Topic 6

ACID RAIN
Acid rain is also known as acid precipitation or
acid deposition.
Acid precipitation is commonly used to mean the
deposition of acidic components in rain, snow,
dew or dry particles.
Acid rain occurs when sulfur dioxide and nitrogen
oxides are emitted into the atmosphere, undergo
chemical transformations and are absorbed by
water droplets in clouds.
The droplets then fall to earth as rain, snow,
mist,dry dust, hail or sleet.
ACID RAIN
The term acid rain is sometimes used more
generally to include all forms of acid deposition
both wet and dry deposition.
Wet deposition occurs when any form of
precipitation (rain, snow, etc) removes acid from
the atmosphere and delivers it to the earths
surface. This can result from the deposition of
acids in raindrops or by the precipitation,
removing the acids either in clouds or below
clouds. Wet removal of both gases and aerosol
are both of importance for wet deposition.
ACID RAIN
Dry deposition occurs via deposition in the absence
of precipitation and can be responsible for as much as
20 to 60% of total acid deposition. This occurs when
particles and gases stick to the ground, plants or other
surfaces.
ACID RAIN/ACID PRECIPITATION
Acid precipitation is not a recent discovery.
Robert Angus Smith, Britains first Air Pollution
Inspector, first used the phrase in the late 1800s.
He was the first person to make the link between
sulfur pollution and acidic rainfall.
NORMAL RAIN/PRECIPITATION
Precipitation is usually somewhat acidic, as the
carbon dioxide (CO2) occurring naturally in the air
dissolves in it, creates a solution of carbonic acid
(H2CO3)
H2O + CO2 H2CO3

Carbonic acid is not stable and dissociates in water

forming hydronium ions and hydrogen carbonate
with a pH around 5.6
H2CO3 + H2O HCO3 + H3O+
So normal rainfall is slightly acidic (pH 5.6)
ACID RAIN/ACID PRECIPITATION
Generally, the pH of 5.6 has been used as the baseline
in identifying acid rain because this is the pH value of
carbon dioxide in equilibrium with distilled water.
Hence, acid rain is defined as any rainfall that has an
acidity level beyond which is expected in non-polluted
rainfall. (below pH 5.6)
CAUSES OF ACID RAIN
Sulfur dioxide and oxides of nitrogen are the
primary molecules that contribute to acid rain.
SO2 emissions are responsible for 60-70% of the
acid deposition that occurs globally
More than 90% of the sulfur in the atmosphere is
of human origin.
Some 95% of the elevated levels of nitrogen oxides
in the atmosphere are the result of human
activities.
The remaining 5% comes form several natural
processes.
SOURCES OF SO2
Main sources of sulfur dioxide include:
1. coal burning coal typically contains 2-3% sulfur
so when it is burned, sulfur dioxide is liberated.
2. The smelting of metal sulfide ores to obtain the
pure metals. Metals such as zinc, nickel and
copper are all commonly obtained in this manner.
3. volcanic eruption
4. organic decay
5. ocean spray
6. petroleum
SOURCES OF NITROGEN OXIDES
The major sources of nitrogen oxides include:
1. Combustion of oil, coal and gas.
2. Bacterial action in soil
3. Forest fires
4. Volcanic action
5. Lightning
Malaysia: NOx Emission by Sources (Metric Tonnes) , 2009
Malaysia: SO2 Emission by Sources (Metric Tonnes) 2009
ACID DEPOSITION FORMATION
Commonly due to secondary pollutants that form
from the oxidation of nitrogen oxides (NOx) or
sulfur dioxide (SO2) gases that are released into the
atmosphere.
Reactions at the earths surface or within the
atmosphere can convert these pollutants into
nitric acid, sulfuric acid and particles of acid-
forming sulfate and nitrate salts
The process of altering these gases into their acid
counterparts can take several days, and during this
time these pollutants can be transported hundred
of kilometers from their original source.
ACID DEPOSITION FORMATION
SO2 and nitrogen oxides are converted into acids by a
complex atmospheric processes involving several
chemical reactions.
It is important to consider both aqueous and gaseous
phase chemistries in the formation of acid rain.
AQUEOUS PHASE CHEMISTRY OF SO2
Partially soluble in water
Consequently, only a fraction of atmospheric SO2
exists in the dissolved aqueous form when there is a
cloud or mist content in the air.
In the aqueous phase, SO2(aq) exists in equilibrium
with sulfite, SO32-(aq) and bisulfite, HSO3-(aq) ions.
AQUEOUS PHASE CHEMISTRY OF SO2
The dissociation of gaseous sulfur dioxide in water occurs
by 3-fold process, as follows:

1. SO2(g) SO2(aq)
2. SO2(aq) + 2H2O(l) H3O+(aq) +HSO3-(aq)
3. HSO3-(aq) + H2O(l) H3O+(aq) + SO32-(aq)

These equilibria are critically dependent upon the pH of the

precipitation (since hydrogen ions are involved in reactions
2 and 3 as well as droplet size. The sulfite and bisulfite
ions may be oxidized by a number of atmospheric
mechanisms to sulfuric acid
AQUEOUS PHASE CHEMISTRY OF SO2
The oxidation of aqueous bisulfite or sulfite by molecular
oxygen relies on a metal catalyst such as Fe3+ or Mn2+ or a
combination of both.
Oxidation by ozone is more appreciable as it does not
require a catalyst .
However, the dominant oxidation process occurs by the
action of hydrogen peroxide (formed in the gas phase from
free radicals) This reaction involves the formation of an
intermediate, possibly HSO4- and may proceed as follows:
HSO3-(aq) + H2O2(g) HSO4-(aq) + H2O (l)
HSO4-(aq) + H+(aq) H2SO4(aq)
AQUEOUS PHASE CHEMISTRY OF SO2
Gaseous sulfur dioxide will also dissolve in water to
form sulfurous acid (H2SO3)
SO2(g) + H2O(l) H2SO3(aq)

The relative concentration of SO2 and H2SO3(aq) are

related by the equilibrium constant for this reaction.
GASEOUS PHASE CHEMISTRY OF SO2
SO2 .OH, O3 several steps
H2SO4 SO42-

SO2 can be oxidized into sulfuric acid

in the gaseous state, Ozone, .OH
radicals and H2O2 play a role here.
AQUEOUS PHASE CHEMISTRY OF NOX
There are three equilibria to consider in the
aqueous oxidation of NOx:

1. 2NO2(g) + H2O(l)2H+(aq) + NO3-(aq) + NO2-(aq)

2. NO(g) + NO2(g) + H2O(l) 2H+(aq) + 2NO2-(aq)
3. 3NO2(g) + H2O(l) 2H+(aq) + 2NO3-(aq) + NO(g)

These reactions are limited by their dependence upon the partial

pressures of NOx present in the atmosphere, and the low solubility of
these oxides. Potential for increase in reaction rate exists with the use
of metal catalysts, similar to those used in the aqueous oxidation of
SO2
GASEOUS PHASE CHEMISTRY OF NO
NO O3, OH2 NO2 OH, M
HNO3 NO3-

The oxidation of NO via ozone and

HO2 radicals produces NO2 firstly and
then nitric acid after the interaction of
impact partner M via OH radicals
EFFECTS OF ACID PRECIPITATION
Acid precipitation has been a major environmental
concern for many decades now. Studies show that it
effects:
lakes and aquatic ecosystems
trees and soils
the atmosphere
architecture
materials
humans
EFFECTS ON LAKES AND AQUATIC ECOSYSTEMS
Several routes through which acidic chemicals can enter lakes.

They may enter directly as dry particles falling through the air or as wet
particles falling as precipitation, including rain, snow, sleet, hail, dew or
fog.
Lakes can be thought of as sinks of the earth, whereby precipitation
falling onto the land is drained into them via surface run-off and ground
water. Acid precipitation falling on to the earth washes nutrients out of
soil and carries toxic metals that have been released from soil into lakes.
An example of this latter method is spring acid shock when snow
melts rapidly due to a sudden temperature change. This releases acid
and chemicals into the soils . The melted snow then runs off into
streams and rivers and gradually makes it way into the lakes. The aquatic
ecosystem does not have time to adjust to the sudden change. Spring is
when many aquatic species like amphibians, fish and insects reproduce.
This sudden pH change is dangerous because the acids can cause serious
deformities in the immature creatures or annihilate whole species since
the young of many such species spend a significant part of their lifecycle
in water.
EFFECTS ON LAKES AND AQUATIC ECOSYSTEMS
Acids in water may affect the fish in lakes in two ways:

a) Direct effects
Acid directly interferes with the fishs ability to take in
oxygen, salt and nutrients. For freshwater fish,
maintaining osmoregulation is key to their survival.
Osmoregulation is the process of maintaining the
delicate balance of salts and minerals in their tissues.
Acid molecules in water irritate the gills of fish, causing
mucus to form that prevents the fish absorbing oxygen
efficiently and eventually suffocate.

Low pH affects balance of salts in fish tissues. Salts of

Ca2+ migrate away from acid waters, depleting calcium in
fish tissue which leads to weak spines and deformities
e.g weak exoskeleton and brittle or weak eggs.
EFFECTS ON LAKES AND AQUATIC ECOSYSTEMS
b) Indirect effects

Acids cause metals to be dissociated and released e.g Al3+ .

Like acid molecules, Al3+ ions irritate the gills of fish,
causing mucus to form and accumulate in their organs to
toxic levels.

In general as acidification starts, and the pH of the lake

decreases, crustaceans start to die out, mainly because of
reproductive problems.
At pH 5.6, algal growth is hindered and some species die.
As the pH falls, larger fish start to die through suffocation
and reproductive problems.
At pH 5, any surviving fish tend to be thin, deformed and
unable to reproduce.
At pH 4.5, lakes are nearly sterile.
EFFECTS ON LAKES AND AQUATIC ECOSYSTEMS
EFFECT ON AQUATIC ECOSYSTEM
EFFECT OF ACID RAIN
EFFECT OF pH
EFFECTS OF ACID PRECIPITATION ON HUMANS
Acid deposition can influence human health through the
following methods:

Toxic metals, such as mercury and aluminum, can be released into the
environment through the acidification of soils. The toxic metals can
then end up in the drinking water, crops, and fish, and are then
ingested by humans through consumption. If ingested in great
quantities, these metals can have toxic effects on human health. One
metal, aluminum, is believed to be related to the occurrence of
Alzheimer's disease.

Metals can be leached into public water supplies from pipes and soils
under acidic conditions. Long term exposure to elevated
concentrations of metals may lead to bioaccumulation in tissues and
subsequent detrimental health effects e.g kidney damage.
EFFECTS OF ACID PRECIPITATION ON
HUMANS

