Aquatic Chemistry

CHE 3212

Dr S Wanniarachchi
Professor in Chemistry
Department of Chemistry
 Learning Outcomes

• Learn special properties of water

• List basic water quality parameters
• Explain how to determine WQP
• Calculate certain WQP
• Interpret analytical results
 Content

• Introduction to aquatic chemistry

• Define basic water quality parameters
• Occurrence/Origin
• Health/Sanitary significance
• Normal methods of analysis
• Pourbaix diagrams
References
 INTRODUCTION

THE PROPERTIES OF WATER

Water has a number of unique properties that are essential to

life and that determine its environmental chemical behavior.

Many of these properties are due to the polar molecular

structure and its ability to form hydrogen bonds.
 Where Earth’s Water is Found

About 97% of Earth’s water is in oceans

Most of the remaining water is in the form of solid snow and ice
Less than 1% of Earth’s water as water vapor and clouds in the
atmosphere, as surface water in lakes, streams, and reservoirs, and
as groundwater in underground aquifers
 THE PROPERTIES OF WATER

- Excellent solvent
- Highest dielectric constant of any common liquid.
- Higher surface tension than any other liquid.
- Transparent to visible and longer-wavelength fraction of
ultraviolet light.
- Maximum density as liquid at 4 oC.
- Higher heat of evaporation than any other material.
- Higher heat capacity than any other liquid except ammonia
• Water has a variety of unusual properties because of
attractions between these polar molecules.

The slightly negative

regions of one molecule
are attracted to the slightly
positive regions of nearby
molecules, forming a
hydrogen bond.

Each water molecule

can form hydrogen
bonds with up to
four neighbors.
 HYDROGEN BONDS

• Hold water molecules • Extraordinary Properties that

together are a result of hydrogen
• Each water molecule can bonds.
– Cohesive behavior
form a maximum of 4
– Resists changes in temperature
hydrogen bonds
– High heat of vaporization
• The hydrogen bonds
– Expands when it freezes
joining water molecules
– Versatile solvent
are weak, about 1/20th as
strong as covalent bonds.
• They form, break, and
reform with great
frequency
 Properties of Water

• At sea level, pure water boils at 100 °C and

freezes at 0 °C.

• The boiling temperature of water decreases

at higher elevations (lower atmospheric
pressure).

• For this reason, an egg will take longer to

boil at higher altitudes
 Cohesion

• Attraction between particles of the same

substance ( why water is attracted to itself)
• Results in Surface tension (a measure of the
strength of water’s surface)
• Produces a surface film on water that allows
insects to walk on the surface of water
 Adhesion
• Attraction between two different substances.
• Water will make hydrogen bonds with others.
• Capillary action-water molecules will “tow” each
other along when in a thin glass tube.
• Example: transpiration process which plants and trees
remove water from the soil, and paper towels soak
up water.
 High Specific Heat

• Amount of heat needed to raise or lower 1g

of a substance 1° C.

• Water resists temperature change, both for

heating and cooling.

• Water can absorb or release large amounts

of heat energy with little change in actual
temperature.
 Water is Less Dense as a Solid

• Ice is less dense as a solid than as a liquid (ice

floats)
• Liquid water has hydrogen bonds that are
constantly being broken and reformed.
• Frozen water forms a crystal-like lattice
whereby molecules are set at fixed distances.
 Water is Less Dense as a Solid
•Which is ice and which is water?
 Water is Less Dense as a Solid

Water Ice
 Density of Water

• Most dense at 4 oC
• Contracts until 4 oC
• Expands from 4 oC to 0
oC

The density of water:

1. Prevents water from freezing from the bottom up.
2. Ice forms on the surface first—the freezing of the water
releases heat to the water below creating insulation.
3. Makes transition between season less abrupt.
 Density change and turnover (ventilation)
Fresh water maximum density at ~4C  Seasonal inversion and
stratification
 AQUATIC CHEMISTRY

Many aquatic chemical

processes are
influenced by the
action of algae and
bacteria in water.

