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Journal of Environmental Management 79 (2006) 173187

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Management of mine spoil for crop productivity with lignite


fly ash and biological amendments
L.C. Rama,*, N.K. Srivastavaa, R.C. Tripathia, S.K. Jhaa, A.K. Sinhaa, G. Singha, V. Manoharanb
b

a
Central Fuel Research Institute, PO-FRI, 828108 Dhanbad, Jharkhand, India
Centre for Applied Research and Development, Neyveli Lignite Corporation Limited, Neyveli 607801, Tamil Nadu, India

Received 3 October 2003; accepted 21 June 2005


Available online 26 October 2005

Abstract
Long-term field trials using lignite fly ash (LFA) were carried out in rice crops during the period 19962000 at Mine I, Neyveli Lignite
Corporation, Tamil Nadu. LFA, being alkaline and endowed with an excellent pozzolanic nature, silt loam texture, and plant nutrients, has
the potential to improve the texture, fertility, and crop productivity of mine spoil. The rice crops were the first, third, fifth, and sixth crops in
rotation. The other crops, such as green gram (second) and sun hemp (fourth), were grown as green manure. For experimental trials, LFA was
applied at various dosages (0, 5, 10, 20, 50, 100, and 200 t/ha), with and without press mud (10 t/ha), before cultivation of the first crop.
Repeat applications of LFA were made at the same dosages in treatments of up to 50 t/ha (with and without press mud) before cultivation of
the third and fifth crops. Press mud, a lightweight organic waste product from the sugar industry, was used as an organic amendment and
source of plant nutrients. Also, a recommended dosage of chemical fertilizer, along with gypsum, humic acid, and biofertilizer as
supplementing agents, was applied in all the treatments, including control. With one-time and repeat applications of LFA, from 5 to 20 t/ha
(with and without press mud), the crop yield (grain and straw) increased significantly (p!0.05), in the range from 3.0 to 42.0% over the
corresponding control. The maximum yield was obtained with repeat applications of 20 t/ha of LFA with press mud in the third crop. The
press mud enhanced the yield in the range of 1.510.2% with various dosages of LFA. The optimum dosage of LFA was 20 t/ha for both onetime and repeat applications. Repeat applications of LFA at lower dosages of up to 20 t/ha were more effective in increasing the yield than the
corresponding one-time applications of up to 20 t/ha and repeat applications at 50 t/ha. One-time and repeat applications of LFA of up to
20 t/ha (with and without press mud), apart from increasing the yield, evinced improvement in the texture and fertility of mine spoil and the
nutrient content of crop produce. Furthermore, some increase in the content of trace and heavy metals and the level of g-emitters in the mine
spoil and crop produce was observed, but well within the permissible limits. The residual effect of LFA on succeeding crops was also
encouraging in terms of eco-friendliness. Beyond 20 t/ha of LFA, the crop yield decreased significantly (p!0.05), as a result of the formation
of hardpan in the mine spoil and possibly the higher concentration of soluble salts in the LFA. However, the adverse effects of soluble salts
were annulled progressively during the cultivation of succeeding crops. A plausible mechanism for the improved fertility of mine spoil and
the carryover or uptake of toxic trace and heavy metals and g-emitters in mine spoil and crop produce is also discussed.
q 2005 Elsevier Ltd. All rights reserved.
Keywords: Lignite fly ash; Mine spoil; Management; Crop productivity; Sustainability

1. Introduction
The generation of huge amounts of mine spoil (four times
the amount of coal), comprising unwanted extraneous shaly
matter and other refuse from opencast miningextensively

* Corresponding author. Tel.: C91 326 2381001-10 (Extn 357/224);


fax: C91 326 2381113/2381385/2381560.
E-mail address: lcramcfri@rediffmail.com (L.C. Ram).

0301-4797/$ - see front matter q 2005 Elsevier Ltd. All rights reserved.
doi:10.1016/j.jenvman.2005.06.008

practiced in India, currentlydisturbs the natural soil strata


and ecological balance. Likewise, production of about
100 Mt/year of fly ash from 82 thermal power plants in the
country poses problems with handling, storage, and disposal
(requiring large areas of land), apart from apprehension
about possible contamination of soil, crop produce, and
groundwater with toxic trace and heavy metals (Furr et al.,
1977; Carlson and Adriano, 1993; Rubeinstein and Segal,
1993) and radionuclides (Ramachandran et al., 1990;
Vijayan and Behera, 1999), especially in view of the
minimal use made of it. In particular, the mine spoil
generated by opencast mining of lignite by Neyveli Lignite

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L.C. Ram et al. / Journal of Environmental Management 79 (2006) 173187

Corporation (NLC), Tamil Nadu, is more problematic, as a


result of its fragile nature, poor porosity, deficient nutrient
level, and failure to offer any appreciable biological activity.
The lignite fly ash (LFA) currently generated by two
thermal power stations (TPS I and II; capacity 2070 MW),
to the tune of w1.0 Mt/year, does not find any major use
(hardly 12%, mainly in civil construction, building
materials, and land fill), and this is distressing. The mine
spoil produced in the extraction of coal and the fly ash
produced in power generation are two major environmental
problems, suggesting a need for a suitable eco-friendly
technology, in one stroke, not only to solve the environmental concerns, but also increase the gainful bulk use of
these materials.
Much research and development (R&D) has been
carried out in the recent past on the use of fly ash in
agriculture and in the revegetation of dumping sites and
surface mine soil (Fail and Wochok, 1977; Bhumbla
et al., 1991), where the potential of fly ash as liming
agent, source of plant nutrients, and soil modifier has been
exploited. The uptake or enrichment of various nutrients
and toxic trace elements in soil after fly-ash amendment
has been investigated, and crop produce has been found
safe for consumption (Sen et al., 1997). At the Central
Fuel Research Institute (CFRI), Dhanbad, investigations
(Singh et al., 1997; Singh et al., 1998; Ram et al., 1999)
of the application of fly ash under various soil types and
agroclimatic conditions have suggested the beneficial
effects of fly ash in agriculture as liming agent, soil
conditioner, source of essential plant nutrients, and a way
to reclaim waste or degraded lands. Though fly ash
contains several essential plant nutrients, it is devoid of
humus and nitrogen (Menon et al., 1990), which can be
supplemented by organic amendments (Adriano et al.,
1978), together with effective reduction in leaching of
metals by chelation (Logan and Traina, 1993).
The LFA of the NLC has been reported to be alkaline
(pHZ1012, Ca, 812%), with a cementitious nature useful
in inhibiting the infiltration of water into sandy (loosetextured) soils and providing plant nutrients essential for
crop growth (CARD (Centre for Applied Research &
Development, 1997)). Like most fly ashes, LFA being
dominated by silt-sized particles (Adriano et al., 1980),
could be expected to improve the texture, bulk density (BD),
water-holding capacity (WHC), and fertility of the mine
spoil of NLC. Practically no detailed R&D was available on
the management of mine spoil through bulk-scale use of
LFA, and hence this study was carried out. The present
paper describes the results of long-term field trials
performed during 19962000 on mine spoil, involving
amendment with various dosages of LFA, with and without
press mud, for cultivation of rice crops. The study includes
the effects on the fertility of mine spoil, crop yield and
nutrient status, trace and heavy metals content, and the level
of radioactivity of the mine spoil and crop produce.

