Module 2.

Environmental aspects

Toxicity of metals, Inorganic & organic compounds:

There are a number of chemicals including a large number of metals and
metalloids in the environment. Some of these are toxic and others non-
toxic. Due to industrial discharge, these elements find their way into air, into
water and into soil in our environment. They get into our biological system
through food chain and disturb the biochemical processes, leading in some
cases to loss of life. The effects of some of the metals, metalloids,
inorganic compounds and organic compounds on the biochemical
processes will be discussed in the following sections.

Toxic elements:

The biosphere has evolved in close association with all the elements of the
periodic table and the organisms harnessed the chemistry of many metal
ions for essential biochemical functions. These elements are required, for
viability of biological processes, although in small doses. When the supply
of that essential element is insufficient, it limits the viability of the organism,
but when it is present in excess, it exerts toxic effects. Thus there are
optimal doses for all essential elements. This optimum varies widely for
elements since chemistry of the element varies. For example comparing
Cu2+ with Fe2+ or Fe3+, the former binds strongly to nitrogenous bases,
including histidine side chain of proteins whereas neither Fe2+ nor Fe3+
strongly bind to nitrogenous bases. Therefore Cu2+ is more likely to
interfere than iron with critical sites in proteins. At higher levels iron is
harmful, partly because it can catalyse the production of oxygen radicals,
and partly because excess iron can stimulate the growth of bacteria and
aggravate infections. Cr (III) is considered as essential element but Cr(VI)
is carcinogenic.

Cadmium along with lead, mercury and arsenic is a Lewis acid, with
particular affinity for Lewis bases, such as the cysteine. Thus it is possible
that the heavy metals exert their toxic effects by bonding with critical
cystein residues in proteins; although the actual physiological
consequences vary from one metal to another.

Mercury:

Mercury enters the environment mainly through industrial discharges from

chloroalkali plants, electrical apparatus production plants, agricultural
industry etc. which use a large number of fungicides for seed dressings.
Sewage effluent from these industries sometimes contains mercury upto 10
times its concentration in natural water. When the mercury is adsorbed on
sediments in the water bodies, the sulphate reducing bacteria in sediments
generate methyl mercury [CH3Hg+and (CH3)2Hg ; they volatilise out) and
release into the water. There it is absorbed by the fish from the water. The
CH3Hg+ ion forms CH3HgCl in the saline biological fluids, and this neutral
complex passes through biological membranes and is distributed
throughout the tissues of the fish. In the tissues the chloride is displaced by
peptide sulphydryl groups, since mercury has an affinity for sulphur ligands,
the methyl mercury is eliminated only slowly and is therefore subjected to
bioaccumulation, when small fish are eaten by bigger fish. Biomethylation
of mercury occurs in all sediments and fish everywhere have some
mercury.
But the levels are greatly elevated in bodies of water for which sediments
are contaminated by mercury from waste effluents. The worst case of
environmental mercury poisoning occured in the 1950s in Minimata, Japan,
where fish accumulated methyl mercury to levels approaching 100 ppm.
Thousands of people were poisoned and hundreds died from the poisoned
fish. Since methyl mercury is able to cross the blood-brain barrier, the
affected people suffered all symptoms of brain dysfunction. Similarly methyl
mercury can pass from mother to fetus, and a number of minimata infants
suffered mental retardation and motor disturbance before the cause of
poisoning was identified.

Elemental mercury enters the body through inhalation and carried by the
blood stream to the brain, where it penetrates the blood brain barrier and
again all symptoms of brain disfunction will occur. is not toxic since it
forms insoluble chloride in the stomach. Hg2+ again is non-poisonous and
forms strong complexes with sulphur containing amino acids and proteins.
This ion however does not get access to biological cell.