algal photosynthesis fixes inorganic carbon from HCO3- ion in

the form of biomass (represented as CH2O) and carbonate ion,
CO32-. Carbonate undergoes an acid-base reaction to produce
OH- or it reacts with Ca2+ ion to precipitate solid CaCO3 .
Oxidation-reduction reactions in water: Most of the many
oxidation-reduction reactions that occur in water are mediated
(catalyzed) by bacteria. For example:
In the oxygen-deficient (anaerobic) lower layers of a body of
water bacteria convert inorganic nitrogen largely to ammonium
ion, NH4+.
Near the surface: where O2 is available bacteria convert
inorganic nitrogen to nitrate ion, NO3-.
Metals in water may be bound to organic chelating agents, such
as pollutant nitrilotriacetic acid (NTA) or naturally occurring fulvic
acids.
 Biologically Mediated Processes in Water

Specialized bacteria in water can utilize oxidized chemical species

with high oxygen contents other than molecular O2 for oxygen
sources.
Example: Nitrate ion, NO3-, acts as an oxidizing agent in the
bacterially-mediated biodegradation of biomass:
C6H12O6 + 3NO3- + 6H+  6CO2 + 3H2O + 3NH4+
By mediating chemical reactions, such as the one above,
microorganisms, particularly bacteria, largely determine the
chemistry that occurs in water.
Dissolved oxygen in water is very important.
Biodegradable organic pollutants cause biochemical oxygen
demand, BOD.
 CHEMICAL PROCESSES IN WATER

Biochemical processes including photosynthesis

2HCO3- (sunlight energy)  {CH2O} + O2 + CO32-
• {CH2O} represents biomass
Acid-base reactions
CO32- + H2O  HCO3- + OH-
Precipitation reactions
Ca2+ + CO32-  CaCO3(s)
Oxidation-reduction reactions, usually carried out by bacteria are
generally ones in which chemical species gain or lose oxygen
Example: Oxidation of S in H2S
H2S + 2O2 SO42- + 2H+
 Oxygen in Water

At 25˚ C the concentration of oxygen dissolved in water is only about

8 milligrams per liter of water (mg/L)

• Readily consumed by biodegradation of biomass (abbreviated

{CH2O}) by oxygen-utilizing bacteria:
{CH2O} + O2  CO2 + H2O
• Only about 8 mg of {CH2O} consumes 8 mg of O2
 O2 solubility and ventilation
O2 solubility is dependent on water temperature:
Usually oscillates between 6-14 mg/L in aerated natural waters. O2
diffusion in surface waters is a slow process aided by turbulent mixing
of water (and cold temperatures)

How much O2 do
aquatic organisms
need?
• 8-15 mg/L: Excellent
• 6-8 mg/L: OK
• 4-6 mg/L: Stressed
• 2-4 mg/L: Critical
• <2 mg/L: Hypoxia
 Acid in Water
The value of [H+] in pure water at 25˚ C is 1.00  10-7 mol/L and the
pH is 7.00.

• Such water is neutral, neither acidic nor basic.

• Water with a pH less than 7.00 is acidic, whereas water with a pH
greater than 7.00 is basic.

The average global concentration of CO2 gas in air in the year 2001
was about 370 parts per million by volume, and going up by about 1
ppm per year.
 pH of water

• The concentration of dissolved carbon dioxide, [CO2(aq)], in

water in equilibrium with 370 ppm atmospheric air at 25˚ C is
1.21  10-5 mol/L.
• Makes water slightly acidic because
CO2 + H2O  H+ + HCO3-
• [H+] = 2.3  10-6 mol/L corresponding to a slightly acidic pH of
5.6
 Humic Substances in Water

Water in nature may contain naturally-occurring chelating agents

called humic substances that are complex molecules of variable
composition left over from the biodegradation of plant material.

Humic substances bind with Fe2+ ion to produce gelbstoffe (German

for “yellow stuff”) which is very difficult to remove by water
treatment processes.
Humic substances produce trihalomethanes, such as chloroform,
HCCl3 during disinfection of water by chlorine
 Water Interactions With Other Phases
Most important chemical and biochemical processes in water occur
at interfaces between water and another phase (usually solid)
 Sediments
Sediments are variable mixtures of minerals, clay, silt, sand, and
organic matter

Formed by

• Erosion
• Sloughing of banks into water
• Washed in from watersheds
Chemical reactions, for example, as the result of photosynthesis:
• Ca2+ + 2HCO3 - + h {CH2O}(s) + CaCO3(s) + O2(g)
• Deposits solid CaCO3 (limestone)
• Deposits biomass, {CH2O}
 Effect of pressure on gas solubility
• The solubilities of solids and
liquids are not affected
appreciably by pressure

