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Soil degradation through industrial effluents
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Contents
• Introduction• Industrial effluents• Degradation of soil• Impact of soil degradation• Remediation• Conclusions
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Soil Degradation
• Decline in soil productivity through adverse changes in the nutritional status, soil organic matter, structural attributes and concentration of electrolytes and toxic elements
Lal and Stewart, 1990
• Occurs due to the interactive effects of anthropogenic and biophysical factors on soil properties and leads to adverse alteration in soil properties, environmental quality, agricultural productivity and sustainability
Lal, 1994
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Types of soil degradation
Physical Chemical Biological Physical Chemical Biological
Soil Degradation
Natural Anthropogenic
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Soil degradation
Components Chemical Physical Biological
ProcessesLeaching, Volatilization
Compaction, Erosion
Organic matter oxidation and biodiversity loss
SYMPTOMSSpecific
AcidificationLow nutrient levelsPollutionSalinizationSodificationAlkalization
CrustingPondingPoor water retentionLoss of top soilPan formation
Less faunal activityDelayed decompositionLower CECStructural weakening
SYMPTOMSGeneral
Low or declining yieldsPoor response to inputs
Lal, 1997
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Industry< 1%
Agriculture
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Industrial effluents
Tannery
Battery
Mining
Chlor-alkaliTextile industry
Electroplating
Petroleum industry
Power plants
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Composition of industrial effluents
• N, P, K, S, Cl etc.• Organic matter• Heavy metals (Zn, Cu, Fe, Mn, Co, Cd, Ni, Pb)• High BOD and COD• Sodium and other salts• Organic chemicals• Petroleum hydrocarbons
Non conventional sources of nutrients and irrigation water
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Industrial effluents
Treated Untreated Partially treated
Surface water bodiesAgricultural land
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Heavy metals??
• Group of toxic metals and metalloids
• Density more than 6 Mg m-3
• Atomic weight more than that of iron (26)
Why heavy metals are Toxic to Living Organisms ?
•Oxidative stress caused by redox active transition metals (e.g. Fe2+, Cu2+) produce free radicals
•Replace other essential metals in pigments and enzymes
•Some metal ions (Hg2+, Cu2+) react to thiol groups to interfere
protein structure and functions
•Some metals occur as radioactive isotopes (238U, 137Cs etc.) will cause
health hazards
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Diverse natureDiverse nature
pH 10-11.5
BOD 400-800 mg/L
COD 900-1500 mg/L
Textile effluents
BOD 50,000 mg/L
COD 95,000 mg/L
pH 4.2
Distillery effluent- spentwash
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Sources of selected inorganic soil pollutantsElement Sources of soil contamination
Arsenic Pesticides, coal and petroleum, mine tailings and irrigation water
Cadmium Electroplating, pigments, batteries, fertilizers
Chromium Stainless steel, chrome-plated metals, pigments, refractory brick manufacture and leather tanning
Lead Combustion of oil, gasoline, coal, paint pigment, batteries
Mercury Pesticides, metallurgy and thermometers
Nickel Coal, Electroplating,batteries,mining
