GEOTECHNICALENGINEERING

CHEMICAL Covers
BACKGROUND 1.Remediation of already y polluted
p
sites
OF GE Engineering 2 The design of containment
2.The
facilities for future sites

1. Dealing
g with already
yppolluted 2. Designing
g g waste containment
sites facilities
Two ways of addressing the problems or to treat the
contaminated materials To developp chemical-resistant barriers
that form part of the containment lining
1. To immobilize the spread
p of contaminants i.e. toxic
chemicals system
t
2. To recover or remove the contaminants from the
soil or groundwater
 Chemicals of Environmental Concern

In any case
case, an understanding is needed for zSummarised Information on chemical
background and quick reference on
1.the
1 th behaviour
b h i off various
i contaminants
t i t iin various chemical terms and concepts
soil and groundwater zDetails to refer to other references
2.The sources of hazardous and non-
hazardous wastes, and
3.The methods to characterize these wastes
((in later chapter)
p )

TOXIC CHEMICALS 1. TOXIC INORGANIC CHEMICALS

zUSEPA identified several toxic chemicals
based on their known or suspected
adverse effects on human health and the
environment.
zThese are known as priority pollutants
pollutants.
zAll these are grouped under three
categories
t i ii.e. toxic i chemicals,
t i iinorganic h i l
toxic organic chemicals, and radionuclides
These chemicals are found in contaminated
sites and in waste leachates
z They include heavy metals such as Cd Cd, Ni
Ni, Pb
Pb,
Cr, and Hg (USEPA, 1977)
z Non
Non-metals
metals such as arsenic and selenium
z Refer to Table 3.1 in textbook for more
z A study of these chemicals is termed inorganic
chemistry (see Section 3.3 of textbook)
z A brief background is in Section 33.4
4 of the book
2. TOXIC ORGANIC CHEMICALS 3. TOXIC RADIONUCLIDES

Those commonly found at contaminated These are found at contaminated sits

sites and waste leachates are: zThe typical radionuclides are: uranium and
z Benzene,
Benzene toulene,
toulene trichloethylene
trichloethylene, endrin
endrin, and thorium (USEPA,1977)
(USEPA 1977)
lindane (USEPA, 1977)
zOthers can be found in Table 3.1
z See Table 3.1
3 1 for more
z Note that toxic organic chemicals are further
zNuclear chemistry is the study and use of
subdivided
subd ded based o on st uctu e & functional
structure u ct o a these substances
groups zSee Section 3.5 for its background
z A studyy of these chemicals is called organic
g
chemistry

(I) INORGANIC CHEMISTRY

Concentration of Chemical Compounds
BACKGROUND
zConcentration of ion or chemicals in solution
is commonly expressed as
z1) molar concentration
concentration, 2) mole fraction
fraction, or 3)
mass concentration
D fi iti
zDefinitions:
Molar concentration
Number of moles2 per volume of solution
e g 1M solution = 1 mole per litre(mole/L)
e.g.
 Chemical Kinetics
DEFINITIONS z All reactions are assumed to be in equilibrium where
concentrations remains constant
z In reality, concentrations often change with time
zThe mole fraction (xi ) is the number of z The rate of reaction depends on the concentration of species
moles of a substance (ni ) divided by the in a reaction
total number of moles
moles. z The rate of reaction p provides a real-time p
prediction of the
concentration of contaminants
zMathematically, xi = ni /ni (where ni is z The rate can also indicate the controlling reactions
the total number of moles z These kinetic reactions may include precipitation-dissolution
reactions and redox reactions, e.g. the time required to
dissolve a metal salt may be predicted based on the rate of
precipitation-dissolutions
z Similarly, if a dissolved contaminant is to be precipitated due
t a redox
to d reactions,
ti the
th rates
t off redox
d reactions
ti could
ld
provide an estimate of the time required for formation of the
precipitates.