• When the pressure of a gas is

increased, as in (b), the rate at
which gas molecules enter the
solution increases

• The concentration of solute

molecules at equilibrium
increases in proportion to the
pressure

• So the solubility of a gas

increases with pressure
Pressure and Solubility of Gases
Solubility decreases as pressure decreases

• Soft drink bottled under

CO2 pressure greater than
1 atm

• When the bottle is

opened, partial pressure
of CO2 above the solution
decreases

• Solubility of CO2
decreases -> bubbles
 Pressure and Solubility of Gases
Henry’s law

The solubility of a gas in a liquid is proportional to the

pressure of the gas over the solution
c is the concentration (M) of the dissolved gas
c = kP P is the pressure of the gas over the solution
k is a constant (mol/L•atm) that depends only on temperature

low P high P

low c high c
Sample Calculation-- Henry’s Law

Calculate the concentration of CO2 in a soft drink that is

bottled with a partial pressure of CO2 of 4.0 atm over
the liquid at 25 °C. The Henry’s law constant for CO2 in
water at this temperature is 3.1  10–2 mol/L.atm.
Using Henry’s Law

•If the solubility of a gas in water is 0.77 g/L at

3.5 atm of pressure, what is its solubility at 1.0
atm of pressure? (The temperature is held
constant at 25°C.)
 Temperature and Solubility

Solubility of most solid solutes in water In contrast, solubility of gases in water

increases with increasing temperature decreases with increasing temperature

Thermal pollution of lakes and streams causes low

oxygen levels in deeper layers
 Physical Characteristics
• Taste and Odor

 Can be found at the source than at the consumer’s end

 Often use the words like swampy, grassy, medicinal, septic,
phenolic, fishy and sweet
 Surface water --- Due to the biological degradation of algae
 Ground water ---- Landfill leachate, dissolution of minerals
bacterial activities
 Taste and Odor
• H2S imparts a rotten egg odor
• Due to the anaerobic bacterial action on organic S, S, SO42- or
SO32-
• Chlorine taste (0.2-0.4 ppm) due to the disinfection
• Dissolved Fe and Mn (Underground water)

Taste and Odor removal

 Aeration
 Activated carbon
 Filteration
 Taste and Odor-Determination
• Judgment based on the sensory evaluation

• This will measure the acceptability of drinking water.

• Instrument used for odor testing --??

• Smoking and eating before the test should be avoided.

• Cl2 taste can be avoided by treating with thiosulfate
• Taste and odor problems may be the first alarm for the
potential contaminants
 Colour
• Make the water supply unacceptable
• Results from Fe and Mn ions, plankton, weeds
• Industrial waste may be an another cause

Colour Measurements

 True colour-Turbidity removed

 Classified by comparison of the sample with
known concentration of coloured solutions
 Colour measurements
• Apparent colour When the turbidity is not removed

Visual comparison method

• Compare the sample with known concentrations of

coloured solutions /glass colour disks

• Report wit the pH value

Colour units (CU) ---Colour produced by 1 mg of platinum /L

(chloroplantinate ion)
Or
Pt/Co Method
 Acceptable colour limits
• 15 true colour units (TCU)
• 10-15 CU- May not notice
• 100 CU- Appearance of a tea

Standards are not based on the health effects

Colour removal
• Coagulation
• Chemical oxidation
• Adsorption
 Temperature
• Almost constant T is required at all time
• Seasonal variations may not be able to avoid
• T values are not normally standardized because of the
insignificant health effects
• T has an influence on the
aquatic life
Taste
Dissolved O2
Solubility of solids
Rare of corrosion
trihalomethane formation increases with T
T readings must be done immediately (on site)
 pH

• raw water pH 4-9

• Slightly basic value is used (7-7.8) to avoid corrosion
• Normal range for dinking water 6.9-7.4
Health effect

• There is no immediate direct effect (apples pH 3, Carbonated drinks pH 3)

pH associated with
• Alkalinity, hardness, chlorination, coagulation, etc
 Alkalinity
• Caused by CO32-, HCO3- and OH-
• Defined as the acid neutralizing capacity of water
• 5-125 mg/L are expected for drinking water
• Should be determined as soon as possible
There are three types:
Hydroxide alkalinity
Carbonate alkalinity
Bicarbonate alkalinity