2. Materials and methods


2.1. Experimental details
The selected mine-spoil area (w6000 m2, filled up to a
depth of 10 m) was properly leveled and ploughed several
times in order to maintain uniform fertility. The
experimental setup was a randomized block design having
18 treatments (T1T18), each in quadruplicate of a 15 m!
4 m area, treated with various dosages (0, 5, 10, 20, 50,
100, and 200 t/ha) of LFA, with and without press mud
(Table 1), where treatment T1 (control) was without LFA
and press mud, and T2 was with press mud only. In
treatments T3, T5, T7, T9, T11, and T13, LFA alone (5, 10,
20, 50, 100, and 200 t/ha) was applied. In treatments T4,
T6, T8, T10, T12, and T14, LFA (5, 10, 20, 50, 100, and
200 t/ha) was applied in combination with press mud; and
in T15T18, LFA (5, 10, 20, and 50 t/ha) was applied in
combination with press mud. For all applications
involving press mud, the dosage was 10 t/ha. One-time
application of LFA was made in T11T18; repeat
applications of LFA were made before cultivation of the
third and fifth crops in T3T10 at the same rate as before
the cultivation of the first crop.
2.2. Crop rotation and other details
The crop rotation was as follows: rice (JanApr 1997)
green gram (AprMay 1997)rice (AprAug 1998)sun
hemp (Dec 1998Jan 1999)rice (JanMay 1999)rice (Dec
1999Apr 2000). The recommended dosage of NPK
fertilizer was 100:50:50 kg/ha as urea (NH2CONH2): single
super phosphate (Ca(H2PO4)2) and muriate of potash (KCl)
for cultivation of each rice crop.

Table 1
Treatments detail
Sl. No.

Treatment

Detail

1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18

T1
T2
T3
T4
T5
T6
T7
T8
T9
T10
T11
T12
T13
T14
T15
T16
T17
T18

Control
Press mud (10 t/ha)
Lignite fly ash (LFA) (5 t/ha)
LFA (5 t/ha)CPM (10 t/ha)
LFA (10 t/ha)
LFA (10 t/ha)CPM (10 t/ha)
LFA (20 t/ha)
LFA (20 t/ha)C(PM 10 t/ha)
LFA (50 t/ha)
LFA (50 t/ha)CPM (10 t/ha)
LFA (100 t/ha)
LFA (100 t/ha)CPM (10 t/ha)
LFA (200 t/ha)
LFA (200 t/ha)CPM (10 t/ha)
LFA (5 t/ha)CPM (10 t/ha)
LFA (10 t/ha)CPM (10 t/ha)
LFA (20 t/ha)CPM (10 t/ha)
LFA (50 t/ha)CPM (10 t/ha)

L.C. Ram et al. / Journal of Environmental Management 79 (2006) 173187


Table 2
Physico-chemical characteristics of press mud
Value
Parameters
pH
Electrical conductivity (dS/m)
WHC (%)
Organic carbon (%)
Moisture (%)
Ash (%)
Volatile matter (%)
Fixed carbon (%)
Ultimate analysis
Carbon (%)
Hydrogen (%)
Sulfur (%)
Nitrogen (%)

7.44
1.874
149.4
13.2
9.4
39.3
47.7
3.6
26.19
2.67
1.82
0.82

2.2.1. Other amendments


Other amendments, such as gypsum (325 kg/ha), humic
acid (20 kg/ha), and biofertilizer (RhizobiumCPhosphobacterium; 8 kg/ha each), were applied, along with basal
dosage of chemical fertilizers, in all treatments, including
control. These amendments were made as supplementing
agents, especially in view of the poor fertility of mine
spoil and the normal practice of using such amendments
by local farmers. No applications of NPK fertilizer and
other amendments as green manure were made for
growing green gram or sun hemp. Press mud, a
lightweight waste product from the sugar industry,
abundantly available in areas nearby the NLC, was used
as a source of organic matter and plant nutrients (Table 2)
to improve the texture and fertility of the mine spoil.
Gypsum, of a locally available, commercial-grade composition, including 14% sulfur, was applied to reduce the
crust formation in the mine spoil. Potassium salt of humic
acid (20% humic acid content), prepared from lignite by a
chemical method at Centre for Applied Research &
Development (CARD), NLC, was applied in the mine
spoil to stimulate microbial growth and to provide some
essential plant elements. Biofertilizer, a composition of
Rhizobium and Phosphobacterium developed in the
CARD microbiological laboratory, was mixed with lignite
to act as a carrier of microbes.
2.3. Collection and characterization of
mine spoil, LFA, press mud, and crop produce
The various samples of dry LFA used for field trials,
mine spoil and press mud before the start of the field
experiment (cultivation of the first rice crop), crop produce
(grain and straw), and mine spoil from control and amended
plots after harvest of each rice crop were collected,
processed, and analyzed by the standard procedure
discussed below.