DEFINITIONS DEFINITIONS

zThe mass concentration is expressed as zOccasionally, concentration is expressed

zOccasionally
the mass of the element or compound in as meq/L
milligrams per litre of solution (i
(i.e.
e mg/L) zIt is the equivalent weight of an element in
zOften called parts per million (or ppm) milligrams in 1L of solution
If the
zIf th SG off solution
l ti iis 11, th
then 1L off Th equivalent
zThe i l t wt.t off an element
l t
solution equals 1000g. Then z= Atomic wt./Oxidation Number
1 /L (1 /1000 mg)) x(1L/1000
1mg/L=(1g/1000 (1L/1000 g)) = 1/106 zExample: Ca2+ with atomic wt. of 40g/mol,
= 1 ppm. Thus, 1 mg/L is 1 ppm has equivalent
q wt. = 40/2 = 20 g
 CHEMICAL REACTION CHEMICAL REACTION

zChemical Reaction Balance z A chemical reaction occurs whenever a chemical

compound is formed from the elements or from the other
zChemical Reaction Equilibrium chemical compounds.
z This
Thi process involves
i l transformation
t f ti off the
th arrangementt
of atoms in molecules of the initial substances, known as
reactants, into a new arrangement of atoms in the
molecules of the final substances called products.
Example: A+B = C+D where A & B are reactants and C
& D are products
z Zn + 2HCl = ZnCl + H2

TYPES OF CHEMICAL REACTIONS 1. ACID-BASE

ACID BASE REACTIONS

Four different types are important in z It is a chemical reaction involves either ggain or loss of a
proton (H ) or the gain or loss of a hydroxyl (OH-)
+

environmental studies. They are: z In general, acid is a proton donor and base is a proton
1 A id B
1.Acid-Base Reactions
R ti acceptort
z Acid-base reactions affect the pH and chemistry of soils
2.Precipitation-Dissolution Reactions & groundwater and have major effect on remediation and
3.Complexation Reactions waste containment.
z Refer to book for the disassociation of water, acids and
4 Oxidation-Reduction
4.Oxidation Reduction Reactions b
bases and
d ttypical
i l acid-base
id b reactions
ti where
h
disassociation refers to when a compound is dissolved in
water, the ions that p packed tightly
g y together
g in the
compound become separated
 2. PRECIPITATION-DISSOLUTION
2. PRECIPITATION-DISSOLUTION REACTIONS
REACTIONS Equilibrium Constant for a precipitation-dissolution reaction
is given by:
z When a solid chemical compound (e.g. chloride and sulphate salts
and metal hydroxides) is added to water, it dissolves to some entent. Keq = [Ab+]a [Ba-
a ]b /[A B (s)] Or K
a b eq = [M ] [OH ] /[MOH(s)]
+ -

This reaction, known as dissolution, is expressed as: Aa Bb(s) =aAb+

+ bBa- where s indicates a solid. As the concentration of solids do not change; thus, instead
z The reaction proceeding from left to right is called dissolution, of the equilibrium constant Keq , the solubility product constant, Ksp is used.
which proceeding from right to left is precipitation Ksp = [Ab+]a [Ba-]b or Ksp = [M+] [OH-]
z Example:
precipitation-dissolution of NaCl is Refer Table 3.3, the Ksp [or = -log10 (Ksp )] of different chemical compounds
NaCl(s) = Na+ + Cl- will help to determine the extent of solubility for selected solid substances.
The lower the Ksp value,
value the higher the dissolution of solid chemical
dissolution-precipitation of a metal hydroxide is compounds. Such information is very useful in geoenvironmental studies,
MOH (s) = M+ + OH- particularly in remedial system design
where M is any cationic metal