Selenium High Se geological formations and irrigation waste water
Brady & Weil, 2002
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Effect of effluents on soil physical propertiesEffect of effluents on soil physical properties Bulk density Water holding capacity Hydraulic conductivity Porosity Aggregate stability
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Physical properties of post harvest soils following effluent treatment
Treatment Bulk density (g cm-3 )
Volumetric water content
Wheat Rice Wheat Rice Control 1.53 1.52 0.37 0.4010% PME 1.41 1.50 0.39 0.4220% PME 1.41 1.52 0.41 0.4130% PME 1.35 1.49 0.40 0.4240% PME 1.36 1.42 0.44 0.41CD (0.05) 0.13 NS 0.05 NS
Pathak et al, 1998Application for four years
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Effect of effluents on physico-chemical Effect of effluents on physico-chemical properties of soilproperties of soil
Properties Treated soil Control soilPorosity (%) 34.7 48.5WHC (%) 15.3 25.0 pH 9.4 6.9 Na (meq 100g-1 ) 8.2 0.4 K (meq 100g-1 ) 2.4 4.8 Ca (meq 100g-1 ) 2.5 17.5 Mg (meq 100g-1 ) 2.2 2.2 Nitrate (mg L-1) 36.0 24.0 Total N (mg L-1) 2020.0 200
Tripathi et al, 1990Chemical and fertilizer effluents
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Effect of effluents on Effect of effluents on micronutrient content in soil and plantsmicronutrient content in soil and plants
Bansal et al, 1992
Micronutrient Micronutrient content (mg kg-1 ) CD (P=0.05)
Years of IWW application
0 2 5
Wheat plant (60 DAS)
Zn 22.0 44.0 59.4 25.8
Cu 6.0 9.9 17.4 1.6
Mn 20.9 16.8 14.6 1.6
Fe 308.0 277.0 444.0 129.0
Soil
Zn 0.8 15.8 45.4 8.5
Cu 1.5 2.0 25.2 1.8
Mn 2.9 8.1 11.1 1.6
Fe 19.5 22.8 58.3 6.9
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Chemical properties of soil irrigated with paper mill effluents (17 years)
Hazarika et al, 2007
Properties STW irrigated Effluent irrigated
pH 5.1 6.41
ESP 2.17 5.86
SAR 2.36 5.19
E C (dSm-1 ) 0.31 1.01
CEC [cmol(p+)kg-1 ] 4.6 12.8
Base saturation (%) 65 97
Exchangeable cations 2.99 12.5
Na 0.10 0.78
Ca 1.78 7.9
Water soluble basic cations
Na 0.19 1.09
K 0.01 0.06
Conc of ions in [cmol (p+)kg-1 ]
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Effect of distillery effluent on soil microflora
Juwarkar and Dutta, 1989
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Effect of distillery effluent on Rhizobia
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Effect of distillery waste water on nodulation and pod formation in groundnut
Treatments Number of nodules a
% variation
Number of pods a
% variation
Tap water (control) 159 - 21 -Raw distillery waste water(RWW) 12 92.45 - -RWW diluted with water(1:1) 57 64.15 5 76.19RWW diluted with stabilization pond effluent (1:1)
141 11.32 20 4.76
Treated distillery waste water(TWW)
102 35.84 9 57.14
TWW diluted with stabilized pond effluent (1:1)
119 25.15 14 33.33
Juwarkar and Dutta, 1989
a Average of 3 replications
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Seed germination (%) under fertilizer factory effluent treatment
Sundaramoorthy et al, 2000
Conc (%) in irrigation water
Germination per cent
G. gram B. gram G’nut Soybean Paddy Sorghum
Control 90 96 94 90 95 93
1 90 99 94 92 97 942.5 92 100 95 95 99 965.0 97 100 97 97 100 10010 100 100 99 80 100 10025 72 80 75 67 82 8550 60 74 68 50 74 7275 55 65 60 42 69 65100 28 40 44 35 62 52
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Microbial population in soils irrigated with textile mill effluent
Rao et al, 2000
Treatment
Microbial population (cfu g-1 soil)
