Environ Geochem Health (2007) 29:237–248
DOI 10.1007/s10653-006-9079-4
ORIGINAL PAPER
Toxic mine drainage from Asia’s biggest copper mine
at Malanjkhand, India
Piyush Kant Pandey Æ Richa Sharma Æ
Manju Roy Æ Madhurima Pandey
Received: 26 January 2006 / Accepted: 24 November 2006 / Published online: 6 February 2007

Springer Science+Business Media B.V. 2007
Abstract This paper has studied the environ-
mental deterioration due to copper mining in
Malanjkhand at Central-east India. No data is
available on environmental degradation at the
studied site although geological aspects are well
studied. Mine drainage from the mines is defin-
itively toxic. The site is also undergoing various
stages of acid mine drainage (AMD) particularly
from the heap leaching sites and the tailing area.
AMD impacted water steam and sediment were
also analysed. Results show substantial level of
contamination of almost all segments of environ-
ment. Presence of elevated level of other heavy
metal viz. Au, Ag, Pb, Cr, Cd, Fe, Cu and base
metals like Na, K in AMD impacted water and
sediments is due to metal leaching effect of
AMD. Bio monitoring with the help of benthic
macro invertebrates and metal accumulation in
plants was also carried to know the impact of the
toxic drainage. Results prove a very significant
impact on the environmental health.
P. K. Pandey (&)
R. Sharma
M. Roy

M. Pandey
Centre for Environmental Science & Engineering,
Department of Engineering Chemistry,
Bhilai Institute of Technology,
Durg 491002 Chhattisgarh, India
e-mail: drpiyush_pandey@yahoo.com
Keywords Copper mining
Toxic mine drainage