Arsenic:

Arsenic occurs in water as a result of mineral dissolution, industrial

discharges or the applications of insecticides. As (III) is more toxic than As
(V), because it binds more readily to sulphydryl groups of an enzyme and
inhibits the enzyme action. The inhibitory action is based on the inactivation
of pyruvate dehydrogenase through its complexation whereby the
generation of adenosine triphosphate (ATP) is prevented. By virtue of its
similarity with phosphorus, arsenic (III) interferes with some biochemical
processes involving phosphorus. In the ATP generation, the enzymatic
synthesis of 1, 3 diphosphoglycerate from glyceraldehydes 3-phosphate
is an important step. As (III) interferes by producing 1-arseno-3-
phosphoglycerate instead of 1, 3 diphosphoglycerate thereby inhibiting the
metabolic processes. It acts to coagulate proteins and forms complexes
with coenzymes. Like mercury, arsenic may be converted to more mobile
and toxic methyl derivatives such as methylarsenic acid and dimethyl
arsenic acid. In another recent discovery, low levels of arsenic were found
to inhibit activation receptors that suppress cancer and regulate blood
sugar and at high levels it is known to trigger diabetes as well as cancer.

Arsenic in drinking water is a slow poison. The first symptoms are

discolourisation of the skin. Later these develop into cancer and the liver
and kidneys also deteriorate.

Lead:

The main sources for lead in the environment are from auto exhausts from
gasoline, paints storage batteries and pipes. Lead can contaminate water
either from lead-based solder used in pipe and fitting connections. In
contact with O2 bearing water, the metallic lead can be oxidised and
solubilised.

The rate of dissolution is strongly pH dependent. The solubility of lead in

soft water is higher when compared to that in hard water which has a high
pH. Carbonates precipitate lead as sparingly soluble PbCO3. Another major
source of lead exposure is leaded gasoline in which lead tetraethyl is
added to improve octane rating by scavenging radicals and inhibiting pre-
ignition. These toxic compounds are readily absorbed through the skin and
in the liver and they are converted to trialkyl-lead ions, R3Pb+, which like
methyl mercury ions are neurotoxins.

The fine particles emitted by automobiles are retained within the lungs and
are absorbed by the body with an efficiency of about forty percent. These
particles can travel far on air currents. However most of the particles settle
out not far from where they are generated, contaminating the dust near
road ways and in urban areas with lead.

Lead enters the blood stream once absorbed in the body, and moves from
there to soft tissues. Lead is deposited in bones, because Pb2+ and Ca2+
have similar ionic radii. The body maintains about 15 25 g of lead per
100g of whole blood. The body responds to any increase in lead intake by
excreting in the urine as much as possible and the remainder is stored
primarily in the bones. At elevated lead levels in blood it inhibits the
enzymes involved in the biosynthesis of haeme, the iron-porphyrin complex
that binds to haemoglobin and serves as a binding site for O2.

The biochemical mechanism for the effects of lead on nerve cells is

uncertain, but the diminution of nerve conduction velocity can be detected
at low blood lead levels; higher levels cause nerve degradation. Studies
have shown that lead even at very low levels (as low as 5mg/dL) was found
to cause impairment in growth, hearing and mental development of
children.

The molecular mechanisms of lead toxicity has not been exactly identified.
It probably involves ability of Pb to bind to nitrogen and sulphur ligands,
thereby interfering with the function of critical proteins. By intravenous
injection of chelating agents, lead can be cleared from the body. The
chelators compete for the protein bind sites, and resulting Pb2+ chelate
complexes are excreted by the kidneys. The chelating agents are
administered as Ca2+ complex, to avoid stripping of calcium or other weakly
bound metals from the body. The strongly binding Pb2+ displaces the Ca2+
and is removed selectively.

Toxicity of Some Inorganic Compounds:

Oxides of carbon (eg., CO and CO2) even though carbon dioxide is a

natural and essential constituent of atmosphere, it may turn out to be a
deadly air pollutant because of it's potential as a green house gas.

sulphur dioxide (SO2) and

Oxides of nitrogen(NOx)

Carbon Oxides:

Carbon monoxide:

Carbon monoxide is a colourless, odourless, and tasteless gas, that is by

far the most abundant of the criteria pollutants.

Sources of CO pollution:

Industrial processes:

Carbon monoxide is formed during the incomplete combustion of carbon

containing compounds.

It is also produced in large amounts during the reaction between carbon

containing materials at high temperatures as in blast furnaces.
 Carbon monoxide is also produced during the dissociation of CO2 at
high temperature.