175

2.3.1. Methods of analysis


The physical properties, such as mechanical composition, BD, porosity, WHC, and hydraulic conductivity, of
LFA and mine spoil were determined by the standard
methods (Piper, 1950; Black, 1965; Jackson, 1967).
Chemical properties, namely, pH, electrical conductivity
(EC), and total and available major secondary nutrients (N,
P, K, S, Ca, and Mg) of LFA and mine spoil were
determined by the standard methods (Black, 1965; Jackson,
1967; Tandon, 1995).
The samples of mine spoil, LFA, and crop produce were
digested in an analytical microwave system (AMS, Prolabo
Microwave Oven), using various Suprapure acids from
Merck, Germany, as reagents for analysis of total contents
of micronutrients (Cu, Zn, Mn, and Fe) and trace and heavy
metals (Pb, Ni, Co, Cd, etc.). For determination of available
trace and heavy metals content in LFA and mine spoil, the
extraction of samples with diethylenetriamine pentaacetate
(DTPA) was carried out by the prescribed method (Tandon,
1995), by which the available content was estimated. The
DTPA-extractable fraction of total content has been found
to be relatively bioavailable for root uptake (Adriano et al.,
2002).
Total trace- and heavy-metals content in various
digested mine spoil, LFA, grain, and straw samples and
available content in DTPA extracts of mine spoils and
LFA were estimated by liquid ion chromatography
(Waters). The determination of Cu, Zn, Mn, Fe, Pb, Ni,
Cd, and Co was made with a C18 column, with sodium
octane sulphonate, tartaric acid, and acetonitrile as eluent;
postcolumn reagent; and ultraviolet light (UV) detector
(520 nm). The IC Pak-A HR column, borategluconate
eluent, and UV detector (365 nm) were used for
determination of Cr (as CrOK2
4 ). The standard sample
for various trace and heavy elements was ICP multielement standard solution IV (Cat. No. 1.11355.0100),
procured from Merck. The detection limit for Cu, Co, Mn,
and Zn, was 5 ppb; and for Cd, Cr, Fe, Ni, and Pb,
15 ppb. The As and Hg were analyzed with a Unicom SP2900 atomic absorption spectrometer by the hydride coldvapor generation method. The detection limit for As and
Hg was 5 ppb.
The g-emitting radionuclides were measured with a
g-ray spectrometer, comprising a high-purity germanium
(HPGe) detector with a resolution of 1.95 kV at 1.33 MeV
and a volume of 77 cm3. The detector was kept at 2p
geometry for counting. The g-rays emitted from the
sample were detected by the HPGe detector, with the lead
shielding lined by 1 mm of aluminum, and were deduced
with a PC-based multichannel analyzer. The data were
analyzed, and radionuclides 226Ra, 228Ac, and 40K were
estimated for various samples of mine spoil, LFA, and
crop produce. The detection limits of these radionuclides
in the mine-spoil and LFA samples was 5 Bq/kg; and for
grain and straw samples, 0.05 Bq/kg. The dehydrogenase

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L.C. Ram et al. / Journal of Environmental Management 79 (2006) 173187

Table 3
Physico-chemical characteristics of mine spoil of experimental site at mine-I, NLC before conduction of field experiments, and of LFA applied at different
stages of field trials

Parameters
Sand (%)

Coarse
Fine
Coarse
Fine

Silt (%)
Clay (%)
Bulk density (g/cm3)
WHC (%)
Porosity (%)
EC (dS/m)
Dehydrogenase activity (mg/kg hK1)
pH
Total major nutrients
Organic C (%)
N (%)
P (ppm)
K (ppm)
S (%)
Ca (%)
Mg (%)
Available major and secondary nutrients
N (%)
P (ppm)
K (ppm)
S (ppm)
Ca (ppm)
Mg (ppm)
Trace and heavy metals
Cu
Zn
Mn
Fe
Pb
Ni
Cd
Co
Cr
As
Hg
Radioactivity (Bq/kg)
220
Ra
228
Ac
40
K
a
b

Total (ppm)
70.63G4.20
79.38G6.03
133.74G8.69
1.63bG0.11
18.80G1.35
44.23G3.01
1.96G0.14
15.54G1.15
36.43G2.48
BDL
BDL

Ava (ppm)
2.30G0.17
1.52G0.15
6.49G0.49
19.61G1.31
BDL
2.11G0.16
0.03G0.002
BDL
BDL
BDL

Original soil (mine spoil)

Lignite fly ash

16.2G1.01
36.9G2.15
14.6G0.91
17.8G0.1
14.5G0.85
1.72G0.12
19.8G1.42
29.2G1.85
0.436G0.02
0.032G0.001
6.50G0.93

30.7137.47
51.2861.6
8.6610.61
0.881.051
41.5950.4
49.2257.81
3.774.52

10.2310.54

0.30G0.02
0.021G0.001
46.0G2.69
77.2G5.17
0.22G0.012
0.16G0.009
0.04G0.002

0.1220.180

72.591.24
816.4993.4
0.961.15
9.2811.28
1.191.53

0.006
2.8G0.13
20.6G0.93
37.8G1.81
40.2G2.13
22.5G1.23

2.863.89
52.5268.25
93.96105.22
16952000
30.2037.01
Total (ppm)
40.5751.47
148.52162.05
162.17192.19
3.97b5.44
12.8817.31
129.13141.82
10.0312.20
19.5424.10
46.8456.88
1.191.44
BDL

15.7G0.67
31.9G1.78
150.3G8.14

Ava (ppm)
1.962.30
1.902.30
15.6020.72
55.9675.66
0.060.10
4.895.23
0.140.30
0.370.54
0.400.66
BDL

74.1984.87
74.5087.52
352.59413.03

Av, DTPA extractable.


Total Fe content in percent.

activity in mine spoil was estimated by the standard


method (Klein et al., 1971).

3. Results and discussion


3.1. Biometric observations

2.4. Statistical analysis


One-way analysis of variance was performed and
computed for the critical difference (CD) value with an
MSTAT package (Russel et al., 1991), to assess the
significance (p!0.05) of the yield data, analysis of the
samples, and various biological parameters. For other cases,
wherever applicable, standard error has been shown in
tables and figures.