Bacteria x 105
Fungi x 103
Actinomycetes x 104
N2 fixers x 102
Nitrifiers x 102
Irrigation with normal water 72.3 20.7 19.7 7.0 92
Effluent irrigation since once year 31.7 5.3 10.7 28.0 92
Effluent irrigation since three years 19.0 3.3 5.0 1.4 35
Abandoned field due to long term effluent irrigation
6.7 0.8 1.9 0.6 4
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Effect of heavy metals on soil microbial communityHeavy metal
Number of heterotrophs CFU/g
Control (0mM) 10mM 25mM 50mM
Zn 4.49 x 108 6.7 x 108 8.03 x 108 8.58 x 108
Pb 4.49 x 108 2.28 x 108* 1.78 x 108* 1.09 x108*
Ag 4.49 x108 2.04 x 108* 1.2 x 108* 8.32 x 107*
*,p<0.01., values compared with control Rabia and Tasneem, 2007
Parameter STW irrigated Pulp and paper mill effluent irrigated
MBC (mgkg-1 ) 140 79***
Soil respiration (µg CO2 - C g-1 soil d-1 )
70.92 64.35***
Organic carbon (%) 1.80 1.88
Hazarika et al, 2007*** P=0.001
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Effect of chromate and cadmium on MPN estimates of nitrifying bacteria
K2 CrO4 (ppm) MPN Nitrosomonas / mL MPN Nitrobacter / mL
None 1.4 X 105 3.3 X 104
0.01 2.2 X 105 7.0 X 104
1.00 0.01 X 105 1.3 X 105
10.00 1 X 100 3.3 X 104
CdCl2 (ppm)
None 1.4 X 105 3.3 X 104
0.1 1.3 X 105 4.90 X 104
10.00 0.79 X 105 4.90 X 104
100.00 0.49 X 105 0.46 X 104
Fargo and Fleming, 1977
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Effect of tannery effluents on VAM colonisation in Vigna radiata and Zea mays
Species Treatt % VAM infection
Mycelium Arbuscles Vesicles Extent (cm/100cm)
Vigna radiata
NFS 87 57 93 56
TECS 100 33 87 42
Maize NFS 100 80 63 69
TECS 97 37 47 54
Javaid et al, 2000TECS - Tannery effluent contaminated soil NFS – Normal field soil
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Heavy Metal Cycle In Soil-Water-Plant-Animal Continuum
Industrial & municipal wastes
Mine spoils
Atmospheric fall out
Fertilizers and agricultural chemicals
Consumers: humans/animals
Plant residue
Decay/waste generation
Earth surface Surface water
Desorption/dissolution/mineralization
Trace elements associated with solid phases (organic/inorganic)
Trace elements in groundwaterSorption/precipitation/immobilization
Trace metals in soil solution
Leaching
Withdrawal
Rattan et al, 2002
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0
20
40
60
Zn Cu Fe Mn
DT
PA e
xtra
ctab
le m
etal
(mg/
kg)
Initial
2 years
5 years
Jamalpur village - Ludhiana
Bansal et al, 1992
Soil as a sink of heavy metals
Effect of industrial effluents on DTPA extractable micronutrients in soil
Industrial waste water
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Dry river beds as potential sink of trace metals
A case study of dry beds of river Ganges, Kanpur city
160.704.28Cr 191.407.35Ni 331.996.10Co 542.254.15Pb 100.050.45Cd 4947.697.1Mn
0.952.83Cu 412.937.08Zn
Leachable metal content as % of total
Leachable (0.01 N HCl extractable)
Total Metal
Metal contents (mg kg-1) in soils of dry river bed of Ganges
Farooq et al,1999
33
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7.87.88.28.29.39.313.113.12.82.820.520.5124.3124.34.24.2Tinda Tinda
3.83.87.57.512.412.410.810.82.52.516.516.531.631.68.38.3Sponge gourd Sponge gourd
1.91.94.24.213.213.2164.8164.89.69.617.117.1290.6290.65.35.3Snake Snake cucumbercucumber
11.711.710.110.114.114.13.73.71.71.714.214.2512.5512.56.86.8Radish Radish
131313.213.210.310.334.534.55.25.276.576.5121.5121.53.93.9Garden Garden spinachspinach
6.96.915.515.56.66.69.49.45.75.739.739.723.123.17.57.5Bitter Bitter gourdgourd