CO emission from vehicle exhaust:

Most of the CO in air comes from vehicle exhaust. Internal combustion

engines do not burn completely to CO2 and water; some unburnt fuel will
always be exhausted, with CO as a component.

CO in vehicle exhaust can be reduced by using partially oxidised fuels like

alcohol and by a variety of after burner devices. It tends to accumulate in
areas where vehicular traffic is more.

Natural processes:

Volcanic action, natural gas emission, electrical discharge during storms,

seed germination, marsh-gas production etc, are the natural processes that
contribute to a small measure for the presence of CO in the atmosphere.
Forest fires contribute to 7.2% of CO emissions and agricultural burning
contributes 8.3% of emissions. The atmospheric back ground concentration
of CO is 0.1 ppm.

Sinks:

In soil, the major CO sink is soil microorganisms. The major sink process in
the atmosphere is however the conversion to CO2 by reaction with hydroxyl
radical. This process is however rather slow and the reduction in CO level
away from the source area is almost entirely a function of atmospheric
dilution processes.

The residence time of CO in the atmosphere is of the order of 4 months

and it is removed from the atmosphere by reaction with hydroxyl radical,
HO:

The reaction of atomic hydrogen with atmospheric oxygen produces

hydroperoxyl radical, as a product:

(M is an energy absorbing third body, usually a molecule of O2 or N2)

HO is regenarated from HOO by the following reactions:

The hydrogen peroxide formed undergoes photochemical dissociation to

regenerate HO:

Toxicity of CO:
At levels of CO that occur in urban air, there are apparently no detrimental
effects on materials or plants, but those levels can adversely affect human
health. After entering the blood stream through the lungs, carbon monoxide
reacts with haemoglobin (Hb) to convert oxyhaemoglobin (O2Hb) to
carboxy haemoglobin (COHb).

Carbon monoxide, in fact, has a much greater affinity for haemoglobin than
does oxygen, so that even small amounts of CO can seriously reduce the
amount of oxygen conveyed throughout the body. With this blood stream
carrying less oxygen, brain function is affected and heart rate increases in
an attempt to offset the oxygen deficit.

Control of CO emissions:

As mentioned earlier since major contribution to CO pollution is from

transportation sources and gasoline fed internal combustions are primarily
accountable for it, control measures have been concentrated on the
automobiles. Carbon monoxide emissions may be lowered by using a
relatively low air fuel mixture, that is one in which the weight ratio of air to
fuel is relatively high. At air fuel ratios (weight: weight) ratios exceeding
approximately 16: 1, an internal combustion engine emits virtually no
carbon monoxide.

Modern automobiles use catalytic exhaust reactors to cut down on carbon

monoxide emissions. Excess air is pumped into the exhaust gas and the
mixture is passed through a catalytic converter in the exhaust systems,
resulting in oxidation of CO to CO2.
The greatest problem with catalytic reactors at present is lack of sufficiently
durable (50,000 driven miles) catalytic material. The catalysts now in use
are subjected to poisoning (deactivation) by the adsorption of materials on
their surfaces. One of the most effective catalytic poisons is lead and this is
one reason for the development of lead free gasoline.

Carbon Dioxide and Global Warming:

It may be recalled that our atmosphere is made of almost nitrogen, oxygen

and other gases and particles. If we focus our attention on other gases,
Carbon dioxide is a relatively insignificant non - pollutant species (present
level 356ppm) in the atmosphere. However its increasing concentration in
the atmosphere is of serious environmental concern. Among the
constituents of the atmosphere methane, chlorofluorohydrocarbons, nitrous
oxide, water vapour and carbon dioxide contribute to global warming. The
relative contribution of active gases that are radiated is shown in the
following Table.

Relative contribution of radiatively active gases to temperature rise

Radiatively active gases that absorb wavelengths longer than 4 mm are
called green house gases. As the fig.2 suggests, CO2 and water vapour
trap good portion of the outgoing thermal radiation attempting to leave the
earth's surface. Thus these green house gases act as thermal blanket
around the globe raising the earth's surface temperature beyond the
equivalent temperature.