Increased concentrations of sulfur dioxide and oxides

of nitrogen have been correlated to increased hospital
admissions for respiratory illness.
Research on children from communities that receive a
high amount of acidic pollution show increased
frequencies of chest colds, allergies, and coughs.
EFFECTS ON TREES AND SOILS
SO2 and acidic aerosols affect the stomata in tree leaves and
hinder photosynthesis.
Minerals in soils (K, Mg, Ca, Na) can be washed away and
replaced with hydrogen ions which inhibit photosynthesis.
These minerals are transferred to soil solutions and
removed as run-off or in groundwater. If this continues, the
silicate structure of the soil is gradually destroyed.
If soils become very acidic, aluminium from clay minerals is
freed and is absorbed by tree roots. So trees in acidic soils
will gradually become starved of their vital nutrients
(calcium and magnesium) and poisoned by the aluminium.
EFFECTS ON TREES AND SOILS
Reductions in soil pH can cause germination of seeds and
the growth of young seedlings to be inhibited.
Many important soil organisms cannot survive is soils
below a pH of about 6.0. The death of these organisms can
inhibit decomposition and nutrient cycling.
High concentrations of nitric acid can increase the
availability of nitrogen and reduce the availability of other
nutrients necessary for plant growth. As a result, the plants
become over-fertilized by nitrogen (a condition known as
nitrogen saturation).
Dry deposition of SO2 and NOx has been found to affect
the ability of leaves to retain water when they are under
water stress.
Acid precipitation can cause direct damage to the foliage
on plants especially when the precipitation is in the form of
fog or cloud water which is up to ten times more acidic
than rainfall.
EFFECT OF ACID RAIN ON TREES
EFFECT OF ACID RAIN ON
TREES
EFFECT OF ACID RAIN ON
TREES
ATMOSPHERIC EFFECTS
Constituents of acid pollution atmospheric nitrates,
sulfates can contribute to haze.
Haze can reduce visibility and interfere with
atmospheric energy processes by absorbing sunlight.
E.g. in the Artic, haze limits growth of lichen, thus
reducing its availability as a foodstuff for caribou and
reindeer.
EFFECTS ON ARCHITECTURE
Acid particles and precipitation deposited onto
stone buildings, monuments and statues cause
corrosion and stone damage.
Many historic buildings have been disfigured or
damaged irreparably by acid deposition.
Many ancient buildings and monuments are
composed of limestone, sandstone and marble.
Limestone (CaCO3) and turn to a crumbling
substance called gypsum (calcium sulfate) upon
contact with the acid, which explains the corrosion
of buildings and statues. Gypsum is readily soluble
and will be washed off the stone surface by the
action of rain, thus leaving a fresh surface of
limestone exposed to further attack
EFFECTS ON ARCHITECTURE
Building materials such as paint, plastic and steel may
be damaged by acid attack.
Any iron that is exposed to acid in the presence of
oxygen will rapidly dissolve and wash away, so
weakening the building structure and exposing fresh
iron to further corrosion.
Economically taxing to replace costly protective
coatings with greater frequency.
EFFECTS ON MATERIALS
Acid rain may damage materials such as fabrics such as
flags being eaten away by acidic chemicals in the
precipitation.
Many old books and works of art have deteriorated because
the ventilation systems of the libraries and museums that
hold them do not prevent acidic particles from entering the
building.
Acidic water corrodes water pipes so leading to more
frequent pipe replacement.
Copper solubility increases sharply below pH 5.0 and also
with increasing temperature.
Metals leached from pipe walls can be consumed and bio-
accumulated by humans, leading to detrimental health
effects.
EXAMPLES OF INDUSTRIES EMITTING SO2
Transport Petroleum
Chemical Refineries
Cement Paper Manufacturers
Fertilizer Metal Smelting
Paper & Pulp Food Preparation
Glass Power Plants
Ceramics Petroleum Products
Iron & Steel Coal Mining &
Nonferrous metals Production
EXAMPLES OF INDUSTRIES EMITTING NOX
Petroleum Nonferrous metals
Paper & Pulp Petroleum Products
Cement Refineries
Ceramics Transport
Iron & Steel
REDUCING ACID DEPOSITION
Using low-sulfur lignite coal.
However, low-sulfur lignite coal has low heating value,
so more coal must be burnt to generate the same
amount of electricity. This increases air pollution by
emitting more CO2, toxic mercury, and radioactive
particles into the troposphere. Also increase costs.
REDUCING ACID DEPOSITION
Looking into alternate affordable and
cleaner energy sources.
Using wind turbines and burning natural gas in
turbines to produce electricity instead of coal.
Other alternative energy sources e.g. solar,
hydroelectric, nuclear, geothermal etc.
REDUCING ACID DEPOSITION
By controlling acid deposition
However, this is a political issue as people and
ecosystem affected by acid rain are usually quite
distant from those who cause the problem.

Reduce coal use

Countries with large supplies of coal e.g
China, India and U.S have a strong
incentive to use it as a major energy resource.
REDUCING ACID DEPOSITION
Adding pollution control equipment