Acid mine drainage
Benthic macro invertebrates

Heavy metal contamination
Enrichment factor
Introduction
Acidic drainage is the worst possible yet inevita-
ble outcome of any base metal mining associated
with sulphide ores. In studies of acidic drainage, a
latency period between near-neutral conditions of
the mine discharges and the onset of net-acidic
drainage is well recognized, generally ranging
from a few days to more than 15 years.
Acid mine drainage (AMD) invariably devas-
tates fish and aquatic habitat in the receiving
waters. The unfortunate aspect of the problem
are that it is virtually impossible to reverse with
existing technologies, and once the AMD has
started at any location then it may require
millions of dollars annually for treatment of the
discharge and this process may continue for
centuries.
Acid mine drainage occurs when sulphide-
bearing minerals in rock are exposed to air and
water, changing the sulphide to sulphuric acid.
This acid can dissolve heavy metals found in
waste rock and tailings such as lead, zinc, copper,
arsenic, selenium, mercury and cadmium, into
ground and surface water. Certain bacteria, nat-
urally present, can significantly increase the rate
123
238
of this reaction. AMD and heavy metals pollution
can poison ground and drinking water.
There are numerous examples of acidic drain-
ages from copper mines from the various parts of
the world. For example the Mount Lyell Mine in
Western Tasmania, Australia was the site of
continuous copper mining and processing from
1893 to 1994. A century of mining with little
control of acid drainage has degraded over 40 km
of rivers and streams which are consequently
unable to support aquatic life of any significance.
The Mount Lyell ore deposit contains in excess of
10% sulphide and acidic discharges from the lease
area carries in excess of two tonnes of copper a
day into downstream catchments. Other examples
of acid drainage from such mines are Spenceville
Copper Mine, Leviathan Sulphur Mine, Iron
Mountain Copper Mine, and Walker Copper
Mine (Custis, 1994).
Materials and methods
Description of the contaminated area
Base metal mine at Malanjkhand in Balaghat
district is the single largest copper ore producer in
India, which constitutes about 40% of the copper
reservoir and its annual production is 2-million
tones of copper ore per anum. Geographically it is
located 90 km NE of the Balaghat town in
Madhya Pradesh and it lies between 2202¢ N
and 8043¢ E.The deposit area is a platitude area
located at altitude of about 575 m above M.S.L.
Malanjkhand froth prospect owned by Hindu-
stan Copper Limited (HCL) produces about
2-million metric tons (MMT) of copper ore per
annum but it does not carry out the metals
smelting operation at Malanjkhand. A concentra-
tion plant of 2-MMT capacity is also located here.
This mine is operating since July 1882. Inspite of
the obvious fact that the environment surround-
ing the copper mine is generally degraded; no
systematic study is available in the literature on
the subject. Location of the Malanjkhand mine
area is shown in Fig. 1. This paper aims to assess
the environmental health of various segment of
environment surrounding Malanjkhand Copper
deposit.
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Environ Geochem Health (2007) 29:237–248
The purpose of this study was to evaluate the
environmental impacts of this active copper mine
on its surroundings. Surveying the area, designing
a sampling strategy, and testing the water and soil
down gradient from the mining area for heavy
metals completed an assessment of the research
site.
Sampling and analytical procedure
Major area sampling of the contaminated area
was carried out in November-2003 followed by
seasonal monitoring at some select locations. The
sampling sites were located to trace the potential
movement of metals, as they are transported from
the mine-site or waste-rock through the soil and
into surficial water. Stations were located along
the dominant flow/deposition paths.
The sampling bottles were cleaned with chro-
mic acid, detergent solution from Merck
(Extran), tap water and finally with double
distilled water sequentially. Duplicate samples
were collected on each sampling site and a
protocol of preservation was followed. All moist
solid samples were dried at 40C in uncontami-
nated petridishes up to complete dryness. All
solid samples were finally crushed and weighted
accurately by digital weighing machine (Denver
instrumental company TX104), 0.5 or 1 g of
sample were taken for digestion in clean, uncon-
taminated Teflon beaker and digested as per the
standard methods (APHA, 1992).
A proper quality assurance and quality control
(QA/QC) protocol was followed which, consisted
of the following steps: First, measurement of
certified calibration standards as samples, maxi-
mum allowed difference was 3%. Second, mea-
surements of calibration check standards with
known analyte concentration but of different
origin than the calibration standards, maximum
allowed difference was 5%. Third, measurement
of sample blanks and laboratory blanks to control
the instrument contamination and the contami-
nation arising out of the sample preparation,
respectively. Fourth, laboratory check samples
were prepared from unexposed containers with
standard addition of elements; maximum devia-
tion allowed was 5%. And fifth, a standard
reference material (SRM) of urban dust from
Environ Geochem Health (2007) 29:237–248
Fig. 1 Location map of Malanjkhand mine area. Sampling sites: 1. Karamsara Lake (S1) 2. Leaching pond effluent (S2)
3. Waste dump (i) (S3) 4. Waste dump (ii) (S4) 5. Tailing pond (S5) 6. Water holes within Copper mine (S6)
National Institute of Standards Technology
(NIST) SRM—1648 was used for ensuring the
quality control.
Elemental standards used were prepared by
dilution of the stock certified single element
solution for AAS supplied by Merck, Germany.
The dilution water used was deionised double
distilled water. All other reagents used were
analytical grade chemicals obtained from Merck,
India/Germany. Background checks were also
made and the intrinsic trace element content thus
deduced was appropriately integrated in the
result. The detection limits (DL) were calculated
as three times the standard deviation of nine
measurements of blanks for every wavelength.
Standard analytical methods were used for all
type of sample analysis i.e., measurement of pH
by single electrode pH meter, conductivity by
conductivity meter, chloride by silver nitrate
method, sulphate by turbidity meter. Na, K, Ca
was analysed by flame photometer. Arsenic was
analysed by Atomic absorption Spectrophotome-
ter with hydride generation and background
correction facility (Chemito 201), occasionally
239
by SDDC method (NEERI, 1977; Stratten &
Writehead, 1962). Metals i.e., copper, cadmium,
zinc, iron, lead, nickel, chromium, molybdenum,
magnesium, manganese were analysed by Atomic
Absorption Spectrophotometer (Chemito, 201).
Result and discussion
One of the challenges of today’s mining opera-
tions is that heavy metals, which pose a potential
environmental hazard, are naturally occurring
elements in the ore that is removed for process-
ing. For a typical copper mine, one ton of waste
rock can contain several pounds of copper, five
ounces of zinc, three ounces of lead, and two
ounces of arsenic. Limits currently exist for heavy
metals in industrial wastewater discharge yet the
base metal mining is known to possess huge
potential for contaminated discharges at unprec-
edented scale. We studied the geology and the
elemental chemistry of the ores and tailings of the
copper mines to understand the potential for
adverse effect.
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240
Geology of Malanjkhand
Precambrian rocks of the central India at the
genetic grade in this area as they are suppose to
be linked with the great deltoic routes in Don-
gargarh Nagpur belt of the Bhandara Craton the
metasedimentory and volcanic sedimentary sup-
per crystals of the Sacoli, Sauser and Chilphi
group are overlain on the older granites and
gneiss (Fig. 2). Malanjkhand area confirms to the
above general geology where two distinct division
of the proterozoic age are visible. The old group
consist of basement granitoids separated by
unconformity from the younger mildly metamor-
phose sedimentary rocks of the Chilphighat
series. The basement complex is of middle pro-
terozoic age, is made of basic rocks aplite, quartz
reef and veins and solid granitoids where as the
metamorphose sedimentary rocks of the Chil-
phighat series consist of shales and phyllites, and
stone, quartzite and arkosic grits, arkoses, con-
glomerate and quartz veins.
The copper reserve is located in area, which is
exposed on the hilly ridges and this position in an
archaic shape over to a length of 2.6 km in NS
direction.
This area is basically confined to sheared
quartz, veins/reef. This reef is having an average
width of 65 M, which shares highly fractured and
Fig. 2 Geologic map of
Malanjkhand (Yedekar,
Jain, Nair, & Dutta, 1990)
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Environ Geochem Health (2007) 29:237–248
fissured planes with granitoids. This highly frac-
tured and sheared geology appears responsible
for hydrothermal genesis of sulphidic ore at
Malanjkhand. The hydrothermal alterations ob-
served in Malanjkhand area are seritization sauc-
erization, chloritization, potassic alteration and
silicification. Among these alterations the min-
eralised granitoids are characterised by potassic
alteration, which most conspicuous and wide-
spread.
Three major type of mineralisation have been
observed at Malanjkhand. Firstly quartz type
confined to the reef quartz. Second are stringer
types with in the quartz/calcite veins in the
granitoids and the third are disseminated rocks.
The primary ore in Malanjkhand area are
chalcopyrite, pyrite, molybdenite, magnetite, and
sphalerite and the secondary ore are chalcosite,
bornite, and covallite. The oxidized ore are
malachite, azurite, cuprite and native copper.
The most prominent ore minerals are chalcopy-
rite. chalcocite and the oxidized ore mineral are
confined to the upper part of the deposit.
Composition of ore and the tailings from HCL
mines and the pollution potential
The average concentration of Cu in the mined ore
is about 1.05% composition of ore (Mill Feed)
Environ Geochem Health (2007) 29:237–248 241