Although the relative share of the radiatively active gases such as

chlorofluorocarbons, nitrous oxide, CO2 and methane has been significantly
increasing each year, the largest effect is still due to CO2. Anthropogenic
production of CO2 from burning fossil fuels exceeds that of the other green
house gases. Although the natural flux of CO2 to the atmosphere due to the
constant respiration of the biosphere is much greater, this flux is in balance
with photosynthesis. Every year the CO2 declines to a minimum
concentration in summer when photosynthesis in forests of northern
hemisphere converts CO2 to biomass and it rises to a maximum in winter
when the dead vegetation days, releasing its stored carbon as CO2 . The
oscillatory pattern is regular from year to year but it is super imposed on a
rising background average CO2 concentration, which increased from 314
ppm in 1958 to 365 ppm in 2000, a 17.5 percent increase in four decades.
Sources of sinks of carbon dioxide

The major important sink for CO2 is ocean. Because sea water is alkaline
and CO2 is acidic, the oceans are vast reservoir of CO2. However only the
surface layer of ocean, the top 75 meters, is in equilibrium with the
atmosphere and its capacity to absorb CO2 is limited. Exchange of surface
layer with deep oceans takes hundreds of years. The location of the
remaining carbon dioxide has been a subject of considerable debate, but it
is now widely accepted that vegetation absorbs much of the CO2. But even
with this natural sink sources, the CO2 level is continuously increasing
resulting in global warming. Global warming can shift the climate zones and
the existing forests may not be able to adapt, especially if the shift is rapid
and again the result may be loss of biomass.
Global warming may also lead to increased evaporation of water thereby
reducing water available for agricultural, municipal, and industrial use.

Sulphur Dioxide Sources and Removal:

The two natural sources of SO2 are volcanic eruptions and sulphur-
containing geothermal sources like geysers and hot springs.

Some important industrial sources of SO2 are (1) nonferrous smelters (2) oil
refining and

(3) paper and pulp manufacture.

Nonferrous smelters: With the exception of iron and aluminium, many

metal ores are sulphur compounds. When the ore is reduced to the pure
metal, its sulphur is ultimately oxidised to SO2. Thus when CuFeS2 ore is
reduced to copper, its sulphur is oxidised to SO2.

Oil refining: Sulphur and hydrogen sulphide are constituents of crude oil
and H2S is released as a gas during catalytic cracking. Since H2S is
considerably more toxic than SO2 it is burnt to produce SO2 before
releasing it in to the air.

Pulp and paper manufacture: The sulphite process for wood pulping uses
hot H2SO3 and thus emits SO2 in air. The kraft pulping process produces
H2S, which is then burnt to produce SO2.

Sulphur dioxide reactions in the atmosphere:

Sulphur dioxide once released can convert to SO3, in a series of reaction

which, once again, involve a free radical such as OH
Sulphur trioxide reacts quickly with H2O to form sulphuric acid, which is the
principal substance in acid rain.

Sulphuric acid molecules rapidly become particles by either condensing on

existing particles in the air or by merging with water vapour to form H2O
H2SO4 droplets. Often significant fraction of particulate matter in the
atmosphere consist of such sulphate aerosols.

The formation is promoted by the presence of hydrocarbons and nitrogen

oxides, which are key components of photochemical smog.

In relatively humid atmospheres, SO2 is probably oxidized by reactions

occurring inside water aerosol droplets, which proceed faster in the
presence of ammonia and catalysts such as manganese (II), iron (II), nickel
(II), copper (II), etc.

Effects of atmospheric sulphur dioxide:

When sulphur in an aerosol, it is possible for sulphur oxides to reach far

deeper into the lungs. The combination of particulate matter and sulphur
oxides can then act synergistically, with the effects of both together being
much more detrimental than either of them separately. Sulphur dioxide is
one of the serious air pollutants which are responsible for smog formation,
which has resulted in several incidents of loss of human lives.

Atmospheric sulphur dioxide is harmful to plants and leaf tissue is killed

with exposure to high levels of gas.

Sulphurous pollutants can discolour paint, corrode metals, and cause

organic fibres to weaken. Airborne sulphates significantly reduce visibility
and discolour the atmosphere.

Prolonged exposure to sulphates causes serious damage to buildings

made of marble, limestone and mortar, as the carbonates of these
materials are replaced by sulphates, which are water soluble.