1. Catalytic converters in cars to remove NOx

2. Remove SO2 particulates and NOx from smokestack gases.
Expensive. Flue Gas Desulfurization (FGD)

3. Adding lime to neutralize acidified lakes or surrounding soil.

Several problems with liming. It is expensive and temporary
remedy that usually must be repeated annually. It can kill some
types of plankton and aquatic plants and can harm wetland
plants that need acidic water. Finally, it is difficult to know how
much lime to put and where to put.
FLUE GAS DESULFURIZATION (FGD)
Tall flue gas stacks disperse the emissions by
diluting the pollutants in ambient air and
transporting them to other regions.
As a result of stringent environmental protection
regulations, SO2 is now being removed from flue
gases by a variety of methods.
Is the air pollution control technology used for
removing sulfur dioxide (SO2) from the exhaust
flue gases in power plants that burn coal or oil.
Certain FGD can remove 95% or more of the SO2
in the flue gases.
FLUE GAS STACKS
METHODS USED TO REMOVE SO2 FROM FLUE GASES
Wet scrubbing using a slurry of sorbent, usually
limestone or lime to scrub the gases.
The highest SO2 removal efficiencies (greater than 90%)
are achieved by wet scrubbers.
Spray-dry scrubbing using similar sorbent slurries (CaO)
This is a dry scrubbing process that is generally used for
low-sulfur coal. Able to achieve sulfur dioxide (SO2)
reduction above 80% with good reagent use. Waste
products are collected either in a baghouse or electrostatic
precipitator.
Dry sorbent injection systems
Dry Sorbent Injection (DRI) achieves between 40 to 75%
removal of sulfur dioxide and acid gases. Waste products
are collected either in a baghouse or electrostatic
precipitator.
SPRAY-DRY SCRUBBING
DRY SORBENT INJECTION
ELECTROSTATIC PRECIPITATORS (ESP)

Remove particulates
from the gas stream
FABRIC FILTERS (BAGHOUSES)

Remove particulates from the gas

stream
WET SCRUBBER
WET SCRUBBING
Wet scrubbers remove dust particles by capturing them in
liquid droplets.
In a wet scrubber, the polluted gas stream is brought into
contact with the scrubbing liquid, by spraying it with the
liquid, by forcing it through a pool of liquid, or by some
other contact method, so as to remove the pollutants.
The design of the wet scrubbers depends on the industrial
process conditions and the nature of the air pollutants
involved.
Inlet gas characteristics and dust properties (if particles are
present) are of primary importance.
Scrubbers can be designed to collect particulate matter
and/or gaseous pollutants.
If the gas stream contains both particle matter and gases,
wet scrubbers are generally the only single air pollution
control device that can remove both pollutants.
ADVANTAGES OF WET SCRUBBERS
For particulate control, wet scrubbers when
evaluated against fabric filters and electrostatic
precipitators (ESPs)
Have the ability to handle high temperatures and
moisture.
The inlet gases are cooled, resulting in smaller
overall size of equipment.
Can remove both gases and particulate matter.
Can neutralize corrosive gases.
DISADVANTAGES OF WET SCRUBBERS
Corrosion
The need for entrainment separation or mist removal
to obtain high efficiencies.
(An entrainment separator or mist eliminator removes
any liquid droplets that may have become entrained in
the flue gas.)
The need for treatment or reuse of spent liquid.
FGD CHEMISTRY WITH WET SCRUBBERS
Scrubbing with basic solid or solution.
SO2 is an acid gas and thus the typical sorbent
slurries or other materials used to remove the SO2
from the flue gases are alkaline.
The reaction taking place in a wet scrubbing using
a CaCO3 (limestone) slurry produces CaSO3
(calcium sulfite) and can be expressed as:
CaCO3(s) + SO2(g) CaSO3(s) + CO2(g)
 FGD CHEMISTRY WITH WET SCRUBBERS
When wet scrubbing with Ca(OH)2 (lime) slurry, the reaction
also produces CaSO3 (calcium sulfite) and can be expressed as
Ca(OH)2(s) + SO2(g) CaSO3(s) + H2O(l)

When wet scrubbing with a Mg(OH)2 (magnesium hydroxide)

slurry, the reaction also produces MgSO3 (magnesium sulfite)
and can be expressed as:
Mg(OH)2(s) + SO2(g) MgSO3(s) + H2O(l)

Some FGD systems go a step further and oxidize the CaSO3 to

produce marketable CaSO4.2H2O (gypsum), used in wallboard
industry
CaSO3(s) + O2(g) + 2H2O(l) CaSO4.2H2O(s)

Wet scrubbers are used in variety of industries such as

acid plants, fertilizer plants, steel mills, asphalt plants
and large power plants.
2006
KEASIDAN AIR HUJAN TAHUN 2006
2007
2008 Keasidan Air Hujan 2008

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