and flotation wastes (Tailings) in the samples is process for extracting the copper from oxide ores.
presented in the Table 1 and based on the The most common indicator of sulphide oxidation
composition it can be seen that more than is sulphate. Some other indicators are iron,
2,230,252 MT of the tailings are being deposited copper, zinc, manganese, lead and cadmium, and
every year on the open ground, which contains major ions such as calcium, magnesium, alumin-
more than about 10,000 MT of sulphur. Exposed ium, sodium and potassium. High sulphate con-
to the environment it is but a certainty that the centrations in drainage and a reduction in
atmospheric oxidation will cause an acid genera- alkalinity, even when the pH is still about neutral,
tion to the tune of about 980,000 MT. This acid is indicates sulphide oxidation. Decreases in pH and
liable to be neutralised to some extent by the increases in metal concentration may lag behind
natural alkalinity but the description of geology the increases in sulphate concentration due to
of the area presented in the preceding paragraphs buffering and neutralisation processes (EA,
makes it clear that the buffering capacity of the 1997).
volcanic rocks of the region is very limited. We This fact is corroborated by the acid impacted
did not witness any measure for the collection and discharges collected from the mine sites
treatment of the acidic water at the mine sites. (Table 2). The examinations of acid impacted
water discharges show a mean pH of 2.7, maxi-
Toxic drainage from mine area mum pH of 3.2 and minimum pH of 2.5 (Table 3).
The acid impacted leachates show the abundance
The entire area is drained by river Banjar that lies of metals in the following order:
2.2 km in NW direction from the copper mining
Major elements: copper, zinc, manganese, nickel,
pit. The entire area in an around the area of
chromium, iron and sulphate.
copper mining is surrounded by moderate to
dense forest and climate is moderately tropical.
Minor elements: molybdenum, magnesium,
The area around the mine site at Malanjkhand
sodium, potassium and calcium.
can be seen to be highly impacted by wide spread
environmental destruction by the acid water Trace elements: silver, arsenic, cadmium, lead.
discharged in the mining, and the froth collection
process.
Another major source of the acid water The mining at Malanjkhand has produced huge
discharge has been identified as the heap leaching waste-rock piles and has exposed material to the
elements of weathering. By extracting copper
from the parent ore, the remaining material
Table 1 Composition of the ore, tailings and concentrate becomes high in concentrations of associated
obtained from the Malanjkhand mine
heavy metals (iron, sulphur, lead, cadmium, zinc,
Ore Tailing Concentrate and manganese). These metals are found to
Yearly production 2,316,845 2,230,252 86,593 leaching into the surrounding area through per-
(MT) colation and drainage. Hence it is affecting the
Cu% 1.053 0.1 26.6 chemistry of the nearby soils, water and thus
Fe% 2.85 2.37 26.8 affecting plant and animal life down stream.
S% 1.47 0.41 29.6
Insoluble % 91.16 92.41 14 The adverse effects of the drainage and perco-
Au (g/t) 0.13 0.03 2.25 lation around and through the existing exposed
Ag (g/t) 3.98 1.43 59.5 parent ore and waste-rock are the formation of
Mo (ppm) 159 46 3197 toxic substances in ground and surficial waters.
Co (ppm) 33 45 198
Cr (ppm) 125 25 120 The deposit chemistry has shown the presence of
Ni (ppm) 13.8 15 50 metallic minerals (such as galena [lead sulphide,
Pb (ppm) 13.5 12.6 70 PbS], chalcopyrite [iron-copper sulphide, FeS.
Zn (ppm) 28.4 23.4 807 CuS], sphalerite [zinc sulphide, ZnS]) in addition
Mn (ppm) 57 87.1 54
to pyrite and pyrrhotite at Malanjkhand. Such a