Nitrogen Oxides In The Atmosphere:

Although there are many oxides of nitrogen known to occur, the only two
that are important in the study of air pollution are nitric oxide (NO) and
nitrogen dioxide (NO2). The most abundant oxide is nitrous oxide. This is
however chemically rather unreactive and is formed from the natural
biological processes in the soil. Nitrous oxide first undergoes
photochemical reaction. Atomic oxygen is formed. It reacts with another
molecule of N2O to give NO. The nitric oxide thus formed reacts with
ozone, thereby causing ozone depletion. They can be represented by the
following equations.
Nitric oxide is formed by the combustion of nitrogen-containing compounds
(including fossil fuels) by the thermal fixation of atmospheric nitrogen.

Thus all high temperature processes produce NO, which is then oxidised to
NO2 in the ambient air.

Nitrogen dioxide is very reactive and a significant species in the

atmosphere. At wavelengths below 398nm it undergoes photodissociation
to oxygen atoms,

giving rise to significant inorganic reactions, in addition to host of

atmospheric reactions involving organic species.

The principal reactions among NO, NO2 and HNO3 are indicated below:

Reactions of NO:
Reactions of NO2:

Removal of HNO3:

Nitric oxide and nitrogen dioxide are important constituents of polluted air.
These oxides, collectively designated as NOx, enter the atmosphere mainly
from combustion of fossil fuels in both stationary and mobile sources.

Harmful effects of nitrogen oxides:

NO, is not an irritant gas; in fact it is often used as an anaesthetic. High

concentrations of NO2 can produce pulmonary edema-an abnormally high
accumulation of fluid in lung tissue. For exposures ranging from several
minutes to one hour, a level of 50 100 ppm, NO2 causes inflammation of
lung tissue for a period of 6 8 weeks, after which time the subject
normally recovers. Exposure of the subject to 150 200 ppm of NO2
causes bronchititis fibrosa oblitera , a condition fatal within 3 5 weeks
after exposure. Death generally results within 2 10 days after exposure to
500 ppm or more of NO2.

NO2 also causes extensive damage to plants through its secondary

products such as peroxy acyl nitrite formed in smog. Exposure of plants to
several parts per million of NO2 in the laboratory causes leaf spotting and
break down of plant tissue. It also causes fading of dyes and inks used in
some textiles. Much of the damage to materials caused by NOx, such as
stress corrosion cracking of electrical apparatus, comes from secondary
nitrates and nitric acid.

Control of NOx emissions:

NOx emissions are difficult to control because efficiency energy conversion

requires high combustion temperatures, whether in cars or power plants.
Moreover there is a trade off between NOx and unburnt gases as the ratio
of air to fuel in the combustion chamber is varied. The NO production rate
is maximum near the stoichiometric ratio (just enough O2 to completely
oxidise the fuel), where the highest temperature is reached. If less air is
admitted to the combustion zone ("fuel-rich"), the NO production rate falls
along with the temperature, but the emission of CO and unburnt
hydrocarbon (HC) increases.

It is possible to lower both NO and HC by carrying out the combustion in

two stages, the first of which is rich in fuel and the second of which is rich in
air. In this way the fuel is burnt completely, but the temperature is never as
high as it would be for a stoichiometric mixture. This two-stage approach is
being incorporated in power plants; it has been tried in cars but with less
success.
The other approach to reduce emissions is to remove the pollutant from the
exhaust gases.

In automobiles, this is accomplished with a three way catalytic converter

(i.e it reduces emissions of HC, CO and NO).

In order to deal with both NO and unburnt gases the converter has two
chambers in succession. In the reduction chamber, NO is reduced to N2 by
hydrogen, which is generated at the surface of a rhodium catalyst by the
action of water on unburned fuel molecules.

In the oxidation chamber, air is added, and the CO and unburnt

hydrocarbons are oxidised to CO2 and H2O at the surface of
platinum/palladium catalyst.

The catalytic converter is quite effective in reducing automotive emissions.

Assignment questions:

1. What happens when carbon monoxide is increased in the air?

2. What harm is caused to environment due to sulphur dioxide?
3. How is carbon dioxide released into the atmosphere?