Paper No.

: 05 Environmental Biotechnology

Module :03 Land Pollution arising from high input of Agriculture

Principal Investigator: Dr Vibha Dhawan, Distinguished Fellow and Sr. Director

The Energy and Resouurces Institute (TERI), New Delhi

Co-Principal Investigator: Prof S K Jain, Professor, of Medical Biochemistry

JamiaHamdard University, New Delhi

Paper Coordinator: Dr Sanjukta Subudhi, Sr.Fellow,

The Energy and Resouurces Institute (TERI), New Delhi

Content Writer: Dr Rajeev Jain, Professor,

Jiwaji University, Gwalior

Content Reviwer: Dr. Nimisha Jadon, Assistant Professor,

Jiwaji University, Gwalior

Environmental Biotechnology
Biotechnology
Land Pollution arising from high input of Agriculture
 Description of Module
Subject Name Biotechnology

Paper Name Environmental Biotechnology

Module Name/Title Land Pollution arising from high input of Agriculture

Module Id 03
Pre-requisites

Objectives

Keywords

Environmental Biotechnology
Biotechnology
Land Pollution arising from high input of Agriculture
 Introduction:

• The environmental scientists have paid their attention towards pollution due to the
industrial activity. Such pollution was largely confined to the urban areas, in cities
and towns. Providentially, it is possible to control such pollution by effectively
arresting the faulty industrial growth and related activities.

• Much worse is pollution of soil and pollution due to pesticide residues. Less attention
has been paid towards this predicament. As a matter of fact arbitrary use of fertilisers
and excessive use of pesticides has created a great hazard.

• Both of these products find their way into food chain. They have direct implications
on human health. In rural areas, the pollution of lithosphere due to fertilisers or
pesticides is widely spread, that in agricultural country like oursit is almost impossible
to control it.

• There is clear data to show that crops are destroyed by industrial effluents, but some
grow well on them. Apart from contemplation of role of nitrogen and phosphorus
which promote eutrophication of effluent, we must also consider the role of elements
like potassium, copper, zinc, iron, manganese, molybdenum and even boron as the
micronutrient in soil. They usually promote growth of crops.

• As such the trace elements from soil, sediments are valuable asset. No doubt the
pesticides are a gift to man, but also they are a curse if not properly used. Majority of
these pesticides are not biodegradable even at elevated temperature. They leave
behind a toxic residue in the environment.

• Such toxicity is determined by LD50 value for pesticides. It is essential to study

agricultural pollution-a term which is attaining new dimension in developing
countries.

Environmental Biotechnology
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Land Pollution arising from high input of Agriculture
 • The interrelationship between pesticides and agriculture is considered. Attempts have
been made to cover the quantitative analysis of pesticides by conventional as well as
by instrumental methods of chemical analysis.

Fig 1: Land pollution

Chemistry of Soil

 Agriculture practices affect the quality of the soil. Such practice should be
environmentally friendly. The pesticide, insecticides or herbicides are important
components of agriculture.
 Soil consisting of minerals and organic matter is fundamental requirement of
agriculture. Weathering of rocks is common to soil. Soil in fact is mixture of
minerals, organic matter and water supporting growth of plant. It has loose texture.
 It contains 5% organic and 95% inorganic matter. Soil show different layers or
horizones. Top soil is used for analysis but subsoil is rarely analyzed. Large amount
of water is needed for the plant cultivation. Soil contains clay which reacts with
water from soil.

Environmental Biotechnology
Biotechnology
Land Pollution arising from high input of Agriculture
  The soluble manganese and iron are usually encountered in soil. Both are toxic to
plants in high dosages. Inorganic colloids from soil absorb toxic matter. The
microorganisms thrive on organic matter from soil.
 Organic humus contains humic and fulvic acids. The humification is process of
formation of the humus. Soil contains H+, Ca2+, Mg2+, K+ and Na+ with low levels of
the Fe2+, Mn2+ and Al3+ in hydrolyzed form. Common anions present in the soil are
HCO3-, CO3-, HSO4, SO4- and halides.
 The humus possess very high cation exchange capacity like ion-exchange resins.
Soil acts as buffer and maintains its pH. Acid sulphates are generated by
interaction of granite in soil. Plants grow if soil has neutral pH of 7.0. In area of
low rainfall soil becomes basic by interaction. The exchange of anions by soil is not
well defined. At low pH anions are held by electrostatic attraction, while at high
pH, the OW ions cleavage to the soil.

