Heavy metal pollution in soil and its possible

mitigation aspect

Speaker: Dr.Tarik Mitran

Agricultural Chemistry and Soil Science

 What is a Heavy Metal?

The term heavy metal refers to any metallic chemical element that has a
relatively high density and is toxic or poisonous at low concentrations.

Examples of heavy metals include mercury (Hg), cadmium (Cd), arsenic

(As), chromium (Cr), thallium (Ti), and lead (Pb).

Heavy metals are those having densities five times greater than water,
and the light metals are those having lesser densities.

Humans consume metallic elements through both water and food.

Sources of heavy metals and their cycling in the
soil-water-air organism ecosystem
Industrial
Products Air Birds
Burned
fuel
Fertilizers
Pesticides Soil Plants Domestic Humans
animals

Rocks
in Water Fish
Earth’s
crust

It should be noted that the content of metals in tissue

generally builds up from left to right, indicating the
vulnerability of humans to heavy metal toxicity
Source: Brady(1994)
 Tannery
Distillery Battery

Anthropogenic
sources of heavy
metals in soil Mining
Electroplating

Steel Smelting Fly ash

Ia IIa
IIIa IVa Va VIa VIIa

Heavy metal

Transition metals Ib IIb

Lanthanides

Actinides
 Chemical Major uses and sources of soil
contamination
Arsenic Pesticides, plant desiccants, animal feed additives, coal
and petroleum, mine tailings and detergents

Cadmium Electroplating, pigments for plastics and paints, plastic

stabilizers and batteries, fertilizers

Chromium Stainless steel, chrome–plated metals, pigments and

refractory brick manufacture

Lead Combustion of oil, gasoline, and coal; iron and steel

production
Mercury Pesticides, catalysts for synthetic polymers, metallurgy,
thermometers

Nickel Combustion of coal, gasoline, and oil; alloy manufacture,

electroplating, batteries

Source: Moore and Ramamoorthy (1984)

 Table: Emission of Cadmium to the atmosphere
Sources Annual Emission (T/year)
Natural Sources
Windblown dust 100
Forest fires 12
Volcanogenic particles 520
Vegetation 200
Sea salt spray 1
Anthropogenic sources
110
Mining, non-ferrous metals
Primary non-ferrous metal Production
1600
Cd
200
Cu
2800
Pb
600
Zn
Secondary non-ferrous metal production
70
Iron and steel production
50
Industrial applications
60
Coal combustion Source: Nriagu (1980) and Vogeli Lange (1989)
 Table: 2 Heavy metals prevailing in soils
and their regulatory limits
Concentration Regulatory limit
Element
range (mg/kg) (mg/kg)
Lead 1-6900 600
Cadmium 0.1-345 100
Arsenic 0.1-102 20
Chromium 0.005-3950 100
Mercury 0.001-1800 270

Copper 0.03-1550 600

Zinc 0.15-5000 1500

Source: Salt et al (1994)
Heavy Metals Limit in Soil

Source: Sherman, 2002

Heavy Metals according to their Toxicity

Cd, As Extremely poisonous

Hg, Pb, Ni, F Moderately poisonous

B, Cu, Mn, Zn Relatively less poisonous

Behavior of Hg in the Environment

Source: US EPA, (1997)

 Table: species of Mercury and their toxicity

Hg species Bio –chemical property

Hg0 It is relatively inert and non-toxic.in vapour
form it is toxic.
Hg2+ Toxicity is low
RHg+(Organo- Highly toxic cause’s irreversible nerve and
mercurial) brain damage can be stored in tissue.
Abortion of baby affecting foetal .Borned
baby suffer mental fat retardation,
convulsion cerebral palsy
R2Hg(diorgano- Low toxicity but in acid medium converted
mercurials) to organo mercurials

HgS Insoluble, adsorbed in soil

Source: Das, 2005
 Fate of selenite in soil (1:10 water extract)
Heavy metal load field experiment: Dr. Imre Kádár, Nagyhörcsök
selenite
1000000
selenite
25000 25000 oxidation
900000