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242 Environ Geochem Health (2007) 29:237–248

Table 2 Major elemental analysis of impacted water streams (values in ppm unless shown otherwise)
Name of sample pH Cu Cd Zn Ni Cr Fe (%) Mn Mo Pb Ag Ca Mg Na K As SO4

Heap leachate 1 3.2 8549.7 5 260 60 100 2.1 168 13 0.09 0.15 35 40 45 25 0.05 3500
Heap leachate 2 2.7 1199.7 6 356 85 204.9 2.6 180 20 0.1 0.2 37 42 40 22 0.06 3800
Discharge pond 2.6 1899.7 0 700 414.9 85 0.93 165 15 0.07 0.13 25 30 38 20 0.02 3700
River discharge 1 2.5 8000 8 300 50 152 0.54 170 10 0.05 0.1 36 41 42 22 0.03 2500
River discharge 2 3 7600 5 250 95 125 2.5 185 15 0.08 0.23 40 35 38 25 0.07 2900
Mine effluent 1 2.6 8500 4 190 85 65 0.85 144 12 0.07 0.12 28 32 40 28 0.08 3000
Mine effluent 2 2.8 555500 3 200 120 130 0.96 120 14 0.1 0.13 26 35 35 23 0.04 2500

combination is known to cause a secondary effect
of the oxidation of the iron-sulphur minerals to
sulphuric acid and ferric iron.
The stable pH developed (2.5–3.0) and the
products of sulphuric acid and ferric sulphate
create conditions where the ferric iron ion itself
can act as an oxidant (above about pH 3 the ferric
ion is itself hydrolysed to ferric hydroxide, which
precipitates as the rust-coloured stain associated
with ARD). In the absence of ferric iron at pH
2.5–3.0, sulphuric acid will dissolve some heavy
metal carbonate and oxide minerals, but has little
reactive effect on heavy metal sulphides. How-
ever, ferric iron ion is capable of dissolving many
heavy metal sulphide minerals, including those of
lead, copper, zinc, and cadmium, by the general
reaction:
impoundment before being attenuated, while less
mobile metals precipitate or adsorb closer to the
surface of the impoundment. The mobility of
metals from any tailing impoundment is generally
considered to be in the order of Fe = Mn > Zn >
Ni > Co > Pb > Cu. A similarly stable mobility
trend is evidenced in the present study, which is
further emphasized by lower values of standard
deviation, kurtosis and skewness, which is possible
due to Gaussian distribution pattern (Table 3).
Correlation analysis of the results follow the
expected trend wherein the acid mobilized ele-
ments viz. Cr, Zn, Ni etc. correlated negatively
with the pH whereas the other metal show a
reverse behaviour (Table 4).
Analysis of the impacted sediment

