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Subject Chemistry

Paper No and Title 4: Environmental Chemistry

Module No and Title 17: Soil pollution: Metals

Module Tag CHE_P4_M17

CHEMISTRY PAPER 4: Environmental Chemistry

MODULE 17: Soil Pollution: Metals
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TABLE OF CONTENTS
1. Learning Outcomes
2. Introduction
3. Pollution from heavy metals
3.1.Metals as soil pollutants
3.2.Sources of metal pollution
3.3.Toxicity of certain metals: Pb, Cd, Hg, As and Cr
3.4.Prevention and Control
4. Summary

CHEMISTRY PAPER 4: Environmental Chemistry

MODULE 17: Soil Pollution: Metals
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1. Learning Outcomes
After studying this module, you shall be able to

• Know about the heavy metal soil contamination.

• Learn the various sources of heavy metals causing soil pollution.
• Gain information about the toxicity and health hazards of certain metals: Pb, Cd, Hg, As
and Cr.
• Identify the prevention and control measures of metal contaminated soil.

2. Introduction

Soil is an essential component of our environment and its quality can be maintained by land
management. We have already discussed about certain urban and industrial activities that cause
soil degradation and this module emphasizes upon the sources of heavy metal soil contamination
and their effect on the environment and the mankind.

3. Pollution from heavy metals

The problem of pollution from heavy metals affects the whole population and considers all the
three receiving sections. The principal emission sources come from the industries such as
petrochemical, extractive, metallurgy, mechanic, chemicals and ceramic. However, the current
module mainly emphasizes on the heavy metal soil pollution and its adverse effects.

3.1. Metals as soil pollutants

Metals are the natural substances that are found in the soil at low levels. Nevertheless, the metals
emitted by the processes such as mining, manufacturing, and the use of synthetic products result
in contamination in urban and agricultural soils. They remain in the soil indefinitely as the metals
don’t degrade.

Excess concentration of heavy metal in soil by direct or indirect means, can transfer through food
chain and are toxic for human health and environment. The problems associated with continuous
exposure to heavy metal results in mental lapse due to ‘Pb’, ‘Cd’ affects kidney, liver, and
gastrointestinal tract, ‘As’ leads to skin poisoning, affects kidneys and central nervous system and
many more diseases are possible due to excess metals. Acute toxicity from heavy metals is
possible through ingestion or skin contact, although is found in rare cases.

CHEMISTRY PAPER 4: Environmental Chemistry

MODULE 17: Soil Pollution: Metals
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The problem causing metallic elements exist in soil as positively or negatively charged species.
Hg, Cd, Pb, Ni, Cu, Zn, Cr and Mn are cations in the soil. On the other hand arsenic,
molybdenum, selenium, and boron are anionic compounds in the form of arsenates, molybdates,
selenides and borates.

3.2. Sources of metal pollution

Natural and anthropogenic both the sources are responsible for environmental pollution which are
hazardous to environment. Some of the natural sources include volcanoes, forest fires, seepage
from rocks into water, sea-salt sprays etc. These are significant but it is human activities that are
more responsible for an increase in the metals into the environment. Some of such activities
include:

Ø Mining: If land is not properly managed during mining, it becomes useless for other
purposes due to high metal levels.
Ø Fossil-fuel combustion: Metals are emitted during the fossil fuels combustion. Metal
particulates contaminates land by settling onto it.
Ø Municipal and Industrial waste-water treatment plants are another sources of metal
pollutants to water.
Ø Metal containing wastes from industries like electroplating, tanneries, textiles etc
disposed of on the land and water are another source of metal pollution.
Ø Fertilizers, pesticides, sewage sludge, and animal wastes applied to the soil also have
higher metal concentrations than natural soil levels, thereby causing metal pollution.

3.3. Toxicity of certain metals: Pb, As, Cd, Hg and Cr

Metal toxicity is the deadly effect of certain metals in definite forms and doses on life form. Some
of the metals are very toxic as they form soluble compounds poisonous in nature. Some toxic
metals replicate the action of essential elements in the body, thereby, interfere with the metabolic
processes to cause illness. It includes Cadmium, lead, mercury and radioactive metals.