800000
1993 20000 1993 20000 2003
700000
ICP-MS signal [CPS]

ICP-MS signal [CPS]

ICP-MS signal [CPS]
600000 15000 15000

500000

400000 10000 selenate 10000

300000

200000 5000 5000

100000 selenate
0 0 0
0 10 20 0 10 20 0 10 20
duration [min] duration [min] duration [min]
organic selenium
Conclusion: selenite will be oxidised in soil to selenate
selenate more available for plants (it is analogous to sulphate)
risk of leaching
 Basic facts of Cr :
• Chromium (Cr) discovered first by the French
chemist Vanquelin in 1798 from red lead ore in the
Siberia.
• Cr is a transitional element in the group VI B.
• Cr (VI) is most toxic usually occurs associated with
oxygen as chromate (CrO42-) or dichromate (Cr2O72-)
oxyanions. Most mobile species.
• Cr (III) less toxic, less mobile & mainly found
bound to organic matter in soil & aqueous
environment.
• Besides organic Cr (III) are known to form complexes
with inorganic ligands (OH-, SO2-, NO3- and CO32-).
Organically complexed (citric and fulvic acids) Cr (III)
prevented from precipitation even upto pH 7.5.

• Hence in most natural systems Cr (VI) occurred as

CrO42- and Cr (III) present as hydroxides and various
organic complexes.

• Cr (VI) is a strong oxidising agent & reduced by

appropriate electron donor

HCrO4- + 7H+ + 3e- →

← Cr 3+
+ 4H2O
 Reactions in Soil – Water System
• In most natural systems, hexavalent Cr6+ present
as CrO42- & major trivalent Cr3+ species include
hydroxides & various organic complexes.

• Cr undergoes various chemical & biological

reactions in natural system that govern
speciation & in turn, environmental behaviour.

• Important among these reactions include

Oxidation or reduction
Precipitation or dissolution and
Adsorption or desorption
 A simple scheme involving reactions of Cr
in soil & water systems
Cr in water

Leachate

Cr3+ Kinetics of Redox Transformation Cr6+

Precipitation Adsorption &

Dissolution Desorption

Water Cr3+ &

Cr6+

Predicted Cr concentration

Source: Rai et al., 1989

 Effect of Cr on plant growth and
development
Process Crop/plant Effect
Germination Bushbean, Lucerne, Reduced germination percentage &
Mungbean, Sugarcane reduced bud sprouting
Root growth Rice, Mungbean, Decrease in root length & dry
Sorghum weight, increase in root diameter &
root hairs. Proportional variation in
cortical & pith tissue layers.
Shoot height Rice, Bushbean Reduction in plant height

Yield & Dry Cauliflower, Cabbage, Upto 50% reduction in yield.

matter Radish, Bushbean, Reduced number of flowers per
production Maize, Finger Millet plant. Reduced grain weight.
Increased seed deformity. Reduced
pod weight.
Source: Patel et al., 1992
Source: Sherman, 2002
Table: Heavy Metal Pollution Through Sewage Water

Soil Heavy metal (ppm)

Available TOTAL

Pb Cf Cr Pb Hg Cd Cr

Surface 1.8 0.02 0.6 43.8 4.6 9.6 23.2

Sub surface 2.3 0.04 0.04 40.3 3.8 10.1 19.8

Source: Som et al.

(1994)
Feer‘s Disease (acrodynia) exanthema
due to Hg Toxicity

Picture Source: www.who.int/ceh

 Table: 10 Sources and Estimates of Daily
Human Exposures to Mercury

Source of Methyl mercury Inorganic Hg Salts (Hg+ Elemental Hg (Hg0)

Exposure (MeHg) (μg/day) +
) (μg/day) (μg/day)
Foods (non-fish) Negligible 0.9 Negligible
Commercial fish 6 <1 Negligible
Sport fish No population-based data No population-based data Negligible
available available
Public supply Negligible <<4 Negligible
water

Private wells Negligible 0.4-4 0.006-0.03

Outdoor air Negligible Negligible 0.04 - 0.2
Indoor air Negligible Negligible No population based data
available
Soil ingestion Negligible >3 Negligible