Biometric observation of the growth and development


stages of rice crops revealed that plant height, number of
tillers, and plant population varied between treatments (data
not shown). One-time and repeat applications of LFA from 5
to 20 t/ha, with and without press mud, significantly (p!
0.05) increased plant growth performance, with the most
promising results from repeat applications of LFA at the
same dosage in treatment T8 (20 t/ha LFA with press mud) of

L.C. Ram et al. / Journal of Environmental Management 79 (2006) 173187

the third crop. The overall growth condition of rice plants was
luxuriant, with less incidence of pests, plant disease, and
weeds; uniform and early maturity; intense color of green
leaves; and bigger size of panicles in the plots amended with
LFA alone and in combination with press mud. However, at
dosages beyond 20 t/ha of LFA, with and without press mud,
particularly at 100 (T11 and T12) and 200 t/ha (T13 and T14),
biometric values dropped abruptly, to even less than the
corresponding control values. However, such lowering of
biometric values diminish progressively during the growth
of successive crops. Also, no apparent symptoms whatsoever
of toxicity due to trace and heavy metals and radionuclides
present in LFA could be observed.
No biometric observations were made of green gram
(second crop) or sun hemp (fourth crop), as these were
grown as green manure.

177

and clay and higher content of silt than mine spoil. The BD
is lower, and WHC and porosity are quite a bit higher, than
in mine spoil. EC and alkalinity (pH 10.2510.54) are much
higher due to the higher content of Ca (9.2811.28%) and
Mg (1.191.53%). The OC (0.120.18%) is much lower
than in mine spoil. Furthermore, LFA is completely devoid
of nitrogen and dehydrogenase activity, and the content of
major and secondary nutrients (P, K, S, Ca, and Mg) is much
higher than the negligible values found in the mine spoil.
Total and available content of micronutrients, such as Zn,
Mn, and Fe, is higher, and Cu is lower. Similarly, total and
available content of trace and heavy metals Ni, Cd, Co, Cr,
and As is higher, and that of Pb is lower. Besides, the level
of radioactivity in respect to g-emitters 220Ra, 228Ac, 40K is
higher. In sum, the LFA could be used to modify the texture
and improve the fertility of mine spoil, provided the
application is eco-friendly.

3.2. Characteristics of mine spoil and LFA


3.3. Crop yield
3.2.1. Mine spoil
From Table 3, it can be observed that the textural class of
the mine spoil is silt loam type with massive structure and
very poor aggregates and no appreciable similarity with
normal arable soils. The sand is the predominant fraction
(53.1%) followed by silt content (32.4%), wherein both
contain a higher content of fine fraction than coarse fraction.
The clay content (14.5%) is quite low. The BD is very high
(1.72 g/cm3), in comparison to arable soil. WHC (19.8%)
and porosity (29.2%) were found to be very low, compared
with the corresponding values of normal fertile soil (ICAR
(Indian Council of Agricultural Research), 1969).
The mine spoil is just acidic (pHZ6.5). The EC is quite
low (0.436 dS/m) indicating the prevalence of a poor saline
condition. Organic carbon (OC) is also lower (0.30%) than
normal for Indian soil, 0.40.6% (ICAR (Indian Council of
Agricultural Research), 1969). Similarly, the concentration
of total and available major and secondary nutrients (N, P,
K, S, Ca, and Mg) and micronutrients (Cu, Zn, Mn, and Fe)
in mine spoil indicates its poor fertility. The total content of
trace and heavy metals, such as Pb, Ni, Co, and Cr, is in the
range 15.544.2 ppm, and Cd is 1.9 ppm. Other trace elements, such as As and Hg, are below detection limit (BDL).
The available content of Ni and Cd is 2.11 and 0.03 ppm,
respectively, and that of Pb, Co, Cr, As, and Hg is BDL. The
dehydrogenase activity, ectomycorrhiza, P-solubilizing
bacteria, and total bacterial count in mine spoil are
practically negligible, compared with the normal soil. The
radioactivity level, particularly with respect to g-emitters
220
Ra, 228Ac, 40K, is 15.7, 31.9, and 150.3 Bq/kg,
respectively. Altogether, the physico-chemical characteristics and fertility of mine spoil compare poorly with normal
agricultural soil.
3.2.2. Lignite fly ash
From Table 3, it can be observed that the LFA applied at
various stages of field trials includes lower content of sand

It is evident from Fig. 1 that because of the increase in the


dosage of LFA (alone) from 5 to 20 t/ha, the grain yield of
the first crop increased significantly (p!0.05) and
progressively in the range from 11.59 to 24.63% over the
control (T1). An additional increase in the crop yield of 1.5
10.2% was due to the combined effects of LFA and press
mud. However, at higher dosages, the yield decreased
sharply and to less than the control, particularly in T11T14
(100 and 200 t/ha LFA, with and without press mud).
Nonetheless, however little the growth, no symptoms of
toxicity were noticed from trace or heavy metals present in
LFA. This observation of increase and decrease in the yield
also holds for the grains of the third, fifth, and sixth crops.
Significant increase (p!0.05), in the range from 3.0 to
42.0% over corresponding control values of individual
crops, with increasing dosage of LFA (520 t/ha), with and
without press mud, and decrease at dosages beyond these
values were observed. The maximum increase in yield over
the control appeared with repeat applications in T8 (20 t/ha
LFA and press mud) of the third crop. Also, a greater
effectiveness was noticed of repeat applications at lower
dosages, up to 20t/ha, of LFA made before cultivation of the
third and fifth crops, compared with both one-time
application at 100 and 200 t/ha of LFA (T11T18) and
repeat applications at 50 t/ha in T9 and T10. Hence, the
optimum dosage of LFA (with and without press mud) is
20 t/ha for both one-time and repeat applications. The
adverse effect of the application of higher dosages of LFA
(beyond 20 t/ha) was observed to decrease in successive
years of growing crops, and the yield was either at par with
the yield of the corresponding control of a particular crop or
slightly higher.
The trend of increased yield with up to 20 t/ha of LFA
(with and without press mud), together with a decrease at
higher dosages, also appeared in straw, where the range of
increase was almost the same, although the decrease was