3.3.1. Lead (Pb)

Optimum concentration of Pb

The Minnesota State Legislature has recognized 100 ppm of Pb as a bare soil standard. The
environmental protection agency of United State and most other states uses more than 100ppm
level of Pb. Around 300 ppm level is used based on risks measured on eating of soil by young
children.

CHEMISTRY PAPER 4: Environmental Chemistry

MODULE 17: Soil Pollution: Metals
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Since the soil lead is not taken by plants in large quantities therefore the level of lead in soil is not
dangerous for plants. Generally, the soil having total lead levels less than 300 ppm is safe but as
the level increases it results in lead poisoning via food chain.

Sources of Pb

The sources of lead contamination: 1) Paints containing lead, as the paint chips from old building
mix with the soil and contaminate it; and, 2) lead from auto emissions, mining, smelting, coal
burning electric power plants, lead acid batteries and incinerators. In present time the level of lead
in paints and gasoline is quite low but once it get deposited on soil it can persist for a long time
therefore to some extent these are the sources of lead contamination.

Generally, the lead is not absorbed by plants but if soil contains high lead content, plants can take
up some amount of it. It is estimated that some crops like corn, beans, squash, tomatoes,
strawberries and apples are not readily contaminated by lead. But leafy vegetables such as lettuce
and root crops e.g. carrots are likely to be contaminated by lead in high concentration.

Health effects of lead exposure

Exposure to lead especially in children results in a variety of adverse health effects. Drinking
water contaminated by lead can affect the mental and physical development of infants and
children. On the other hand young children show slight demotion in their learning abilities. In
adults the continuous exposure of lead may result in kidney and high blood pressure problems.
They can also have fertility problems and cataracts. Other symptoms are abdominal pain,
anaemia, and lesions of the central and peripheral nervous systems.

3.3.2. Arsenic (As)

Optimum concentration of As

The lethal dose of ingested arsenic trioxide is about 1-3 mg per kg body weight for adults, while
even a lower exposure of 1-4 mg per day can cause serious health hazards, including fatalities in
small children.

Sources of As

The concentration of arsenic is highest in contaminated water. From many years, coal based
power plants, ore-smelting operations and inorganic arsenic chemicals that are used in
agriculture, results in contamination of soil in local areas by introducing arsenic oxides. The
inorganic arsenical pesticides and oxides of arsenic when incorporated into the soil under
oxidation conditions get convert into arsenates. In some properties the arsenate ion is similar to
orthophosphate and can be absorbed by iron and aluminum components. This will affect the
deposition of arsenic in soils and hence its availability to plants.

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Smelting industries contributes in arsenic exposure. Also, the microelectronics industry (as
gallium arsenide), coal power plants, use of pesticides and glass manufacturing treat arsenic as a
preservative.

Health effects of arsenic exposure

Arsenic is said to be a 'slow killer'. The allergy (blisters) on hands and feet are symptoms of
arsenic exposure, which can be even turn into gangrenous and cancerous level. Its exposure can
also attack the internal organs of the body like the lungs and kidneys, which can result in cancer.
Signs of arsenic intoxication also include nausea, headache and several abdominal pain due to
damage to the gastro-intestinal mucous membranes, violent vomiting and diarrhea caused by
paralysis of the capillary control in the intestinal tract. Eventually, the gastrointestinal epithelium
may be sloughed off, followed by a decreased blood volume, decreased blood pressure, disturbed
heart action, failure of vital cardiovascular and brain functions and ultimately death.

3.3.3 Cadmium (Cd)

3.3.4 Cadmium
Optimum concentration of Cd
Cadmium concentration in commercial phosphate fertilizer has been reported in the range of 1-
91mg/kg. The Cd content of sea water vary from 0.05-0.12micro g/l. It is one of the most
dangerous heavy metal as its exposure to soil can readily absorbed by plants through and its high
concentration can accumulate in the plants tissues without showing stress. In this way, Cd may
affect the human health through food chain.

Sources of Cadmium

Cadmium enters the environment from mining and metallurgical operations, electroplating
industries, manufacturing vinyl plastics, electrical contacts, etc., various anthropogenic activities
are responsible for cadmium exposure to the soil and may affect environmental health.
Microorganism maintain the fertility of the soil. The toxic effects of heavy metal like Cd on soil
and activities of microorganism can be study under controlled laboratory conditions. Soil from
sewage sludge containing number of heavy metals and organic substances is used to study the
interaction between Cd and microorganism. It may have a toxic effect on the microorganisms
present in the soil which play an important role in maintaining the soil fertility.