Dental amalgams Negligible Negligible .3-17

Source: Charles, 2000

 Table: 13 Important hyperaccumulators
for metal remediation
Elements Plant species Max. reported
conc. (mg/kg)

Cadmium Thlapsi caerulescens 500

Copper Ipomoea alpina, 12300

Cobalt Haumaniuastrum robertii 10200

Lead Thlapsi rotundifolium, Brassica juncea, Zea mays 8200

Nickel Alyssum lesbiacum, Sebertia acuminata 47500

Zinc Thlapsi caerulescens, Brassica oleracea, B. 51600

campestris
Selenium Brassica juncea, B. napus 900

Chromium Brassica juncea, Helianthus annus 1400

Surce: Sarkar, 2005
 Lead
Lead is by far the most common contaminant of soils.

Lead in soil is virtually a permanent resident. Organic matter,

especially, will bind and hold itself in other metals very
effectively.

Sources: Number one source contamination: lead-based paint

Other sources: gasoline exhaust
motor oil
automobile tires
industrial activity
coal combustion, and pesticides.
 Mercury
• Mercury occurs in two forms:
- organic
- inorganic
• Inorganic forms most often occur when mercury is combined
with chlorine, sulfur or oxygen.
• Organic forms occur when mercury combines with carbon.

Sources: Metallic forms of mercury are not absorbed by plants, but

are converted by microorganisms to organic forms such
as methyl mercury, which are taken up by plants.
Environmental sources include thermometers, pesticides,
metallurgy, and vapors from burning coal and other
fuels.
Toxic Effect of Hg and Pb in Plants
Mercury in Plants
• The uptake of mercury:
- decreases growth
-induces disorientation of roots and shoots, plant
tissue, and finally the cell wall.
• A major portion of Mercury is tightly bound and remains in the
roots.
Lead in Plants
• Lead in plants:
- Absorbed through roots
- Lead builds up in both leaf and root tissue
- Causes lower concentration of chlorophyll
- Lead compounds absorb UV light
- Plants biomass declines, which includes roots,
shoots, and fruits.
Boreysza, Fabritus,Laures, 2006
 Darcy’s Law

Radius of influence

Vadose zone
WT
D
R
A
W
D
O
W
N
Arseno Pitticite
pyrite
Cone of
Depression
Source: Arsenic is a new terror; Asit Kumar Roy; Desh, 2004
Effect of Arsenic Pollution
 Arsenic uptake by different plant parts of crops
grown in Gotera, Chakdah
Crop Arsenic conc. (mg/kg) at harvest

Leaf Stem Root Eco. Produce

Elephant Foot 4.30 8.0 - 4.0
yam
Green gram 5.10 4.9 4.7 4.3
Cowpea 4.91 5.1 5.2 2.1
Maize 3.30 6.2 5.2 2.6
Rice (boro) 10.2 5.7 5.9 10.0
Jute 3.5 8.0 6.8 4.0
Potato 3.9 9.3 - 5.9
Mustard 7.1 9.8 5.7 3.3
Ground nut 2.0 2.0 2.2 4.0
Sesame 2.0 2.0 4.0 0.6
 Crops were subjected to irrigation with water containing 0.22 mg As / lit of water
 Soil had an Olsen-extractable arsenic content of 1.23 to 1.37 mg/kg of soil (initial)

Source : Prof. S. K. Sanyal,2005

Then what is the way out???

THE GREEN-CURE TECHNOLOGY

PHYTOREMEDIATION
 What is phytoremediation?

 “Use of green plants to remove pollutants from the

environment or render them harmless.”

 This concept has emerged from a broader philosophy

of Bioremediation where besides plants, soil micro-
organism are also used for amelioration of organic and
inorganic contaminants.