Determination
 Total alkalinity: Titration with H2SO4 acid with MO
indicator and expressed as mg/L CaCO3 equivalent
 Determination of alkalinity
• Sample pH Values > pH 8.3
– Two Step Titration
– Step 1. Indicator used is Phenolphthalein (endpoint at
pH 8.3 )
– neutralises alkalinity due to strong bases (OH- , CO32-)
– CO32-  HCO3-

– Step 2. Indicator used is Methyl Orange (endpoint at pH

4.5 )
– neutralises alkalinity due to weaker bases (HCO3-)
– HCO3-  H2CO3
 Alkalinity calculation
• 25.00 mL of water sample is titrated with 0.01 M H2SO4 using
phenolphthalein as the indicator. Colour change was observed
when 16.50 mL of H2SO4 is consumed. To the same flask, few
drops of methyl orange indicator was added and titration was
continued until the end point. Now the total volume is 23.50
mL.

• Calculate total alkalinity

• Calculate phenolphthalein alkalinity
 HW Problem
A 100 mL sample of water is tested for alkalinity. The normality
of the sulfuric acid used for titrating is 0.02 N. If 0 mL is used to
pH 8.30, and 7.60 mL titrant is used to pH 4.5, what is the
phenolphthalein and total alkalinity of the sample?
• Alkalinity provides buffering to resist changes
in pH value
• It is significant in many uses and treatments of
natural waters and wastewaters.
 Hardness
• Represents the total concentration of Ca2+ and
Mg2+ ions and reported as CaCO3
• There may be some contribution from other
poly valent ions
• Impacts the taste of water
• Hard water requires more soap to produce form
• Surface raw water is softer than ground water
Degree of hardness
 Carbonate hardness

• CO32- and HCO3- salts of calcium and

magnesium

Temporary hardness
• Dissolved calcium and magnesium bicarbonates
• can be removed by boiling
 Permanent hardness

• Hardness that cannot be removed by boiling

• Salt waters are not classified as a contribution
to hardness
 Advantages and disadvantages of hardness

• No adverse health effects

• Hard water taste is better
• It is thought to reduce number of heart illnesses
• Prevent pipe corrosion
• Deposited on kettles and pipes
• More soap is required for washing
 Methods of determination

• Titration with EDTA

(ethylenediaminetetraacitic acid)
• Indicator: EBT
2+ 2- 2- +
C a + H 2Y C aY + 2H
2+ 2- 2- +
M g + H 2Y M gY + 2H

2+ 2- - +
M g + H In M g In + H
- 2- 2- 2- +
M g In + H 2Y M gY + H In + H
 Determination of temporary hardness

• When water is boiled, temporary hardness

producing substances (bicarbonates) are
precipitated as insoluble carbonates or
hydroxides.
• This precipitate can be removed by filtration.
And the filtrate is used in the next step

Temporary Hardness = Total Hardness - Permanent

Hardness
 Solids
• Measure all suspended and dissolved solids
• Up to 500 ppm is allowed in drinking water

Total Dissolved Solids (TDS) : Residue upon evaporation

of filterable sample
Settleable Solids : Solids settle by gravity. Period of time
must be recorded
Total Suspended Solids (TSS) : is the portion of fine
particulate matter that remains in suspension in water.

Total Solids (TS) : All solids in a water sample determined

by evaporation and drying
 Conductivity

• Will give a quick determination of minerals

• More ions—more conductivity
• Conductivity is usually measured in micro- or
millisiemens per centimeter (uS/cm or mS/cm) or
(umhos/cm or mmhos/cm)
• Specific conductance is a conductivity measurement
made at or corrected to 25° C
Conductivity and TDS
 Turbidity

• Measure the amount of fine suspended matter

• Mostly Colloidal matter
• Clay, organic matter, plankton,
• Depends on light scattering and absorbing
properties
• Should be maintained under 5 units, ideally less
than 1 NTU
• Nephelometric turbidity Units (NTU)

international standard unit is called Formazin Nephelometric

Unit (FNU)
 Method of measurement

• Nephelometric method
• Give an indication of light scattered in one particular
direction
• Comparison is made with a standard reference
suspension.
• Formazin polymer is used

A suspension of 1.25 mg/L hydrazine sulfate and

12.5 mg/L hexamethylenetetramine in water has a
turbidity of one FTU
 Formazin polymer

Turbidity standards of 5, 50, and 500 NTU

 dissolved oxygen (DO)