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L.C. Ram et al. / Journal of Environmental Management 79 (2006) 173187

Fig. 1. Effect of one-time and repeat applications of different dosages of LFA with and without press mud on the grain yield of rice crops (CD at 5% for Crop
I0.031, Crop III0.030, Crop V0.034, Crop VI0.031).

less. Such adverse effects on the yield were well


corroborated in a separate investigation (CARD, 1997),
and they are possibly attributable to compaction of the
surface (hardpan formation, observed clearly during
cultivation) resulting in poor aeration and root penetration,
owing to the highly pozzolanic nature of LFA containing the
CaAlSi type of minerals and to the higher soluble salts
and silt content with moisture. However, the gradual
decrease in the adverse effects on crop yield at higher
dosages of LFA (beyond 20 t/ha, with and without press
mud), together with progressive improvement in growth
performance, during the course of growing successive crops
(on the basis of the biometric observations discussed above),
indicates the progressive amelioration of the conditions of
mine spoil, favorable for crop growth. Furthermore, it seems
that both green gram and sun hemp grown as green manure
have contributed to enhancing the yield of the next crop. As
an illustration of the point, the yield of grain, 1.92 and
2.05 t/ha in the treatments T1 (without any amendment) and
T2 (with press mud only), respectively, of the third crop was

considerably higher than that of the corresponding


treatments of the first crop (1.38 and 1.58 t/ha), which
clearly indicates the positive effect of green manure. Thus,
the overall beneficial effect of LFA applications of up to
20 t/ha, alone and in combination with press mud, in
significantly (p!0.05) increasing the yield of various crops
over the corresponding controls (even up to the last crop),
suggests better mine-spoil health and sustainability.
3.4. Effect of LFA application on characteristics
of mine spoil
3.4.1. Physico-chemical characteristics
A trend was observed in the mine soil with increasing
dosage of LFA, up to 200 t/ha (with and without press mud),
after the harvest of the first crop: a decrease from control
values for sand, from 52.8 to 47.8%; for clay, from 14.5 to
14.2%; and for BD, from 1.71 to 1.64 g/cm3and an
increase for silt, from 32.7 to 38.0%; for WHC, from 20.1
to 24.2%; and for porosity, from 30.5 to 34.8% (Fig. 2).

L.C. Ram et al. / Journal of Environmental Management 79 (2006) 173187

179

(b) 45
(a) 60

40
35

50

30
Silt (%)

Sand (%)

40
30

25
20
15

20

10
10

5
0

0
T1

T2

T7

T8

T9

T10 T11 T12 T13 T14

T1

T2

T7

T8

T9

T10 T11 T12 T13 T14

T1

T2

T7

T8

T9

T10 T11 T12 T13 T14

T1

T2

T7

T8

T9

T10 T11 T12 T13 T14

(d) 30

(c) 18
16

25

14
20
WHC (%)

Clay (%)

12
10
8

15
10

6
4

2
0

0
T1

T2

T7

T8

T9

T10 T11 T12 T13 T14


(f) 1.74

(e) 40

1.72
35
1.70
BD (g/cc)

Porosity (%)

30
25
20

1.68
1.66

15

1.64

10

1.62

1.60

1.58
T1

T2

T7

T8

T9

T10 T11 T12 T13 T14

Fig. 2. Effect of LFA on texture (sand, silt, and clay), WHC, porosity and BD of mine spoil after harvest of first crop.

This observation is important in agriculture, especially as


regards the easy penetration of the root and better plant
growth. The morphological structure of fly ash is such that it
has a spherical hollow shape, and it is possible that smallsized particles of LFA, containing a larger proportion of silt
(54.058.0%) than mine spoil (33.4%), accumulate in voids

created by bigger-sized particles of mine spoil. This


contributed to the modification of the texture of mine
spoil (Khan et al., 1996). Furthermore, with increased
dosage of LFA, up to 200 t/ha (with and without press mud),
an increase occurred in pH, from 6.50 (control) to 7.69;
and in EC, from 0.413 (control) to 0.795 dS/m (Fig. 3).

9.0

0.9

8.0

0.8

7.0

0.7

6.0

0.6

5.0

0.5

4.0

0.4

3.0

0.3

2.0

0.2

1.0

0.1

0.0

OC (%)/EC (dS/m)

L.C. Ram et al. / Journal of Environmental Management 79 (2006) 173187

pH

180

0.0
T1

T2

T7
pH

T8

T9

T10

EC (dS/m)

T11

T12

T13

T14

OC (%)

Fig. 3. Effect of LFA on pH, EC and OC values of mine spoil after harvest of first crop.

The increases in the pH and EC values could be ascribed,


respectively, to the alkaline nature and the higher solubility
of the inorganic constituents of LFA. In fact, the increase in
EC could be considered high and likely to suppress normal
growth, especially as the EC values in the range 0.51.0 dS/
m can reduce germination and cause burning or wilting of
sensitive crops (CSTPA (Council of Soil Testing and Plant
Analysis), 1992). Probably, enhancement of EC, particularly enhancement beyond 20 t/ha of LFA, is one of the
factors responsible for poor growth and low yields. The
increase in OC, from 0.31 to 0.43%, could be ascribed to the
application of organic matter, such as press mud,
biofertilizer, and humic acid.
The available major and secondary nutrients (N, P, K, S,
Ca, and Mg) in the mine spoil after the harvest of the first
crop increased distinctively with various dosages of LFA

of up to 200 t/ha, with and without press mud (Fig. 4).


For example, Ca increased in the range from 40.6 (T1) to
44.3 ppm (T13) and from 41.3 (T2) to 45.1 ppm (T14),
respectively, with increasing dosage of LFA of up to 200 t/
ha, alone and in combination with press mud. The increase
of Mg for corresponding treatments was in the range from
22.8 (T1) to 25.7 ppm (T13) and from 23.4 (T2) to 26.9 ppm
(T14). This increase in the content of Ca and Mg reflects the
gradual increase in pH of mine spoil with increasing dosage
of LFA. The available micronutrients (Cu, Zn, Mn, and Fe)
were similarly enhanced (Fig. 5). This observation is close
to findings by others (Sims et al., 1994). Along with this, a
higher increase in nutrient status was noticed in combination
treatments (LFA with press mud) than in individual ones,
which may possibly be ascribed to the benefit for crop
growth of the complementary nutrient status of these

Fig. 4. Effect of LFA on available content of major and secondary nutrients in mine spoil after harvest of first crop.