2.92.91.11.127.827.8107.8107.88.28.232.332.341.641.612.312.3Bottle gourd Bottle gourd
Cr Cr Ni Ni Co Co Pb Pb Cd Cd Mn Mn CuCu ZnZn VegetableVegetables s
Farooq et al, 1999
Metal contents (mg kg-1) in some vegetables grown on dry river bed of Ganges
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Crops as sink of heavy metals
• One of the principal sinks of the heavy metals
•Metal contaminated edible portions may be toxic for human beings and other living organisms
• Bio-magnification along the food chain
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Heavy metal levels in edible parts, non edible leaves and shoot of plants
050
100150200250300350400
Zn Cu Cd Pb
Edible Part
Non-edible
Leaves
Non-edible
ShootHea
vy m
etal
con
tent
(m
g/kg
)
Barman and Lal, 1994
12 varieties of crop
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Water as Sink of heavy metals
• Potential of contaminating the drinking water bodies and aquifers
Element WHO standards
As 0.05Cd 0.01Cr 0.05Cu 1.0Fe 1.0Pb 0.1Mn 0.5Hg 0.001Zn 5.0
International standards (mg/L) for drinking Water
Underground water of the wells adjoining stream and river around the Zinc smelters in Dabari contained: Zn Zn 0.0 - 7.2 (mg L 0.0 - 7.2 (mg L-1-1)) Cd 0.0 - 0.93 (mg LCd 0.0 - 0.93 (mg L-1-1) ) Fe 0.1 - 0.6 (mg LFe 0.1 - 0.6 (mg L-1-1))
Totawat, 1993
De, 2000
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Deterioration of water quality at Coimbatore
More than 30,000 small, medium and large industries
Element WHO standards
(mg/L)
As 0.05Cd 0.01Cr 0.05Cu 1.0Fe 1.0Pb 0.1Mn 0.5Hg 0.001Zn 5.0
Heavy metal concentrations(µg/L) in water of wetlands
Location Zn Cu Fe Mn Cd Pb Ni Cr
SelvachinthamaSelvachinthamani lakeni lake
Singanallur lake Singanallur lake
Ukkadam lakeUkkadam lake
Perur lake
Valankulam lakeValankulam lake
Ammankulam lakeAmmankulam lake
Selvampatti lakeSelvampatti lake
Kumaraswamy lakeKumaraswamy lake
493 177 8080 1257 10 375 6.94 3.87
95 44 520 255 1 26 23 52 34 18 1525 55.2 0.5 10.5 6.4 29.8
53 30.3 1735 71 0.5 4.5 8.6 43
99.5 24.5 640 346.2 2 25.5 24.9 48.5
101 44.1 3285 63.6 0.5 4.5 11.8 42.4
52.5 26 3405 82.9 0 15.5 11.5 34.7
69 28.2 1165 54.5 0 14.5 6.1 61.9
De, 2000Mohanraj et al,2000
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Rocks in the Earth crust
IndustrialBurned fuelsFertilizersPesticides
Plants
Domestic animals
Birds
Fish
Humans
Bio-magnification of heavy metals along the food chain
Haan and Lubbers, 1983
Water
Air
Soil
Impacts of soil degradation
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Impacts of effluent induced soil degradation
Inhibition of photosynthesis and respiration Carlson et al,1975
Affects germination and mineral composition of crops
Alteration of plant-water relations, causing water stress and wilting
Poschenrieder et al,1989
Increased permeability of root cell plasma membrane, rendering roots less ion selective
Loneragan et al ,1987
Adverse effects on the activities of metabolic enzymes and pigments
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Mineral composition of 7 days old seedling (% dry weight)
Mineral Polluted soil plants Control soil plantsNa 1.62 0.71 K 0.15 0.75 Ca 0.72 0.89 Mg 1.31 1.05
Germination percentage of Wheat
Laboratory conditions Field conditions
Effluent Well water Polluted soil Control soil
90 98 52 86
Tripathi et al, 1990
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Period of IWW application ( years)
Grain yield ( q/ha)
Micronutrient elements(mg kg-1 dry weight)
Zn Cu Mn Fe