• DO is essential for the maintenance of healthy lakes

and rivers.
• It is a measure of the ability of water to sustain
aquatic life.
• Analysis of dissolved oxygen is an important step in
water pollution control and wastewater treatment
process control.
• In a healthy body of water such as a lake, river, or
stream, the dissolved oxygen is about 8 ppm
• The minimum DO level of 4 to 5 mg/L or ppm is
desirable for survival of aquatic life
 Sampling for determination

• During the sampling, it is necessary to minimize

exchange of oxygen, which typically results in
contamination by atmospheric oxygen.
• If the sample is being collected from a bucket,
carefully immerse the BOD bottle into the water
so that water gently fills the bottle without
creating bubbles.
• Rinse the sample bottle twice with the sample
water.
 Experimental procedure

• At the time of sampling, DO is fixed by the addition of Mn(II)

under basic conditions, resulting in a brown precipitate,
(MnO(OH)2).
• Prior to analysis, the sample is acidified to pH 1.0-2.5.
• This causes the precipitated hydroxides to dissolve, liberating
Mn(III)/Mn(IV) ions.
• Mn ions oxidize previously added iodide ions to iodine. The
iodine is then titrated with thiosulfate solution using starch as
the indicator
• The thiosulfate solution is not stable and therefore must be
standardized with a primary standard, typically potassium
iodate (KIO3)
Theory
 Problem 3

• In a DO determination experiment, a student

titrated 50.00 mL of water sample with 0.0025 M
Na2S2O3 solution and observed the colour change
when 13.35 mL of Na2S2O3 was added. Calculate DO
in the water sample.
Calculation
 The Azide Modification

• Nitrite oxidizes I- to I2 under acidic conditions.

• When the reduced form of nitrite (N2O2) is oxidized
by oxygen, it is converted to NO2- again, establishing
the cycle that can result in erroneous results

When interference from nitrites is present, it is impossible to

obtain a permanent end. As soon as the blue colour of the starch
indicator has been discharged, the nitrites formed reacts with
more iodide ions to produce I2 and the blue colour of the starch
indicator will return
 How to overcome

• The nitrite interference is easily overcome with use

of sodium azide (NaN3), which is incorporated in the
alkali-KI reagent. When sulfuric acid is added,
following reactions happen.
Biochemical Oxygen Demand (BOD)

Definition
• The quantity of oxygen utilised by a mixed
population of micro-organisms to
biologically degrade the organic matter in
the wastewater under aerobic condition
• BOD is an important parameter in water
pollution control

• It is used as a measure of organic pollution

as a basis for estimating the oxygen needed
for biological processes, and as an indicator
of process performance.
 microorganism

Organic matter + O2 CO2 + H2O + new cells

• BOD test, 5-day at 20 oC

3-day at 30 oC
 Experimental Determination

1. Known amount of water sample is placed in a

BOD bottle.
2. Add dilution water. Dilution water is prepared by
adding phosphate buffer (pH 7.2), magnesium
sulphate, calcium chloride and ferric chloride into
distilled water. Aerate the dilution water to
saturate it with oxygen before use.
3. Measure DO in the bottle (DOi)
4. Closed the bottle and placed it in incubator for 5
days, at temperature 20 oC
5. After 5 days, measure DO in the bottle (DOf).
 Calculation

DOi  DO f
BOD 
P

Where
BODf = biochemical oxygen demand,
mg/L
DOi = initial DO of the diluted wastewater
sample, mg/L
DOf = final DO of the diluted wastewater sample
after incubation for five days, mg/L
P = dilution factor
P = dilution factor
=

Volume of sample
Volume of sample  Volume of distilled water
 Why dilution is needed?

• For a valid BOD test, the final DO should not

be less than 1 mg/L. BOD test is invalid if DOf
value near zero.

• Dilution can decrease organic strength of

the sample. By using dilution factor, the
actual value can be obtained.
 Example:

A BOD test was conducted on a wastewater

at 20 oC. The wastewater portion added to a
300 mL BOD bottle was 25.00 mL and the initial
and final dissolved oxygen values were 7.4
ppm and 2.1 ppm. Calculate BOD5
 Chemical Oxygen Demand (COD)

Definition
• The quantity of oxygen needed to
chemically oxidize the organic compound
in sample, converted to carbon dioxide and
water.
 Determination

• Add known amount of potassium

dichromate, sulphuric acid - silver sulphate
reagent, and a measured volume of sample
into a round bottom flask.

