ACID RAIN

Topic 15
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 (CO
2
) occurring naturally in the
air dissolves in it, creates a solution of carbonic
acid (H
2
CO
3
)
H
2
O + CO
2
H
2
CO
3

Carbonic acid is not stable and dissociates in
water forming hydronium ions and hydrogen
carbonate with a pH around 5.6
H
2
CO
3
+ H
2
O HCO
3

+ H
3
O
+

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.
SO
2
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 SO
2
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
ACID DEPOSITION FORMATION
Commonly due to secondary pollutants that form
from the oxidation of nitrogen oxides (NO
x
) or
sulfur dioxide (SO
2
) 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
SO
2
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
SO
2
Partially soluble in water
Consequently, only a fraction of
atmospheric SO
2
exists in the dissolved
aqueous form when there is a cloud or
mist content in the air.
In the aqueous phase, SO
2
(aq) exists in
equilibrium with sulfite, SO
3
2-
(aq) and
bisulfite, HSO
3
-
(aq) ions.

AQUEOUS PHASE CHEMISTRY OF SO
2
The dissociation of gaseous sulfur dioxide in water occurs
by 3-fold process, as follows:

1. SO
2
(g) SO
2
(aq)
2. SO
2
(aq) + 2H
2
O(l) H
3
O
+
(aq) +HSO
3
-
(aq)
3. HSO
3
-
(aq) + H
2
O(l) H
3
O
+
(aq) + SO
3
2-(
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 SO
2
The oxidation of aqueous bisulfite or sulfite by molecular
oxygen relies on a metal catalyst such as Fe
3+
or Mn
2+
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 HSO
4
-
and may proceed as
follows:
HSO
3
-
(aq) + H
2
O
2
(g) HSO
4
-
(aq) + H
2
O (l)
HSO
4
-
(aq) + H
+
(aq) H
2
SO
4
(aq)


AQUEOUS PHASE CHEMISTRY
OF SO
2
Gaseous sulfur dioxide will also dissolve in
water to form sulfurous acid (H
2
SO
3
)
SO
2
(g) + H
2
O(l) H
2
SO
3
(aq)

The relative concentration of SO
2
and
H
2
SO
3
(aq) are related by the equilibrium
constant for this reaction.
GASEOUS PHASE CHEMISTRY
OF SO
2
SO
2

.
OH, O
3
several steps
H
2
SO
4
SO
4
2-

SO
2
can be oxidized into sulfuric acid
in the gaseous state, Ozone,
.
OH
radicals and H
2
O
2
play a role here.


AQUEOUS PHASE CHEMISTRY
OF NO
X
There are three equilibria to consider in the
aqueous oxidation of NO
x
:

1. 2NO
2
(g) + H
2
O(l)2H
+
(aq) + NO
3
-
(aq) + NO
2
-
(aq)
2. NO(g) + NO
2
(g) + H
2
O(l) 2H
+
(aq) + 2NO
2
-
(aq)
3. 3NO
2
(g) + H
2
O(l) 2H
+
(aq) + 2NO
3
-
(aq) + NO(g)

These reactions are limited by their dependence upon the partial
pressures of NO
x
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 SO
2
GASEOUS PHASE CHEMISTRY
OF NO

NO O
3
, OH
2
NO
2
OH, M
HNO
3
NO
3
-

The oxidation of NO via ozone and
HO
2
radicals produces NO
2
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
Ca
2+
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
Al
3+ .
Like acid molecules, Al
3+
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

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
SO
2
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 SO
2
and NO
x
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.
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 carbon 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 (CaCO
3
) 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 SO
2
Transport
Chemical
Cement
Fertilizer
Paper & Pulp
Glass
Ceramics
Iron & Steel
Nonferrous metals
Petroleum
Refineries
Paper Manufacturers
Metal Smelting
Food Preparation
Power Plants
Petroleum Products
Coal Mining &
Production

EXAMPLES OF INDUSTRIES
EMITTING NO
X
Petroleum
Paper & Pulp
Cement
Ceramics
Iron & Steel

Nonferrous metals
Petroleum Products
Refineries
Transport
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 CO
2
, 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 NO
x


2. Remove SO
2
particulates and NO
x
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, SO
2
is now being removed from flue
gases by a variety of methods.
Is the current state of the art technology used
for removing sulfur dioxide (SO
2
) from the
exhaust flue gases in power plants that burn
coal or oil.
FGD can remove 95% or more of the SO
2
in the
flue gases.

FLUE GAS STACKS
FLUE GAS DESULFURIZATION
METHODS USED TO REMOVE SO
2
FROM
FLUE GASES
Wet scrubbing using a slurry of sorbent,
usually limestone or lime to scrub the
gases.
Spray-dry scrubbing using similar sorbent
slurries.
Dry sorbent injection systems
The highest SO
2
removal efficiencies
(greater than 90%) are achieved by wet
scrubbers.
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.
The need for treatment or reuse of spent
liquid.
FGD CHEMISTRY WITH WET
SCRUBBERS
Scrubbing with basic solid or solution.
SO
2
is an acid gas and thus the typical sorbent
slurries or other materials used to remove the SO
2

from the flue gases are alkaline.
The reaction taking place in a wet scrubbing
using a CaCO
3
(limestone) slurry produces
CaSO
3
(calcium sulfite) and can be expressed
as:
CaCO
3
(s) + SO
2
(g) CaSO
3
(s) + CO
2
(g)
FGD CHEMISTRY WITH WET
SCRUBBERS
When wet scrubbing with Ca(OH)
2
(lime) slurry, the
reaction also produces CaSO
3
(calcium sulfite) and can
be expressed as
Ca(OH)
2
(s) + SO
2
(g) CaSO
3
(s) + H
2
O(l)

When wet scrubbing with a Mg(OH)
2
(magnesium
hydroxide) slurry, the reaction also produces MgSO
3
(magnesium sulfite) and can be expressed as:
Mg(OH)
2
(s) + SO
2
(g) MgSO
3
(s) + H
2
O(l)

Some FGD systems go a step further and oxidize the
CaSO
3
to produce marketable CaSO
4
.2H
2
O (gypsum)
CaSO
3
(s) + O
2
(g) + 2H
2
O(l) CaSO
4
.2H
2
O(s)

















2006
KEASIDAN AIR HUJAN TAHUN 2006





2007
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Keasidan Air Hujan 2008



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