 The atmospheric carbon dioxide reacts with silica, carbon, calcium carbonate to return to
lithosphere as the great atmospheric sink. This in turn return these materials to
hydrosphere through water vapour and micronutrients from the soil.
 Soil contains considerable amount of organic matter. Primary minerals such as silica,
limestone and dolomites account for 70% of soil mass. Biological activity in soil depends
upon the form of water present in it.

 The microorganisms present in soil are also of great relevance. The important
microorganisms are algae, protozoa and actinomycetes. If they are present such soils become
productive. These microorganisms play an important role in mineral and fertilizer
breakdown in soil formation.

Pollution arising through agriculture and its effect on Human Health

 Soil has definite influence on health of man. Soil promoting good growth of plants
was due to presence of higher organic matter in soil. In India usually the excessive
pesticide applications contaminates the quality of soil.

Environmental Biotechnology
Biotechnology
Land Pollution arising from high input of Agriculture
  A pesticide called `heptachlor' causes cancer as it is carcinogenic compound.
Pesticides from agricultural use are degraded as chemical, photochemical and
biodegradation materials.
 The term desertification refers to loss of fertility of soil. While deforestation is
serious loss of forests. Water and wind cause soil erosion. The prevention of soil
erosion is called soil conservation.
 One such method includes the perennial plant growth as it prevents soil erosion. The soil
conservation and protection of water resources are interlinked with one another. The
land reforestation conserves both soil and water.
 The agricultural activity influences the chemistry of environment in several ways; like
disposal of animal plant or food processing waste; the contamination from application
of pesticides and fertilizers; depletion of natural soil nutrients and finally salt and
mineral accumulation from irrigation.
 Thus, agricultural waste is more serious than the solid or liquid waste generated due
to industrial activity. The waste from food and milk industry shall pose a serious
problem in future.
 The food processing industry produces more than 60% of waste from fruit peels. No
doubt it can be used for animal feed and as manure in soil. Cotton waste is useless
as it contains a good amount of pesticide residue, which in the long run is harmful
to animal or cattle.
 There is no substantial evidence to prove that fertilizers cause water pollution or
contamination but it leads to excess release of nitrogen and phosphorous in soil.
Nitrate is the worst enemy of high-yield farming.
 Nitrate is reduced to nitrite in the digestive system and causes a disease called
methemoglobinemia. Phosphate is also a widespread pollutant in agriculture. It travels
much slower in the soil as compared to nitrate, but it promotes eutrophication of
effluents with algal bloom.
 Nitrogen and phosphorus pollution illustrate far reaching chemical consequences of
man's agricultural activity. The agricultural activity removes these materials from
lithosphere and drops them into the sea, which is a permanent sink for chemicals.
 This agricultural pollution represents a permanent and irreversible depletion of the
resources of the lithosphere and steps must be taken to mitigate this menacing
problem.

Environmental Biotechnology
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Land Pollution arising from high input of Agriculture
 Function of nitrogen, phosphorus and potassium in the soil

 Potassium, calcium and magnesium are called macronutrients in soil, however the
presence of NPK are most essential in soil. The calcium is rarely deficient in soil.
Only in alkaline soil such deficiency is noted.
 The availability of magnesium depends upon the ratio of Ca/Mg in soil as at high
ratio magnesium is present less in soil. Sulphur promotes growth of plant when
present in amino acids, thiamin and biotin.
 NPK plays an important role in determining the quality of soil. 90% of nitrogen
in soil is organic nitrogen, generated by biodegradation of plants and animals. The
soil fertility is controlled by organic nitrogen.
 The presence of high nitrogen yields high proteins which are nutritious. Nitrate
is beneficial for plant growth. It was provided by legumes—a kind of plants.
Ammonium (NH4+) is strongly bound to soil and is conducive for growth of rice
and paddy, while Phosphorus is present in low concentrations.
 It is present as P034, H2PO4 or HP024- but first species is most common. So little
phosphorus is used as fertilizer in the soil.
 Finally, the role of potassium is important. It activates some enzymes and it
balances level of water in plants.