3. COMPLEXATION REACTIONS 3. COMPLEXATION REACTIONS

z This refers to a process where some ions or z The pproperties

p of metal complexes
p mayy be qquite different
molecules dissolved in water will combine with a from those of the metal itself, e.g. the solubility of a metal
complex may be much higher than that of the metal itself
variety of other ions or molecules to form several
z Complex
C l reactions
ti are considered
id d carefully
f ll when
h
different species, known as complexation.
designing remedial systems to either enhance
z Example: containment removal or immobilise the containments in
z Mn2+ + Cl- = MnCl+ Keq = [MnCl+ /[Mn2+ ][Cl- ] soils and groundwater.
z The stability constants provide information on the
z Note: complexation reactions can also occur
preference of contaminants to complex with various
stepwise with equilibrium constant known as ligands
stepwise formation constants
4. OXIDATION-REDUCTION REACTIONS IMPORTANT PROPERTIES OF ORGANIC
z Also known as REDOX reaction
COMPOUNDS FOR GE ENGINEERING
z It is a chemical reaction in which an atom or ion loses electrons to
another atom or ion
ion. z Details in later chapters
p
z During the reaction, one compound loses electrons and another gains z These properties are measured by
them experiments or calculated using
z The redox reactions are important for chemicals that can exist in
different valence states (e.g. carbon, arsenic, chromium, copper, iron,
th
theoretical
ti l equations
ti andd correlations
l ti
mangenese, nitrogen and sulphur) z For many organic compounds, these
z The form of a chemical can significantly affect a remedial process
process, e e.g.
g properties have been reported in
chromium exists as trivalent chromium under reducing conditions and
hexavalent chromium under oxidising conditions
standard chemistry handbooks
z Since the properties of these two chromium forms are quite different
different, z Quantitative values of these properties
the remedial processes may have to different. for different organic compounds will be
cited in succeeding chapters, as
applicable
li bl

IMPORTANT PROPERTIES OF ORGANIC

COMPOUNDS FOR GE ENGINEERING NUCLEAR CHEMISTRY BACKGROUND
z A specialty
p y not commonly y dealt with by
y GE
professionals
1. Aqueous solubility z But once dealing with radioactive wastes or with sites
contaminated with radionuclides, an understanding of it
2
2. V
Vapour pressure is most essential
z Only basic concepts and terminology are provided,
3. y law constant
Henrys more details in other references.
references
4. Octanol-water partition coefficient z In nature, some elements have nuclei with unfavourable
proton/neutron ratios that they spontaneous breakdown
5
5. R t off biodegradation
Rate bi d d ti t achieve
to hi a more stable
t bl form.
f During
D i breaking
b ki down d
energy is released and unstable nuclei emit ionising
radiation in the form of particles, particles and
rays, a process known
k as radioactive
di ti decay
d

NUCLEAR CHEMISTRY BACKGROUND
All elements with atomic number >83
zAll 83 (termed
radionuclides) are unstable, examples of
common natural radionuclides are: uranium and
thorium. Other examples: plutonium, strontium,
cesium,
ces u ,a and
d coba
cobalt.
t z t1/2 and k are related by the equation t1/2 =0
zAll of these radionuclides are used extensively
for nuclear weapons and nuclear power
generation.
CHEMICAL ANALYSIS METHODS
zAccurate determination of the nature of
chemicals and their concentrations is
critical in geoenvironmental studies
zThe focus here is on toxic inorganic and
organic contaminants
contaminants, as they are the
most common contamination at most sites.
NUCLEAR CHEMISTRY BACKGROUND
z Radioactive decay is described by a first-order
reaction, dN/dt = -kN where N is the number or mass
of the undecomposed nucleide and k is the decay
constant.
constant
z More commonly, the radioactivity of a substance is
described by its half-life, t1/2, which is the time required
for 50% of a given number of radioactive atoms to
decay.
0.693/k
693/k
z The unit of radioactivity is the curie (Ci; 1Ci=3.7x1010
disintegrations per second)
z Radioactive contamination is common at Department
of Energy sites and nuclear power plant sites. These
are limited in number but their remediation is
complicated and challenging that requires special
expertise in nuclear chemistry
STANDARD REFERENCES
Two standard references routinely used in the US to
measure the organic and inorganic contaminants are:
1. Standard Method for Examination of Water and
Wastewater by American Public Health Association
2. Test Methods for Evaluating Solid Wastes by
US
USEPA
 METHODS USED TO MEASURE TOXIC
EQUIPMENT & ANALYSIS PROCEDURES INORGANIC CHEMICALS IN WATER
1. Atomic Absorption Spectrophotometry (AAS)
zEquipment and analysis procedures are Suitable for q
quantifying
y g the concentration of inorganic
g
available to detect chemical concentration chemicals (esp. metals) in water
between p parts pper billion ((10-9) to parts
p p
per
trillion (10 )
-12 Procedure:
A sample is aspirated and atomised in a flame. A light
zStrict QA/QC is required
q to ensure beam from a hollow cathode lamp is directed through the
accuracy of the analysed results flame into a monochromator and onto a detector that
zA QA/QC p plan is p
prepared
p conforming g to measure the amount of absorbed light. Absorption
d
depends
d on the
th presence off the
th unexcited
it d ground-state
d t t
this plan during testing & documentation atoms in the flame. Because the wavelength of the light
prepared for each project. beam is characteristic only of the metal being
determined, the light energy absorbed by the flame is a
measure of the concentration of that metal in the sample.