L.C. Ram et al. / Journal of Environmental Management 79 (2006) 173187

181

Fig. 5. Effect of LFA on available content of micronutrients and trace metals in mine spoil after harvest of first crop.

amendments. It is pertinent to mention that though


the availability of nutrients increased in the mine spoil
when LFA was increased beyond 20 t/ha (with and without
press mud), the enhancement of EC values, along with
hardpan formation, probably predominated to cause both
poor growth and low yield.
The results on available trace and heavy metals in mine
spoil after the harvest of the first crop reveal that even after
the addition of various dosages of LFA of up to 200 t/ha,
with and without press mud, the concentration of Cr, Pb, Co,
Cd, and As remained BDL. Conversely, an appreciable
increasing trend in Ni was noticed, in the range from 2.06
(T1) to 2.45 (T13) and 2.10 (T2) to 2.48 ppm (T14), up to the
highest dosage of LFA of 200 t/ha, alone and in
combination with press mud (Fig. 5), which is well within
the permissible limits (Srivastava and Gupta, 1996). The
physico-chemical characteristics of mine spoil on amendment with LFA, alone and in combination with press mud,
improved appreciably, depending on the dosage and
characteristics of the amendments, where the rice crop
was not affected due to build up of salinity, particularly up
to 20 t/ha of LFA. Others have made similar studies of the
effects of coal ash in improving physico-chemical characteristics of mine spoil, with no adverse symptoms of toxicity
(Hill and Lamp, 1980; Molliner and Street, 1982).
Analogous to the observations made of mine spoil after
the harvest of the first crop, a trend of decreased sand, clay,
and BD and increased silt, WHC, and porosity was noticed in
the mine spoil after harvest of the third, fifth, and sixth crops,
where the range of values shows a gradually improved
texture. The same trend could be observed for pH, EC, and
OC; available major and secondary nutrients (N, P, K, S, Ca,
and Mg); and micronutrients and trace and heavy metals (Cu,
Zn, Mn, Fe, and Ni) in the mine spoil with these crops with
increasing dosage of LFA, with and without press mudwith

only slight variation. This variation occurred in a slightly


higher range for chemical properties and nutrient content and
in a lower range for trace and heavy metals than for the mine
spoil of the preceding crops (data not shown), depending
on the overall effects of the amendments discussed above.
However, other trace and heavy metals remained BDL.
The improvement in the physico-chemical properties of
amended mine spoil indicates its possibly beneficial impact
on crop yield, where the role of press mud and other organic
matter, via their decomposition and N demineralization, is
crucial (Adriano et al., 1982). The acidifying tendency of
protons from organic-matter decomposition of press mud,
biofertilizer, humic acid, and even gypsum would offset the
alkalizing tendency of the CaO and MgO present in LFA,
which maintained near-neutral pH (6.88) of the mine spoil
after the harvest of the last crop (sixth). As a result, the wide
gap between the pH values of mine spoil (6.5) and those of
LFA (10.2310.54) and the increase in buffering capacity do
not matter much and result in no toxicity due to the
controlled carryover of toxic trace and heavy metals by crop
produce. Here, the hypothesis can also be considered that
mixing fly ash with biosolids produces a material with more
balanced properties (e.g. neutral pH and the presence of
essential elements) and less potential for environmental
contamination than in either material applied alone
(Stevenson, 1982; Sims et al., 1993; Wong, 1993). The
beneficial effects have been reported of sewage sludge and
other amendments, such as lime and gypsum, added to coalash material in maintaining pH, changing the water-soluble
OC and EC, and releasing N, P, and K for assimilation by
plants during the revegetation of the soil (Martens and
Beham, 1976; Pietz et al., 1989). Similarly, a reduced
incidence of pests in LFA-amended plots might also have
enhanced crop yield (Narayanaswamy and Nambirajan,
2000). Thus, after application of various dosages of LFA, up

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L.C. Ram et al. / Journal of Environmental Management 79 (2006) 173187

to 200 t/ha, alone and in combination with press mud and


other amendments as supplementing agents, the physicochemical properties and fertility of the mine spoil improved,
but with uptake of trace and heavy metals within
permissible limits. However, hardpan formed, and the
soluble salt content increased, particularly at dosages
beyond 20 t/ha of LFA, which were, of course, gradually
annulled in the course of successive crops.
3.4.2. Radioactivity level
The radioactivity levels in the mine spoil after the harvest
of the last crop (sixth), with respect to g-emitters 220Ra,
228
Ac, and 40K, were observed to have gone above the
control value, from 14.2 to 26.1, 29.7 to 41.6, and 145.2 to
170.3 Bq/kg, respectively, with the application of the
maximum dosage of LFA of 200 t/ha alone (data not
shown). But the levels of the radionuclides were well within
permissible limits and in agreement with the findings by
others (Ramachandran et al., 1990; McMurphy and
Rayburn, 1996).
3.4.3. Biological activity
The biological activity of the mine spoil, almost
negligible initially, was found to have improved significantly
(p!0.05) as a result of the addition of LFA of up to 20 t/ha,
alone and in combination with press mud. After the harvest
of the first crop, a significant (p!0.05) increase occurred in
microbial activities over the control. The ectomycorrhiza
increased from 0.0 (T1) to 38.0 spores/g; P-solubilizing
bacteria, from 0.01 (T1) to 1.5 CFU!104; total bacterial
count, from 0.18 (T1) to 4.5 CFU!104g; and dehydrogenase
activity, from 0.035 (T1) to 0.068 mg/kg hK1, up to the
dosage of 20 t/ha of LFA alone (T7). A similar trend was
observed for treatments of up to 20 t/ha of LFA in
combination with press mud (T8), with enhanced ranges of
difference (data not shown). This trend was also observed in