Source: Salt et al.(1998)

 D iffe r e n t a p p r o a c h e s o f p h y to r e m e d ia tio n

Phytoremediation

Phytoextraction Phytodegradation Rhizofiltration Phytostabilization Phytovolatilization

A c c u m u la ti U s e o f p la n ts U s e o f p la n t R e d u c tio n in U se o f
o n o f a n d r o o ts to le a c h in g , p la n ts to
m e ta ls in a s s o c ia te d a b so rb a n d r u n o ff, s o il v o la tiliz e
sh o o t m ic r o b e s to a d so rb e r o s io n a n d p o llu ta n ts
tis s u e s d eg ra d e m e ta ls fr o m b io a v a ila b ility
fo llo w e d b y o r g a n ic a q u eo u s o f to x ic
h a r v e s tin g p o llu ta n ts w a ste str e a m m e ta ls
Pteris vittata (Chinese brake) – a reported hyper-
accumulator for arsenic
Disposal of hyper-accumulator plant refuse

Controlled disposal of
ash to underground –
away from root zone
Harvest and aquifer

Phytomining
Jade green alkaloid from cut stem of
Incineration Phyllanthus palawanensis contains
88,580 µg Ni g-1 dry weight
 Contents of some heavy metals in
fertilizers and sludges
Source Metal mg/kg dry material

Cd Cr Cu Pb Zn

Ammonium 1.1 2.5 3.6 5.4 11.7

Niitrate (A/N)
SSP 16.6 157.0 22.6 20.6 244.0

Compound 4.9 54.3 8.3 3.2 97.5

8-10-8
Sewage Sludge 20.0 500.0 250.0 700.0 3000.0

Source: Pain et al., 1991

Accumulation of Heavy Metals in Soil and Plant (mg/g)
Zn Cu Pb Cd Cr
Soils of Dhapa 1038-1256 154-196 79-113 0.38-0.52 9.1-17.0

Spinach 320-340 60-72 60-82 0.8-2.2 6.5-15.8

Cauliflower 300-1100 20-30 30-90 Trace 5.2-5.7

Head

Source: Gupta et al., 1997

Accumulation of Heavy Metals in Rohu fish (1.5 kg)

on dry weight Basis (g/g)
Parts Zn Cu Pb Cd Cr
Brain 3.2 trace 2.9 0.4 11.3
Muscle 29.1 3.4 2.4 0.5 0.9
Liver 53.1 79.5 3.3 6.1 3.2
Kidney 62.6 8.9 11.9 12.3 14.9
Source: Bhattacharyya, 1997
Effect of Heavy Metal Pollution on Microbial
Diversity in soil (experiment conducted in
Portugal, 2006)
Micro-organism Contaminated soil Uncontaminated soil

2003 2004 2003 2004

Aerobic heterotrophic
3.9 1.5 7.4 4.6
bacteria (106 cfu/g)

Actinomycetes (104
8.3 6.6 10.4 9.6
cfu/g)

Fungi (105 cfu/g)

2.8 1.2 4.3 1.8

Asymbiotic Nitrogen
2.5 0.8 9.5 3.5
fixer (104 cfu/g)

Source: Oliveira et al. (2006)

 Some of the cultivated species can also act as
efficient metal hyper-accumulators

Hordeum vulgare

Brassica juncea Avena sativa

 Remedial / Mitigation Options
1. Optimum conjunctive use of ground & surface water
[ e.g. harvested rainwater]

2. Irrigation with pond-stored groundwater – decontamination facilitated

by rainfall and sedimentation

3. Recharge groundwater resource

4. Enhance water use efficiency (optimum water management)

5. Prefer low-water requiring farmer-attractive cropping sequences

(especially for the lean period)

6. Increased use of FYM and other manures + green manure crops,

inclusion of pulses/other legumes as well as application of appropriate
amendments (Zn/Fe salts as and where applicable)

7. Cost-effective phytoremediation options

8. Creation of general awareness: Mass campaigning, holding of farmers’

day, field demonstrations, socioeconomic factors
(Source: Sanyal, 2008)
The chemicals to which life is asked to make
its adjustment are . . . the synthetic creations
of man's inventive mind, brewed in his
laboratories, and having no counterparts in
nature.
Rachel Carson
Silent Spring