METHODS USED TO MEASURE TOXIC METHODS USED TO MEASURE TOXIC

INORGANIC CHEMICALS IN WATER ORGANIC CHEMICALS IN WATER
2. Inductively coupled plasma-mass spectrometry 1. Gas Chromatography (GC)
(ICP-MS) Suitable for the analysis
y of organic
g compounds
p that can
be volatilised without changing chemical structure that it
Suitable for detection and quantification of a large can be used to determine large numbers of volatile
number of inorganic
g chemicals simultaneously y in hydrocarbons.
hydrocarbons
water
Procedure:
Procedure: A liquid sample is injected into the instrument which
A sample is ionised at a high temperature in a vaporise the chemicals. They then travel at different
plasma (a high temperature ionised gas) and then speeds
d through
th h a GC column
l andd exit
it att different
diff t times.
ti
send to the spectrometer, which detects and By recording the chromatograph (i.e. pattern that is
quantifies individual atoms by
q y matchingg the existed by the chemicals as they exit), the nature and
signatures of various chemicals with those of the quantities of organic compounds present in the sample
known chemicals can be determined.
 METHODS USED TO MEASURE TOXIC
ORGANIC CHEMICALS IN WATER
2. Gas Chromatography mass spectrometry (GC-MS)
Suitable for the identification and quantifying a large
number off organic compounds, including volatile and
semivolatile organics.
Procedure:
A small sample is injected into the instrument, where the
sample vaporises instantly.
instantly Individual molecules travel
through a narrow column (tube) in the instrument at
different speeds, exit out of the column, and enter the
mass spectrometer
spectrometer, where the electronic beam breaks
them into fragments. By studying the pattern formed by
the broken molecules and their abundance, the nature
and quantity of the chemicals present in the sample can
be determined.
SUMMARY
1 Brief review of environmental-concerned
1. environmental concerned
chemistry in water or aqueous solutions, a
background essential for understanding the
behaviour of chemicals in soils and water i.e.
geochemistry is presented
2. Basic concepts like chemical concentration, equilibrium
reactions, acids and bases, kinematic, redox reactions,
and gas laws are key parts of understanding inorganic
contaminants
3. The characterization, classification, and properties of
organic compounds are important aspects of
understanding organic contaminants
4
4. Knowledge of radioactivity at the atomic level is essential
in understanding radionuclide contaminants
METHODS USED TO MEASURE TOXIC
ORGANIC CHEMICALS IN WATER
3. High performance Liquid Chromatography (HPLC)
y g less volatile compounds
Suitable for analysing p that are
not suitable to be tested with GC. It is used to identify
and quantify organic compounds such as polycyclic
aromatic hydrocarbons (PAHs)
Procedure:
A sample is injected into the instrument along with a
solvent. The detector in the instrument identifies the
compounds d
SUMMARY (continue)
5. A background in inorganic, organic, and nuclear chemistry is
essential for an understanding of the cause of contamination and to
develop technologies for its removal.
6. An in-situ remediation method known as chemical oxidation, for
example, is based on redox reactions between organic/inorganic soil
contaminants and a given oxidant.
7. It is important to be familiar with chemical processes that determine
whether the oxidant will alter the contaminant successfully and
which new substances will be produced by the reaction.
8. Nuclear chemistry is important if one is dealing with radioactive
contamination which, however, is far less common than organic and
inorganic contamination
9. When situation in (7) above arises the problem must be resolved
promptly and efficiently perhaps by a well-trained personnel in the
field