the mine spoil after harvest of succeeding crops, with


progressively increased ranges of difference. With applications of LFA beyond 20 t/ha, the total bacterial population
decreased (as was also evident from a decrease in the enzyme
activities), probably as a result of hardpan formation and
development of anaerobic and waterlogging conditions.
These enhanced microbial activities in the mine spoil
might have played a crucial role in improving the soil
fertility and yield of various crops appreciably. Here, the
organic amendment as supplementing agent might have
contributed to the improvement in the condition of the mine
spoil by increasing cation exchange capacity (CEC) and
organic-matter (humus) content, resulting in better fertility
and enhanced microbial activity, besides enhanced immobilization of toxic elements and other factors inhibiting
microbes (Chaney and Giardono, 1977). As well, the role of
the improved texture of the amended mine spoil in enhancing
biological activity cannot be ruled out (Lyon et al., 1952).
These observations are in agreement with findings by others
(Pitchel, 1990; Lai et al., 1999).
3.5. Effects of LFA on the characteristics of crop produce
3.5.1. Characteristics of grain
Fig. 6 shows that the total major and secondary
nutrients, such as N, P, K, S, Ca, and Mg, in the grain
samples from treatment T7 (20 t/ha of LFA alone) after
harvest of the first crop increased over the control (T1),
from 1.28 to 1.34, 0.059 to 0.071, 0.66 to 0.75, 0.068 to
0.70, 0.035 to 0.42, and 0.019 to 0.026 ppm, respectively.
Concomitantly, an increase occurred in the total content
of these nutrients in the grain sample from treatment T8
(20 t/ha of LFA with press mud), with notably enhanced
ranges of difference. With applications beyond this
amount, the concentration of these nutrients decreased,
similar to the crop yield.

Fig. 6. Effect of LFA on concentration of total major and secondary nutrients in grain samples of first crop.

L.C. Ram et al. / Journal of Environmental Management 79 (2006) 173187

183

Fig. 7. Effect of LFA on concentration of total micronutrients and trace and heavy metals in grain samples of first crop.

The concentration of micronutrients and trace and heavy


metals also increased over the corresponding control values
in the LFA treatments (with and without press mud) of up to
20 t/ha, for each element (Fig. 7). In a trend quite similar to
that of the results obtained for yield and major and
secondary nutrients, the concentration of micronutrients
decreased with the increase in LFA dosage beyond 20 t/ha,
which suggests that such high dosages of LFA have no
appreciable impact on the nutrient status of grain. Likewise,
the concentration of the trace and heavy metals Cr, Pb, and
Ni in the grain samples from treatment T7 (20 t/ha LFA
alone) increased over control T1, from 1.64 to 2.39, 1.22 to
1.38, and 5.21 to 6.33 ppm, respectively. This observation is
also pertinent to the grain sample from treatment T8 (20 t/ha
LFA with press mud) with a notably higher range of
difference. However, there was also a decrease at dosages
beyond 20 t/ha of LFA (with and without press mud). But
the concentrations of Co, Cd, and As were BDL in all LFA
treatments. The trend observed for major and secondary
nutrients, micronutrients, and trace and heavy metals was
also observed for the grains from succeeding crops, with
ranges of difference being a little on the high side in the case
of major secondary nutrients and being on the low side in
the case of micronutrients and trace and heavy metals.
The small increase in trace and heavy metals content is
suggestive of low availability of trace and heavy metals,
which gradually decreased because of the increase in the pH
of the mine spoil with increasing LFA dosage (Fulekar,
1993), the presence of metals in oxide form (Page et al.,
1979), an increase in adsorption of metals by soil with
increased pH, and the resulting marginal uptake by crop
produce (Adriano et al., 1980). However, the possibility of
metals becoming more soluble after a long duration cannot
be entirely ruled out, as the liming effect of fly ash
application is prone to diminish due to natural or
anthropogenic soil acidification processes (Sims et al.,

1995). The carryover of toxic trace and heavy metals in


grain depends on several factors, such as pH, OC, CEC,
micro-organisms, concentration of metals, and their form of
occurrence, and the mobility of such elements to the root,
their transport from root surface to root interior, and their
translocation from root to shoot (Chaney and Giardono,
1977) plays a significant role. The Pb and Cr absorbed by
roots normally remain in the root and are not readily
translocated to the shoot (Alloway, 1995), whereas Cd can
readily be translocated from root to shoot, but it is the higher
values of Zn and pH that reduce the uptake of Cd. Probably
for this reason, the uptake of these toxic trace and heavy
metals in the grain was well within the critical toxicity limits
(MacNieol and Beckett, 1985; Alloway, 1995; Srivastava
and Gupta, 1996). As far as the higher uptake of Ni, from
5.21 to 6.35 ppm, is concerned, it is probably because of its
readily mobile characteristics in plants, leading to its
extensive accumulation in the seeds (Alloway, 1995),
which is also not alarming. Furthermore, the concentrations
of Co, Cd, and As were below detection limits, which is
obviously due to their relatively lower initial content in both
mine spoil and LFA. As a result, the grain samples from
treatments at the optimum dosage of LFA had improved
nutrient status, whereas the carryover of toxic trace and
heavy metals was well within permissible limits. The
decrease in concentration of nutrients in grain at dosages
beyond 20 t/ha of LFA is probably due to hardpan formation
in the mine soil, together with an increase in its salt content,
resulting in poor growth. This observation is well bolstered
by other studies (Pitchel et al., 1994; Sen et al., 1997).
3.5.2. Characteristics of straw
Concomitantly with the variation in the characteristics of
the grain samples after the harvest of the various rice crops
with different dosages of LFA, alone and in combination
with press mud, the characteristics of the straw samples also

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L.C. Ram et al. / Journal of Environmental Management 79 (2006) 173187

Fig. 8. Effect of LFA on gamma radioactivity of grain samples from different crops.