Health hazards of Cd

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Acute cadmium toxicity may cause flu like symptoms such as chills, fever, and muscle ache also
known as "the cadmium blues." These symptoms may resolve after a week but only if there is no
damage to the respiratory system. Severe exposures results in tracheo-bronchitis, pneumonitis,
and pulmonary edema. Symptoms may be observed after some hours of exposure which includes
cough, headache, irritation in nose and throat, fever, chills and chest pain.

Cd exposure results in bones softening (osteomalacia), as mineral density in bones decreases and
they become weak. This results in joints and back pain and can also cause fractures.

3.3.4. Mercury (Hg)

Optimum concentration of mercury

Mercury levels in soils have been reported ranging from 0.01to 2 ppm. High values of Hg in
soils/sediments have been reported near outfalls around industrial units. The Hg near outfall of
chlor-alkali industries range from 9-110 ng/g of soil/sediments.

Toxicity of mercury

Mercury is highly toxic in nature. It can be introduced in the environment by several processes
and can be found naturally. Even very low concentration of Hg causes potential hazards via food
chains. Although ingestion of elemental mercury will not cause any damage to the digestive
system. But if other form of it like its salt HgCl2 is ingested it will damage the gastrointestinal
tract and results in kidney failure.

Sources of Hg

Maximum source of mercury is in the chlor alkali industry, mercury catalysts (HgCl2) in thre
manufacture of vinyl chloride plastics and acetaldehyde, electrical industry (production of
battery, lamps, and circuit breaker), pulp and paper industry, paints, fungicides, jewellery,
pharmaceuticals and in research processes. Thermometer contain elemental mercury therefore if
broken down released Hg(0).
Health hazards of Hg

Continuous inhalation of its vapors result in tremors gingivitis. Elemental mercury is

comparatively less toxic than methylmercury that is found in high concentration near gold mine
sites, as it is used to extract gold. If fish contaminated with methylmercury is eaten by people and
wildlife, it will affect the immune system. It also damages the genetic, enzymatic and nervous
system of the body. Developing embryo being very sensitive mostly get affected by it. It is more
dangerous because it is ingested readily and excreted slowly than any other form of mercury.

CHEMISTRY PAPER 4: Environmental Chemistry

MODULE 17: Soil Pollution: Metals
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3.3.5. Chromium (Cr)

Optimum concentration of Chromium

Wastes arising from tanneries are reported to have Cr concentration ranging from 10-50 mg/l.
Textile mills wastes are reported to contain Cr to the extent of 5-20mg/l.

Sources of Cr
Major sources of chromium exposure are chromate steel, cement, leather goods, tanneries and
textiles mills and welding fumes.

Toxicity of Cr
Cr is toxic in high concentration to both plants and animals. It is reported to cause perforations,
bronchiogenic carcinoma etc. Hexavalent Cr may be released from chromium metal by the
corrosive action of sweat and penetrate the skin. Cr(VI) is subsequently reduced to Cr(III).
Inhalation of corrosive Cr(VI) compounds lead to ulceration of the nasal septum. Exposure to
chromate dust increases the chances of lung cancer, and oral administration of 50ppm of
chromate has been associated with growth depression, liver and kidney damage.

3.4. Prevention and Control

The pollution caused by heavy metals is critical because it is extremely expensive and difficult to
clean the soil contaminated by it.

Traditional Remediation of Contaminated Soil

The metals that contaminate the environment cannot be easily removed. As they do not degrade
like organic molecules. But microorganism can be used to transform mercury and selenium.

Traditional treatments are expensive when the concentration of contaminated soil is large.
Treatments can be done in situ or ex situ. Some of them are:

1. Treatments under high temperature conditions

2. Solidifying agents
3. Washing process

Management of Contaminated Soil

It is an effective method to prevent uptake of pollutants by plants by leaving them in the soil. In
this case soil act as a sink, which results in breaking of the soil-plant animal or human cycle and
exerts toxic effects. The following management practices are not helpful in the removal of heavy
metal contaminants, but will help in reducing the potential for adverse effects from the metals –
depending upon the kind of metal.

