl C2H4Cl2 C2H3Cl3

Once: Production of • Solvent Solvent – banned in

tetra ethyl-lead • Intermediate in 1996 due to ozone
Now: production of chemical syntesis depletion concerns
ethylcellulose
 ALOGENATED VOCs

Cl
Cl C
C Cl TCE (Trichloroethylene, Trichloroethene)
H
Very common solvents
Cl
Cl C
C Cl
Cl
Source
PCE DNAPL
Tetrachloroethylene,
Groundwater Dissolved fraction of NAPL
Tetrachloroethene flow
Bedrock
http://www.clu-in.org/contaminantfocus/default.focus/sec/Trichloroethylene_(TCE)/cat/Overview/
http://www.clu-in.org
Trichloroethylene is a man-made chemical that does not
occur naturally in the environment. The clear, colourless,
nonflammable liquid evaporates quickly and has a sweet
chloroform-like scent. The chemical is used primarily as a large
volume degreasing agent for metal and electronic parts. It
also has found use as an extractant for oils, waxes, and fats, a
solvent for cellulose esters and ethers, a dry cleaning fluid,
refrigerant and heat exchange fluid, and as a feedstock for
manufacturing organic chemicals. In homes, trichloroethylene
can be found in typewriter correction fluid, paint, spot
removers, carpet-cleaning fluids, metal cleaners, and
varnishes.
Trichloroethylene also is known as trichloroethene, and is
commonly referred to as TCE.
http://www.clu-in.org/contaminantfocus/default.focus/sec/Trichloroethylene_(TCE)/cat/Overview/
http://www.clu-in.org
Industrial processes are the main sources of TCE in the
environment.
It is commonly found in air and water. Once it is released into
the air, TCE will break down within a week or less. TCE breaks
down more slowly in surface water and soil than in air, and it
can pass through the soil into underground water.
Most TCE in air comes from metal degreasing activities
associated with tool and automobile production. TCE also
can enter groundwater and surface water from industrial
discharges or from improper disposal of industrial wastes at
landfills.
TCE has been found in many drinking water supplies in
the United States.
http://www.clu-in.org/contaminantfocus/default.focus/sec/Trichloroethylene_(TCE)/cat/Overview/
http://www.clu-in.org
Health effects
The health effects from TCE differ depending on the amount
of TCE to which a person is exposed and how long the
exposure lasts.
Levels of TCE in the normal environment generally are well
below levels of those in the workplace.
TCE exposure can be associated with several adverse
health effects, including neurotoxicity, immunotoxicity,
developmental toxicity, liver toxicity, kidney toxicity, endocrine
effects, and several forms of cancer.
 Organic Semivolatile (SVOCs)
Henry’s law constant and vapour pressure
moderately low

Main groups:
Alogenated
Chlorophenols
Chlorobenzenes
Non Alogenated
PAH
 Organic SVOCs
Alogenated
Cl Chlorophenols
Chlorophenol
C6H5ClO disinfectant
HO

EPA classifies PCP as probable human carcinogen

- First produced in the 1930s

Cl Cl
- Herbicide, insecticide,
Pentachlorophenol
fungicide, wood preserving
HO Cl

C6HCl5O
Cl Cl Solubility: 0,020 g/l
Density: 2 g/cm3
 Organic SVOCs
Alogenated

Chlorobenzene has been used in the manufacture of some

pesticides

Cl Cl Solvent
C6H3Cl3

Cl 1,2,4-triclorobenzene
Cl Cl
Esachlorobenzene
Cl Cl Fungicide
C6Cl6
Cl Cl
 Organic SVOCs
PAH Polycyclic Aromatic Hydrocarbons (IPA)

Naphtalene
C10H8 PAHs occur in petroleum products,
asphalt and coal tar and are
Pyrene byproducts of fuel burning
C16H10 (incomplete combustion of fossil
fuel).
Some of them are also found in
cooked food (grilled meat)
Different compounds have different biodegradability
 Organic SVOCs
PAH Polycyclic Aromatic Hydrocarbons (IPA)

Benzopyrene is found in coal

tar, exhaust gas from vehicles,
tobacco smoke etc.

The link between benzopyrene

and cancer is proven, although
it is difficult to link cancers to Benzo(a)Pyrene C20H12
the specific benzopyrene
sources (inhalation or
ingestion?). Source
DNAPL

Groundwater Dissolved fraction of NAPL

flow
Bedrock
 Organic SVOCs
PAH Polycyclic Aromatic Hydrocarbons (IPA)

Phenanthrene
C14H10

Anthracene
C14H10
 Polichlorobiphenils (PCB)
X X X X X = Cl o H

More than 200 possible

X X combinations

X X X X

Source
DNAPL

Groundwater Dissolved fraction of NAPL

flow
Bedrock
http://www.clu-in.org/contaminantfocus/default.focus/sec/Polychlorinated_Biphenyls_(PCBs)/cat/Overview/

http://www.clu-in.org

Polychlorinated biphenyls (PCBs) are mixtures of up to

209 individual chlorinated compounds called congeners.
The compounds are man-made, with no known natural
sources.
PCBs appear as colorless to light yellow oily liquids or
waxy solids.
These chemicals have no known smell or taste. Many
commercial PCB mixtures are known in the United States
by the trade name Aroclor.
http://www.clu-in.org/contaminantfocus/default.focus/sec/Polychlorinated_Biphenyls_(PCBs)/cat/Overview/

http://www.clu-in.org
PCBs have been used as coolants and lubricants in
transformers, capacitors, and other electrical equipment
because they don't burn easily and are good insulators.
The manufacture of the compounds stopped in the United
States in 1977 because evidence showed that they build up
in the environment and can cause harmful health effects.

Though PCBs are no longer manufactured in the United

States, the levels of these compounds in various media with
respect to health and safety are regulated by the EPA,
Occupational Safety and Health Administration (OSHA), and
the Food and Drug Administration (FDA).
http://www.clu-in.org/contaminantfocus/default.focus/sec/Polychlorinated_Biphenyls_(PCBs)/cat/Overview/

http://www.clu-in.org
PCBs have entered the air, water, and soil during their
manufacture, use, and disposal (hazardous waste sites,
illegal or improper disposal of industrial wastes and consumer
products); from accidental spills and leaks during their
transport; and from leaks or fires in products containing PCBs.

PCBs do not readily break down in the environment and thus

may remain there for very long periods of time. Some PCBs
can exist as a vapor in air that can travel long distances and
be deposited in areas far away from the point of release. In
water, a small amount of PCBs might remain dissolved, but
most stick to organic particles and bottom sediments.
PCBs also bind strongly to soil.
http://www.clu-in.org/contaminantfocus/default.focus/sec/Polychlorinated_Biphenyls_(PCBs)/cat/Overview/

http://www.clu-in.org

PCBs are taken up by small organisms and fish in water.

They also are taken up by other animals that eat these
aquatic animals as food. PCBs accumulate in fish and
marine mammals, reaching levels that may be many
thousands of times higher than in water.