Soil - Micronutrients

 B, CF, Cu, Fe Mn, Mo and Zn are generally considered as essential

micronutrients for plants it present at low concentration.
 They function as components of enzymes. Mn, Fe, Cl-, Zn are involved in the process
of photosynthesis while Na, Si, Co are favorable nutrients. Boron is isomorphously
substituted for silicon in soil.
 Cu, Cr, Co, As, Se, Ni, Pb and Cd are specific minerals including sulphur. Some
plants accumulate high dose of micronutrients. They are called as the
hyperacumulators (1 mg/g of soil). e.g. Ni, Cu get hyper accumulated in soil.
Phytoremediation is process where plants accumulate metals in it.
 The addition of sequestering agents in soil like oxalate enhance the accumulation of
micronutrients in soil e.g. uranium with oxalic acid. is accumulated as its anionic

Environmental Biotechnology
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Land Pollution arising from high input of Agriculture
 complex. Mineral contents of the soil gets depleted due to rain, seepage, growth of
plants and crops.
 The soil deficient in mineral contents is unsuitable for further cultivation.
Nitrogen, phosphorus and potassium are essential for growth of plants, but they are
replenished through organonitrogen and organophosphorus compounds, which are
dumped in soil as the sink by plant and vegetable kingdom.
 However, vitally more important are elements like iron, manganese, zinc, copper,
molybdenum, and boron, which are most essential for the healthy upkeep of soil.
Each and every plant or crop does not need all of these metals, but they thrive better
on at least one of them.
 The plants have a tendency to extract one or more of these elements. The contents
of such an element is termed as 'available element' contents, while whatever is
available in total soil is termed as the 'total amount of a particular element' in the
soil.
 There is good availability in soil of molybdenum, copper, zinc and to a lesser
extent iron, manganese, cobalt and aluminium. Calcium, potassium, magnesium,
nitrogen, sulphur and phosphorus are otherwise present in substantial concentrations
in the soil. Micronutrients are not available to plants.

Soil – Characterization

 In early years microscopic examination of the soil was carried out to know its quality
but now chemical analysis is preferred, because it gives information on the
composition of soil.
 Soil is studied from the viewpoint of better plant growth for the human consumption.
For chemical analysis soil sample is extracted in acetic acid or ammonium acetate
hydrochloric acid or EDTA solution.
 Such analysis available nutrient reveals in soil. Potassium chloride is used to extract
nitrogen from soil. The particle size distribution of soil is important. This is shown
in Table 1 .

Table 1. Classification based on particle size

Environmental Biotechnology
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Land Pollution arising from high input of Agriculture
 Kind Particle Size (mm)
Coarse 2000-200
Fine 200-50
Silt 50-2
Clay 2-0

 The soil analysis can be roughly done by visual symptoms shown by plants. Before
the analysis sampling and sub sampling technique is most essential. Usually
random sampling is preferred.
 Soil depth must be also recorded during sampling. Soil sample is biologically active
hence dry sample is not taken. Over dying of sample destroys micro-organisms.
Bulk sample should be divided in subsamples. The dissolution of soil sample
depends upon its contents. It can be fused with sodium carbonate in crucible.

pH of Soil

 It is pH of soil-water in equilibrium system. The pH gives idea about its metal

contents and its exchange capacity. Agricultural soil has pH of 5.0 to 8.0 Zn Mn
Fe, Cu are more mobile at low pH in soil.
 A high pH induces trace element deficiencies. Microbiological activity is also
dependent upon pH. The organic acids or aluminum have buffering action on soil
with the formation of hydroxide as ultimate product. Excess of carbon dioxide
increases the pH. Acid base indicators also identify pH of the soil.

Necessity of Lime for Soil

 Lime is added to soil if its pH is acidic and is too low. Now how much lime is to
be added for lowering pH of soil is determined by soil analysis in terms of the
exchange capacity, climate, soil, particle size. Type of soil decides the dose of lime
to be added to soil so as to lower down its pH.

Analysis of Phosphorous

 We use 0.2 M sodium bicarbonate solution at pH 8.2 to know available

phosphorus in the soil. The extracted phosphate in solution of bicarbonate is analysed
colorimetrically with ammonium molybdate and potassium antimonyl tartarate to give

Environmental Biotechnology
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 molybdenum blue in the presence of reducing agent like ascorbic acid. The colour
is measured spectrophotometrically at 882 nm against reagent blank.

Analysis of Nitrogen

 The method for the analysis of the available nitrogen is different than for total
nitrogen. Nitrogen is converted to ammonia and determined titrimetrically as usual if
amount is less than 2%.
 The total nitrogen throws light on stock of organic nitrogen which is mineralized in
typical environment. The nitrogen is determined by the Kjeldahl method by
conversion to ammonia so formed is measured by titration or colorimetric analysis
as usual.