• The mixture is refluxed for two hours. The

oxidation of organic matter converts
dichromate to trivalent chromium.
Organic matter CO2
+ +
Cr2O72- H2O
+ +
H+ 2Cr3+
• The mixture is titrated with ferrous
ammonium sulphate (FAS) to measure the
excess dichromate remaining in sample.

• A blank sample of distilled water is carried

through the same COD testing procedure as
the wastewater sample.
• Ferroin indicator is used to indicate the
colour change.

• Colour change : Green to reddish brown

 Calculation

O 2 + 4H + + 4e 2H 2 O
Cr 2 O 7 2- + 14H + + 6e 2C r 3+ + 7H 2 O

Fe 2+ :1/6 C r 2 O 7 2- 1 C r 2 O 7 2- =3/2 O 2

1Fe 2+ = 1/4 O 2
 Calculation of COD
8000(a  b)
COD   [Fe(NH4)2(SO4)2 ]
V

Where:
COD = chemical oxygen demand, mg/L
a = amount of ferrous ammonium sulphate
titrant added to blank, mL
b = amount of titrant added to sample, mL
v = volume of sample, mL
8000 = multiplier to express COD in mg/L of oxygen
 Sample calculation:

In a COD determination experiment 50.00 mL

wastewater is titrated with 0.24 M FAS. Volumes
of FAS used for blank and the sample are 24.55
mL and 12.80 mL, respectively. Calculate the
COD concentration for the sample.
 Theoretical COD

K
C8HO
5 4 +O
2 K
2O+ H
2O+C
O2

• Balance the equation and Calculate COD

theoretical COD of 1.176 mgO2/mg
 Heavy Metals

What are heavy metals?

➢Metallic elements that are denser than other

common metals

➢Mercury, lead, cadmium and arsenic present the

greatest environmental hazard
❖Extensively used
❖Toxic
❖Widely distributed

➢Ultimate sink for heavy metals are soils and sediments

 Toxic Heavy Metals: Hg, Pb, Cd and As

Toxicity of the heavy metals:

➢Of the four, Hg is highly toxic in the elemental form

➢Exposure through inhalation of Hg vapor from

liquid Hg

➢All four are dangerous in the following form:

➢Cations (e.g. from soluble compounds)

➢Organometallic (i.e. bonded to organic molecules)

 Toxic Heavy Metals

Why are they toxic?

Mechanism of heavy metal toxicity

➢Due to strong affinity of metal cations (Mn+) for sulfur

Found in proteins

❖Sulfhydryl groups, - SH, in many enzymes, react

with ingested Mn+

❖Can deactivate the enzyme

=> stops or alters metabolic processes
 Mercury
Toxic forms:
➢Elemental (Hg liquid/vapor), and
➢Compounds of mercury
❖Inorganic salts – ex. mercuric nitrate, Hg(NO3)2
❖Organometallic – ex. methylmercury

Mode of entry:
➢Elemental Hg through inhalation
➢Ingestion
➢organomercury can also enter the body by absorption
through the skin
Toxic Heavy Metals: Mercury

Organomercury effects – Ex. methylmercury

➢Exposure in the womb can adversely affect a baby's

growing brain and nervous system

➢Impacts on cognitive thinking, memory, attention,

language, and fine motor and visual spatial skills have
been seen in children exposed to methylmercury in the
womb

Microorganisms convert Hg2+ into organomercury species

 methylmercury, CH3Hg+, and dimethylmercury, (CH3)2Hg
 methylmercury poisoning

❖Outbreaks of methylmercury poisoning occurred in

Minamata, Japan during the 1950s due to industrial
discharges of mercury into the Minamata bay. More than
3000 people died due to Minamata disease

❖Widespread mercury poisoning occurred in rural Iraq in

1971-1972, when grain treated with a methylmercury-based
fungicide intended for planting only was used by the rural
population to make bread, causing at least 459 deaths
 Minamata disease

1907 Chisso Corp. builds a fertilizer plant in the Minamata.

Plant begins dumping untreated wastewater into Minamata Bay

Plant begins to produce acetaldehyde to be used in the

production of plastic, perfume and drugs

30-70 tons of methyl mercury was dumped into the Bay

10,000 people affected by Minamata disease.