varied (data not shown). The observed trend of decreased


concentrations of major and secondary nutrients, micronutrients, and trace and heavy metals in the straw, like in the
grain, beyond 20 t/ha of LFA is possibly due to the same
reasons discussed above.
3.5.3. Radioactivity level in crop produce
Fig. 8 shows the radioactivity level of g-emitters 226Ra,
228
Ac, and 40K in the grain samples of various crops from
plots amended with higher dosages of LFA in T11 (100 t/ha
LFA) and T13 (200 t/ha LFA), suggesting a slight increase,
particularly in 226Ra and 228Ac. But in 40K, the increase was
substantial, from 40.2 (control) to 52.6 and 64.8 Bq/kg in
T11 and T13, respectively, in the grain sample of the first
crop. This observation also holds true in the case of straw,
with lower ranges of difference (Fig. 9). Furthermore, in the
grain and straw samples of the succeeding crops, a similar

trend of progressive increase from one crop to the next crop


has been observed, but with levels well within permissible
limits (Eisenbud and Thomas, 1977; Boweh, 1996). Thus,
the radioactivity levels of these emitters increased only
marginally, except in the case of 40K, probably as a result of
the application of LFA containing a higher content of 40K,
170.3 Bq/kg, than mine spoil (145.2 Bq/kg). Although the
radioactivity of muriate of potash (KCl) was not measured,
it is possible that its application as one of the components of
the basal dosage of chemical fertilizer (NPK) during
cultivation might have contributed to the enhanced level
of 40K in crop produce (Srivastava and Gupta, 1996). In a
separate study, Geerardo (2001) expressed concern about
the radioactivity in crop produce resulting from the
application of chemical fertilizers, including KCl. The
application of phosphatic fertilizers, liming, and manures
to reduce the uptake of radionuclides in crop plants

Fig. 9. Effect of LFA on gamma radioactivity of straw samples from different crops.

L.C. Ram et al. / Journal of Environmental Management 79 (2006) 173187

(Skiba, 1987) through reduction in exchangeable fraction of


radionuclides has been investigated (Butnik and Ishenko,
1990).
3.6. Plausible mechanism for improvement
of soil health
The overall beneficial effects of fly ash on soil health may
be ascribable to the cumulative effect of the improvement in
physico-chemical and biological characteristics of the soil.
Because of the presence of CaSi minerals with a
pozzolanic nature (zeolite formation), along with the
moisture of the soil (Fulekar and Dave, 1986), fly ash
brings about improvements in various physico-chemical
properties, such as BD, porosity, WHC, and the available
water in the soil. In particular, the fly ash has a higher silt
content than soil, and the infiltration rate of sandy soils or
mine spoil is drastically checked because of the increase in
silt (Furr et al., 1977), whereas in the clay-rich type of soils,
the reverse is the case, with better water movement and
workability, apart from decreased plasticity or crack
formation after drying. As fly ash has most of the essential
plant nutrients other than nitrogen and humus (Menon et al.,
1990), applying it to the soil naturally improves its fertility
by enriching it with these elements, and this results in
increased crop yield. The organic amendments made with
fly ash also help in improving the humus and microbial
activities of the amended soil or mine spoil, besides
adjusting the pH by way of decomposition and N demineralization (Adriano et al., 1982; Stevenson, 1982; Sims et al.,
1993; Wong, 1993), controlling the availability of metals
to the plant by chelation, and releasing nutrients during
vegetation (Logan and Traina, 1993).
The formation of a zeolite layer on the surface of fly-ash
particles results into two exchangeable sites, one with 6-fold
coordination and the other with 12-fold coordination, to
accommodate micro- and macronutrients, respectively, so
that each ash particle becomes a repository of nutrients and
a potential nutrient pump (Sahu, 1999). Besides, adsorption,
desorption, and exchange being pH dependent, the mineral
pump is energized selectively for nutrient transfer to
achieve rapid growth of plant in the fly-ash-amended
soils. Furthermore, during the ashwater interaction,
oxyhydroxide of iron (goethite) is formed and acts as a
great scavenger of trace metals. The oxyhydroxide
flocculates, either as coating or as discrete grains, and thus
immobilizes the heavy metals, leading to their reduced
availability (Leekie et al., 1980). Consequently, the loss of
nitrogen from the soilbecause of volatilization, leaching,
and denitrificationis significantly reduced, and this
improves the N-utilization efficiency of nitrogenous
fertilizers and minimizes soilwater pollution. The plants,
then, take up nitrogen in phases, as and when needed. Fly
ash also helps in the retention of the chemical fertilizer
applied through inorganic sources in the soil system for
longer periods (CFRI, 2000), leading to residual effects of

185

fly-ash application. The uptake and carryover of trace and


heavy metals in grain depend on several factors, such as pH,
OC, CEC, micro-organisms, concentration of metals and
their form of occurrence, their mobility to the root and
transport from root surface to root interior, and their
translocation from root to shoot.

4. Conclusions
LFA acts as an excellent soil modifier and conditioner, a
very good liming agent, and a source of essential plant
nutrients for appreciably improving the texture and fertility
of the mine spoil, with significant (p!0.05) increase in the
crop yield (about 42%) over the control, together with better
residual effects, especially up to 20 t/ha of LFA, with and
without press mud. In general, the optimum dosage of LFA
is 20 t/ha for both one-time and repeat applications, and
overall maximum yield was obtained on repeat application
of the same dosage of 20 t/ha of LFA with press mud. No
adverse effect on the quality of mine spoil or crop produce
was observed up to the optimum dosage of LFA
applications, except for hardpan formation in mine spoil
and the enhancement of soluble salt content at dosages
beyond the optimum, which, in fact, decreased progressively during cultivation of succeeding crops. The uptake and
carryover of certain trace and heavy metals and g-emitters
in mine spoil and crop produce were well within permissible
limits. Therefore, aside from restoring the ecology of a
mine-spoil area and making it agriculturally worthwhile, the
judicious application of LFA, with and without press mud,
provides a gainful and eco-friendly solution to the problem
of the disposal of LFA.

Acknowledgements
The authors express their sincerest gratitude to Standing
Scientific Research Committee (SSRC), Department of
Coal, India for providing financial assistance. They are also
thankful to the Director, CFRI, and NLC authorities for
providing infrastructure facilities and permission to publish
the paper.

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