Analysis of Exchangeable Cation

 The factor of the exchangeable cation shows the abundance and presence of nutrient
elements in the soil. Ammonia is used to leach cations from soil. Such leached
solution is analysed by atomic absorption spectroscopy.
 Usually, the amount of sodium, potassium, magnesium and calcium is ascertained by
AAS method. Usually ammonium acetate or calcium carbonate is used for the
preparation of soil extracts before analysis.

Soil Analysis- Trace Element

 Usually, AAS is used for their analysis as it avoids time consuming separation
technique. Only spectral interference must be prevented during analysis e.g., Ca2+
with P034 forms salt thereby decreasing absorbance during calcium analysis if
silicate is present.
 It suppresses absorbance of the calcium, magnesium or iron. To prevent such
interferences Lantham salt is added as the releasing agent. The interference of
incomplete volatilization is usually eliminated by using hotter flame.
 Physical interference due to variation in density or surface tension or viscosity of
sample is eliminated by matching of sample and standard from same solution. The
mineral structure of soil is ascertained by X-ray diffraction e.g., clay minerals.

Environmental Biotechnology
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  In addition thermal methods are also used for mineralogical investigations e.g.,
TGA or DTA. The trace elements are accumulated by plants. They are called as
hyperacumulators (dose more than 1 mg/g).

Environmental Pesticides

 These are the chemicals used to kill pests. Though they are good to protect crop, they
are the worst enemies of the environment. Pesticides are generally divided in to
three categories as (i) Herbicides like carbamates, triazines, (ii) insecticides like
organophosphorus or organochlorine compounds and (iii) fungicides like
dithiocarbamates. Rodenticide is fourth uncommon class having a-naptholthiourea as
member.
 Chlorinated Hydrocarbon Pesticides

 DDT is important member of this class. These pesticides can be subdivided in to

alkanes, alkenes and aromatic hydrocarbous. DDT was obtained from chloral
condensation with monochlorbenzene.
 The other members are heptachlor, lindane, eldrin, dieldrin, chlordane, endrin and
mirex,. First four belong to cyclodione group. Endosulphone also belongs to this
class. They have low polarity and dipole moment and are Lipophillic.
 Their environmental degradation is slow, with half-life ranging from 2.0 to 15.5
years in soil. They all ultimately degrade to H2O and CO2 and other products. All
compounds are neurotoxic.

 Organophosphorus Insecticides

 They have high mammalian toxicity. Insecticides like parathion, dichloros,

dimethate, acetylchloline are of this group They have better water solubilities.
Dichlororos is most soluble (1 x 10 5 mg/L). They hydrolyse in water.

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  The maximum half-life is 40 days. The bioaccumulation for them is minimum.
They arrest enzyme of ester splitting process. Choline stearase facilities nerve
impulse. All of these insecticides cause interference of muscular function.
 All of them usually contain pentavalent phosphorus. Dichloros kills flies. Parathion
contains sulphur and kill bees. Malathione is more toxic with more sulphur and is
used to kill insects in backyard.

 Carbamates Insecticides

 They are more expensive than organophosphorus compounds e.g., Baygon and
carbonyl belong to this class. Carbamatic group is hybrid between ester and amide
group and is polar.
 They are relatively soluble in water and possess limited life in the environment, with
half-life of 1.5 days to one month at the most. In water they act like
organophosphorus insecticide by interference with enzyme mechanism.
 They are derivatives of carbonic acid. They readily react with water and undergo
decomposition. Carbofuran, carbaryl and aldicarb all have the LD 50 dose ranging
from 0.8 to 300 mg/kg in rats. Sevin is trade name for pesticide Pyrethrin is natural
pesticide obtained from dried flowers but it is unstable.

 Pyrethrins and Pyrethoriods

 These natural insecticide from flowers of chrysanthemum. They contain (> = 0) polar
group and hence oil liquids are Lipophillic, have high boiling point with high
molecular weight.
 They are used in mosquito coil. Pesticide vaporizes in air and kills mosquitoes, they
absorb UV radiation to undergo light induced photochemical reactions. They are
neurotoxic. They are absorbed on insect skin. They exhibit 'knock down effect' i.e.,
temporary paralysis in insects. Allethrin was first synthetic product of this group,
with low toxicity.

 Phenoxyacetic Acid Herbicides e.g., Auxins

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  They are hormone weed killers are polar and highly soluble in water; with low
toxicity. Dioxins contain toxic compounds (e.g., TCDD i.e., tetrachlorodibenzo-
doxin). 2, 4, 5 T belongs to this category or 2, 4 D is dichlorophenoxyacetic acid.
Both are used to kill weeds in farms 1,4 dioxin is most toxic pesticide.