0 26.0 36.0 4.5 13.0 37.0
2 24.0 60.4 6.3 5.7 38.2
5 21.0 75.8 7.5 4.1 50.4
CD (P=0.05) 11.6 1.5 1.4 7.7
Micronutrients in grain and straw of wheat
Bansal et al, 1992
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Industrial effluent effect on groundnut seedlings
Parameter Effluent value ISI standardpH 8.5 6.5-8.5EC (µ mhos/cm) 11.5 2.25Total dissolved salts (mgL-1)
611 500
Cr (mgL-1 ) 0.071 0.05Pb (mgL-1 ) 0.108 O.1Cd (mgL-1 ) 0.028 0.01Zn (mgL-1 ) 6.73 5Co (mgL-1 ) 0.311 0.05BOD 53.6 -COD 128.66 -
Physicochemical characteristics of biomass power plant effluent
Nagajyothi et al, 2008
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Treatment 120 hours 192 hours Total
Control 5.67 2.67 8.34
25% 6.33 (11.75)ns 3.33 (24.971)ns 9.66 (16)ns
50% 5.33ns 2.33ns 7.66ns
75% 4.33ns 2.33 ns 6.66ns
100% 3.0 (-52.6)ns 2.33 (-41.6)ns 5.33 (-36)ns
Germination percentage of groundnut at different time intervals
Values in bracket : % change from control
• Root length and shoot length also followed the same trend
Change in total chlorophyll content ( mg/g fr. wt) at different time intervalsTreatment 10th day 15th day 25th day 30th day
Control 2.05 3.58 1.81 1.51
25% 2.45(19.64)ns 4.22** 2.44* 2.14(41.9)***
50% 1.64* 2.8** 1.38* 1.24*
75% 1.54* 2.35*** 1.05* 0.86**
100% 1.41(-31.28)* 1.99** 0.89* 0.612 (-59.5)**
Nagajyothi et al, 2008*p<0.01, **p,0.001,***p,0.0001 ns – non significant
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HEAVY METAL SYMPTOMS ON PLANTS
Brassica sp.
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Selenium Toxicity(9 mg/day)
Deformed finger nails in human
Alkali diseases in animal
Human and animal Health
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Cadmium Toxicity (200µg kg-1 fresh wt)• Metal –binding protein found in liver and kidney
• Has very high affinity for Cd and Zn
• Cd disrupts the normal functions of Zn and Ca
itai-itai disease is a multi-system disorder characterized by:
Severe osteoporosis and bone fragility
Disruption of calcium metabolism (increased excretion)
Nutritional deficiencies (Vit. D, Ca)
White-tailed ptarmigan
X-ray image of a ptarmigan
shows a fracture caused
by Ca deficiency triggered by Cd-damaged kidneys
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Mercury Toxicity (>0.1µg/Kg BW)• Tissue distribution primarily to CNS, foetus & red blood cells
• Methyl Hg can also cross blood brain barrier by molecular mimicry
Molecular mimicry
CH3Hg + SH-CH 2 -CHCOO-N H3+(cysteine)
CH3Hg -S-CH2-CH COO-N H3+(methyl mercury complex)
CH 3 -S-CH2-CH2-CHCOO-N H3+(methionine)
Minamata disease (Japan 1953-60) Mercury contaminated fish caused loss of lives Contamination by methyl mercury (27-102 ppm)
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Arsenic Toxicity (3mg/day)• Skin cancer• Hyperkeratosis• Hyperpigmentation• Black foot• Cancer of internal organs
Other Impacts• Genotoxic and mutagenic effects
• Teratogenic effects
• Nitrate pollution of ground water – Methaemoglobanemia
• Eutrophication
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Preventive measures
• Treatment of effluents before disposal to environment• Mixing of effluents with good quality irrigation water• Avoid continuous use• Legislative measures
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Legislative measures
Parameters Discharge to land
Suspended solids 100
Temperature Should not exceed 50 C above ambient temperature of receiving body
pH 6.0 – 9.0
Cyanides as CN- 0.2
Ammoniacal nitrogen 50
Total residual chlorine
