soil degradation through industrial effluents

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Soil degradation through industrial effluents


Contents

• Introduction• Industrial effluents• Degradation of soil• Impact of soil degradation• Remediation• Conclusions


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


Types of soil degradation

Physical Chemical Biological Physical Chemical Biological

Soil Degradation

Natural Anthropogenic


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


Industry< 1%

Agriculture


Industrial effluents

Tannery

Battery

Mining

Chlor-alkaliTextile industry

Electroplating

Petroleum industry

Power plants


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


Industrial effluents

Treated Untreated Partially treated

Surface water bodiesAgricultural land


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


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


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


Effect of effluents on soil physical propertiesEffect of effluents on soil physical properties Bulk density Water holding capacity Hydraulic conductivity Porosity Aggregate stability


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


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


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


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 ]


Effect of distillery effluent on soil microflora

Juwarkar and Dutta, 1989

© 2004 By Default!A Free sample background from www.awesomebackgrounds.comJuwarkar and Dutta, 1989

Effect of distillery effluent on Rhizobia


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


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


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


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


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


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


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


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


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


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


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


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


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


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


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


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


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


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


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


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


HEAVY METAL SYMPTOMS ON PLANTS

Brassica sp.


Selenium Toxicity(9 mg/day)

Deformed finger nails in human

Alkali diseases in animal

Human and animal Health


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

http://osu.orst.edu/dept/ncs/photos/ptarmig.jpg

http://osu.orst.edu/dept/ncs/photos/fracture.jpg


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)


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


Preventive measures

• Treatment of effluents before disposal to environment• Mixing of effluents with good quality irrigation water• Avoid continuous use• Legislative measures


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


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


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


Bioremediation

• Using microbes• Phytoremediation

Phytoextraction Phytodegradation Rhizofiltration Phytostabilization Phytovolatilization


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%)


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


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


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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soil degradation through industrial effluents

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