 Polychlorinated Biphenyl (PCB)

 They are not truly insecticides but are toxic. They do not easily degrade. They are
insoluble in water, but soluble in hydrophobic media. They have low VP, good
electrical insulators and plasticizers property.
 By heating they give furans. The cooking oil if contaminated by PCB or furan leads
to skin discoloration. So we must destroy PCB at 1200°C. Similar to PCB,
furan is another polyaromatic hydrocarbons which is also great environmental
hazards.

Classification of Pesticides

 The pesticides are classified largely into five groups as shown in table 2. The
important class is chlorinated hydrocarbons containing aldrine, BHC, DDT,
lindane, chlorodane, while organic phosphorus pesticides include malathion,
parathion (ethyl and methyl); the third category of the pesticide is carbamate
compounds containing zectrion and carbaryl.
 The inorganic pesticides i.e., fungicides are copper, nickel, lead and arsenic salts,
while herbicides are arsenic trioxide, arsenious acid. Based on their use of killing
insects, rodents, they are termed as insecticides, herbicides, fungicides, etc.,

Table 2. Classification of Pesticides

S.N Types Classification Example

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 1. Insecticides Chlorinated Hydrocarbons Aldrin, chlordane, BHC,DDT

2. Insecticides Organophosphorous compounds Malathion, guthion, parathion

3. Insecticides Carbamate compounds Zectrion, carbaryl (sevin)

4. Fungicide Inorganic compounds CuSO 4, NiCl2, PbO2, AS2O3

5. Rodenades α- napthylthiourea Carbaryl organic Mercurials

Effects of Pesticides on Human Health

 Such effects have been extensively studied. In absence of pesticides crop

production would decrease due to the consumption by insects (- 5 to 15% loss). They
control diseases spread by insects e.g., DDT kills mosquito and stops spread of
malaria (malaricuses diseases 750,000 to 1500 persons).
 Insects on constant use develop immunity and are not killed by the insecticides. Pests
on frequent use of pesticides demonstrate resistance to DDT and similar
compounds. The resistance was also problem with use of antibiotics.
 Pesticides also cause harm to species (e.g., bee) which are useful to us. They cause
great changes in ecosystem. The consequences on human health are serious. They
promote occupational illness. Organophosphorus pestic ide can cause
instantaneous death.

Use of Pesticides in Agriculture and its Pollution

 Herbicides and insecticide are the integral part of agriculture production,

which in turn related to soil. The market is large for minor pesticides.
40%of the monetary value of agricultural pesticides stays in its minor use.
The contamination of soil occurs due to its interaction with water
containing pesticides.
 Those used to control invertebrates are called as the insecticides while for
control of snails is used mollusc acids and round worms are controlled by
nematicides.
 Vertebrates are killed by rodenticides (to kill rodents) avicides are used to
repel birds. Pesticides control fish population herbicides are used to kill

Environmental Biotechnology
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Land Pollution arising from high input of Agriculture
 plants while fungicides are used to kill fungi, just as bactericides are used
to demolish by algicides.
 The application of insecticides or herbicides in agriculture is most
important as excess had bad effect on health of man. In view of the
importance of pesticides in environment we would consider effects of the
pesticides like DDT, organophosphorous insecticides, carbamates,
herbicides, and polychlorinated biphenyls.
 The pesticide are the worst enemy of man on this planet. It not only
contaminates lithosphere, but also pollutes the atmosphere. Pesticides
include herbicides, insecticides, fungicides or rodenticides.
 These are persistent pollutants obtained during interaction of lithosphere
and biosphere. They are cumulative poisons in the body, they usually
accumulate in food chain and are hence hazardous.
 Few of them undergo metabolic formation and biodegradation. The
pesticides residue so formed by degradation is more dangerous than the
parent compound.
 The reaction in body involves interaction with iron porphyrins. Several
residues are carcinogenic. The metabolic products are also dangerous.
Some arsenic pesticides have made soil p ermanently infertile.
 They may sometimes increase instead of decreasing pest population due to
the effects of immunisation. A pesticide like DDT changes fertility of
mammals. Pesticides thus pose an alarming problem for mankind.
 DDT kills mosquitoes which spread malaria. In spite of this its use in
developed countries has gone down due to its harmful effects. However,
the production has remained same due to its consumption by developing
countries. Its indiscriminate application poses a serious problem.

Environmental Biotechnology
Biotechnology
Land Pollution arising from high input of Agriculture
 Environmental Biotechnology
Biotechnology
Land Pollution arising from high input of Agriculture