3,000 died
❖On August 14, 1996, Karen Wetterhahn, a Dartmouth
College chemistry professor, spilled a small amount of
dimethylmercury on her latex glove. She began
experiencing the symptoms of mercury poisoning five
months later and, despite aggressive chelation therapy,
died a few months later from brain malfunction due to
mercury intoxication.

❖On March 19, 2008, Tony Winnett, 55, inhaled mercury

vapors while trying to extract gold from computer parts (by
using liquid mercury to separate gold from the rest of the
alloy), and died ten days later.
 Lead
➢Elemental form is not an environmental problem until
it dissolves into Pb2+ (or the less stable Pb4+)
Mode of entry:
➢Pb2+: Usually through ingestion of contaminated water and
food
Effects:
➢Pb2+ can inhibit the synthesis of hemoglobin
➢Adverse effect on the nervous systems and the kidneys

➢Interferes with the normal development of children’s brains

❖Behavioral effects, including lack of attentiveness
Sources of Pb contamination in the environment:
➢Lead industries, mining and smelting
❖Air and dust emissions (processing or smelting of lead
ores)

➢Vehicle emissions (in many countries)

❖The U.S., Canada and Europe use unleaded gasoline

➢Piping, fixtures and solder

❖Common source of Pb2+ in drinking water

➢Leaching from landfills (discarded batteries and

other Pb- containing products)
 Cadmium
Mode of entry:
➢Mostly through ingestion of contaminated food (in the
form Cd2+)
❖Seafood, organ meats have the highest levels
among food
Effects:
➢Cd is acutely toxic (lethal dose ~ 1 g)
❖Fortunately, low levels of Cd (as Cd2+) is complexed
by a sulfur-rich protein and is eliminated by urination

➢Kidney disease may result from chronic exposure to

high levels of Cd
❖Excess Cd (not complexed by proteins) is stored in
the liver and kidneys
Cadmium
➢Acute environmental problem in the Jintsu River Valley
region, Japan
Source of contamination:

❖Contaminated (with Cd2+) irrigation water drawn from

the river, used for rice cultivation
❖Zinc mining/smelting plant upstream = source of Cd2+

Results of contamination
❖Degenerative bone disease called itai-itai (“ouch-
ouch”) in 100s of people
➢Severe pain in the joints
➢Resulted from Cd2+ replacing Ca2+ in the bones
Porous bones; Easily fractured
 Arsenic
❖ Elemental arsenic occurs in two solid modifications:
yellow, and grey or metallic.
❖ The element is a steel grey, very brittle, crystalline,
semimetallic (metalloid) solid. It tarnishes in air, and when
heated rapidly oxidises to arsenous oxide which has a
garlic odour.
❖ Arsenic and its compounds are poisonous
 Arsenic
Mode of entry:
❖Mostly through ingestion of contaminated water
❖As2O3 can be absorbed through the lungs and intestines
Effects:
❖A known carcinogen
❖Acute dose can be lethal
➢Causes gastrointestinal damage –severe vomiting;
diarrhea
❖Coagulates proteins and complexes with coenzymes
❖Inhibits production of ATP

Note: As (III) is more toxic than As (V) – presumably due to

stronger binding with S-containing proteins
Arsenic
Uses:
➢Pesticides (compounds of As) – prior to use of organic
pesticides
➢Doping agent in solid-state devices such as transistors

Sources of environmental contamination:

➢From the continued use of its compounds as pesticide
(e.g in CCA-treated wood, Chromated copper arsenate)

➢Unintended release during mining and smelting of

gold, copper, etc.
➢Lead and steel production
Arsenic’s lethal effect when consumed in acute dose is due to
gastrointestinal damage
Causes severe vomiting and diarrhea

➢Major problems from high levels of arsenic occur in the

Bengal Delta

❖Up to 40 million people in Bangladesh and in the West

Bengal region of India drink As rich water
❖WHO called this the “largest mass poisoning of
population in history.”
 Chromium
Common oxidation +3 and +6
states:
Trivalent, Cr3+ Hexavalent, Cr6+ (soluble)
(insoluble)

Relative toxicities
Cr (VI) (soluble, ionic) > Cr (III) (insoluble)

Sources of contamination
❖Industrial emissions (metal plating)
❖Leaching from hazardous waste sites
❖Unintended release during mining and smelting of gold,
copper