1.0
Cadmium 2.0Nickel 3.0
Zinc 5.0Chromium (VI) 0.1Total Chromium 2.0Copper 3.0Oil & grease 10
Electroplating industry –Discharge standards
Parameter Disposal to Land
Suspended solids
200
BOD, 3 days at 270 C
100
pH 6.0-9.0
Chlorides as Cl 600
Chromium (VI) 0.1
Chromium (Total)
2.0
Sulphides -
Sodium(%) 60
Boron 2.0
Oil & grease 10
Leather industry - discharge standards
EPA, 1987All conc. in mg/L
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Remediation
• In situ remediation – treatment of soil in place • ex situ remediation – physical removal of soil and it’s
treatment expensive
In situ Remediation
• Immobilization of toxic metals using ameliorants• Bioremediation• Cropping system management
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Ameliorants for remediation• Lime, phosphates and organic matter
Ameliorants Water soluble
Exchangeable Specifically adsorbed
Organically bound
Control 0.96 18.6 50.1 33.3Lime (2.5% 0.64 17.9 58.7 43.3Lime (5%) 0.30 15.3 53.1 36.8FYM (2.2 g kg-1 ) 0.76 18.1 66.4 38.3
FYM (4.4 g kg-1 ) 0.58 19.2 64.1 47.6
BGS (2.2 g kg-1 ) 0.72 17.9 61.7 36.6
BGS (4.4 g kg-1 ) 0.54 19.4 65.8 40.4
HMO (0.5%) 0.48 16.5 67.5 44.8HMO (1%) 0.42 15.3 64.6 41.6CD (P=0.05) 0.22 1.0 2.4 2.9
Effect of different ameliorants on distribution of various fractions of Ni (mg kg-1) in soil
Mathavan et al, 2009
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Bioremediation
• Using microbes• Phytoremediation
Phytoextraction Phytodegradation Rhizofiltration Phytostabilization Phytovolatilization
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Phytoextraction
• Hyper-accumulator plants
Shoot metal concentration (oven dry basis) should be more
than 1% for Mn and Zn; 0.1% for Cu, Ni, and Pb and 0.01% for
Cd and As Should be fast growing with high rate of biomass production Should be able to accumulate metals even from low external
metal concentration Should be able to transfer accumulated metals from root to
shoot (above ground) quite efficiently (often more than 90%)
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Elements Plant species Maximum reported
conc. (mg/kg)
Cadmium Thlaspi caerulescens 500
Copper Ipomoea alpina 12300
Cobalt Haumaniuastrum robertii 10200
Lead T rotundifolium, Brassica juncea, Zea mays 8200
Nickel Alyssum lesbiacum, Sebertia acuminata 47500
Zinc T caerulescens, B j, B oleracea, B campestris 51600
Selenium Brassica juncea, B napus 900
Chromium Brassica juncea, Helianthus annus 1400
Important and widely reported hyper-accumulators for metal remediation
Chhonkar, 2004
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Conclusions
• Industrial effluents are rich source of plant nutrients and an
alternative source of irrigation water• Use of industrial effluents have diverse effects on different soil
properties• Continued use of these effluents leads to the build up of heavy
metal concentration in soil to toxic levels• Build up of heavy metals have immense detrimental effects on
plants, animals and human beings• Integrative approaches can only check the soil degradation
through industrial effluents
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Future aspects
• Implementation of environmental standards for disposal of
effluents• Periodical monitoring of effluent composition• Screening of plants species and genotypes for effective
phytoremediation• Studies on long term effects of industrial effluents on soil
degradation and its environmental impacts
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