1. Increasing the soil pH to 6.5 or higher.

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When the pH is low cationic metals are more soluble, so if the pH is high they are less available
to plants thereby reducing its effect on humans through ingestion of contaminated plants. Also
results the increasing the pH has negative effect on anionic elements.

2. Draining wet soils.

It will improves soil aeration and oxidation of metals by decreasing their solubility. But
chromium is present in its oxidized form therefore opposite is true for it. Active organic matter
can be used for reducing the chromium availability.

3. Applying phosphate.

Applying of heavy phosphate reduces the availability of metal cation, but anionic metal such as
arsenic is negatively affected by it. It also requires proper care as its high concentration can cause
water pollution.

4. Selection of plants for use on metal-contaminated soils

The leaves of plants contains higher metal concentration than their fruits or seeds. Leafy
vegetables like spinach has high risk of this contamination.

Plants for Environmental Cleanup

It is observed that plants can help in cleaning up of contaminated soil. This process of removing
soil pollutants e.g. pesticides, heavy metals, solvents, polyaromatic hydrocarbons, crude oil and
landfill leacheates by plants is known as phytoremediation.

In the recent study in Kuwait, it is seen that Wildflowers helps in degration of hydrocarbons from
an oil spill. Pesticides, ammunition compounds such as TNT can be removed by hybrid poplars.

Plants for Treating Metal Contaminated Soils

Plants can be used for removal of metal contaminates from soil and water.

Phytoextraction is the process of growing plants in contaminated soil. Metal contaminates from
this soil are then translocated by plant roots to the portion of plant above the ground. Metals can
be recycled by harvesting and then incineration of grown plant. . There are many crop growth
cycles which decreases the contamination level of soil. . Ash obtained from plants incineration,
must be disposed of in a landfill, but its volume is much smaller than the volume of contaminated
soil if dug out and removed for treatment. hyperaccumulators, are plants which absorb metals in
higher concentration therefore can be used in phytoextraction. Metals such as nickel, zinc, and
copper can be easily phytoextracted. More than 3% of the zinc is taken by several plants in the
genus Thlaspi (pennycress). As the metal concentration is high they can be used as ore.

Rhizofiltration is a process in which root adsorption of contaminants that are in solution

surrounding the root zone takes place (rhizosphere). Rhizofiltration is used to remove ground

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water contamination. Plants in greenhouses are grown in water instead of soil. For this plants are
grown on contaminated ground water and roots take up this contaminated water. The plants are
harvested along with roots if it get saturated with the contaminant. In Chernobyl, Ukraine,
Radioactive contaminates are removed from groundwater in the same way by making use of
sunflower (EPA, 1998).

Phytostabilization is used by non-harvested plants for stabilization of soil and water

contaminates. Roots absorb the metals or they precipitated within the rhizosphere. Metal-tolerant
plants can be used if natural growth of vegetable is not taking place. This will decrease the risk of
soil erosion. Phytostabilization basically reduces the velocity by which contaminants are growing
into groundwater or the air

Example of Disposal

Plants for Treating Metal Contaminated Soils

Lead is considered to be most toxic metal for soil. Naturally the lead is not absorbed by plants it
requires a chelator such as EDTA (ethylenediaminetetraacetic acid) which makes the absorption
of lead by plants possible. Lead can be extract by using Indian mustard. Phytotech (a private
research company) has reported that in New Jersey Indian mustard is used in order to reduce the
lead contamination sites below the industrial standards.

Plants can be used for removal of zinc, cadmium, lead, selenium, and nickel from soils. The
plants that are accumulated by metals in higher concentration it will produce low biomass.
Currently the efforts made by genetic engineering at USDA in Beltsville, MD, results in
development of pennycress (Thlaspi) that is extremely zinc tolerant. These taller-than normal
plants would have more biomass, thereby taking up larger quantities of contaminating metals.

Traditional cleanup and removal of contaminated material may cost $10.00 to $100.00 and
$30.00 to $300 per cubic meter. In comparison to this, phytoremediation only cost $0.05/ m3.

4. Summary

• Heavy metals are present in soil as pollutants.

• Pb, Hg, Cd, As and Cr as pollutants in soil.
• Their optimum concentration, sources of pollution, toxicity effect and well known real
world cases of heavy metal poisoning.
• Prevention and control methods.

CHEMISTRY PAPER 4: Environmental Chemistry

MODULE 17: Soil Pollution: Metals