MS þ nFeþþþ ¼ Mnþ þ S þ nFeþþ
Where: MS = solid heavy metal sulphide;
Fe+++ = aqueous ferric iron ion; Mn+ = aqueous
heavy metal ion; S = sulphur; Fe++ = aqueous
ferrous iron ion.
Oxidation reactions in the unsaturated zone in
tailings cause major changes in the solid phase
geochemistry (Ribet, Ptacek, Blowes, & Jambor,
1995). The most major change is the depletion of
sulphidic phase by oxidation reactions, which
then leads to the release of trace metals (in waste
rock or tailings) like Cu, Ni, and Co to the
aqueous phase.
Oxidation reactions that generate acid also
cause the depletion of carbonate minerals
through neutralization reactions in the unsatu-
rated zone. The zones of accumulation can be
used to determine an order of metal mobility;
more mobile metals travel further into the tailings
It was aimed here to see the levels of contami-
nation of sediment and the conditions and quan-
tity of metals, which may be mobilised under
different conditions. Contaminated sediment is a
major cause of environmental problems and a key
factor in many of the impairments to beneficial
uses of the water bodies. Hence, it is imperative
to assess the quantity of metals, which may easily
mobilise because it can play an important role in
aquatic health and the human risk assessment.
Sediment with high metals concentration can play
important role to the ground water quality
because sediments usually act as a sink for
pollutants. Consequently, sediments associated
contaminants can influence the concentration of
trace metal in both the water column and biota if
they are desorbed or become available to benthic
organisms. One of the major problems that heavy
metals cause with respect to their effect on
aquatic organisms is their long biological half-life.

123
Environ Geochem Health (2007) 29:237–248 243

3128.57

3000.00

0.04
2500.00
3800.00
–1.96
205.54

543.80
We collected some sediment samples in and
around the mining sites and the selected sites

SO4
were not directly impacted by flow of effluents.
The sediment analysis also demonstrates a high

–1.20
0.05
0.01
0.05
0.02

0.00
0.02
0.08
As metal loading in the surficial waters. Based on
the results of sediment it is surmised that the
23.57

23.00

20.00
28.00
1.00

2.64
0.08
0.50
recycling of metals from the sediments to the
K

water column is likely to increase in response to

1.21

3.20
0.47
0.32
39.71

40.00

35.00
45.00
any future decrease in metal concentrations in the
Na

overlying water. The toxic metal mobility in the

sediments can be related to the bulk composition
1.76

4.65
36.43

35.00

–1.74
–0.10
30.00
42.00
Mg

(specifically iron and manganese content) and the

redox status of the sediments. As the studied
2.26

5.97
32.43

35.00

–2.06
–0.19
25.00
40.00

sediments contain a moderate concentration of

Ca

Fe (Mean 1.8% with a similar median value) the

0.15
0.02
0.13
0.05

0.95
0.10
0.23
–0.29

metal sequestration capacity of the sediment is

Ag

not very high (Table 5). It also known that the

mobility of toxic metals in sediments is correlated
0.08
0.01
0.08
0.02

0.05
0.10
–0.53
–0.46
Pb

with sediment toxicity that is the reason that

sediment of studied region already appears to be
1.18

3.13
1.85
0.91
14.14

14.00

10.00
20.00

toxic to the aquatic life.

Mo

The results of sediment contamination were

8.52

0.99
22.54

–1.19
161.71

168.00

120.00
185.00

compared with the threshold effect levels (TEL)

Mn

value for the freshwater sediments as laid down

by Environment Canada (1994) to find out the
1.50
0.33
0.96
0.87

0.39
0.54
2.60
–2.27

enrichment factor (EF) of the contaminated

Fe

sediments. The EF was calculated as follows:

EF = metal concentration in the studied sedi-
0.54
0.72
17.55

46.44

65.00
123.13

125.00

204.90

ments/concentration of metal in threshold effect

Cr

levels in uncontaminated sediments.

129.99

127.70

414.90
6.29
2.47
48.27
85.00

50.00

The values greater than 1 indicate enrichment

Ni

tin the studied medium. The calculation (Table 6)

shows a high enrichment in case of Cu (69), Ni
Table 3 Descriptive analysis of AMD impacted water

66.49
322.24

259.64
175.91

190.00
699.64
4.77
2.10

(38.5), Zn (11.4) and significant to moderate in

Zn

case of Cd, Cr and Fe.

Problem with the sequestration capability of
–0.59
4.43
0.95
5.00
2.51
1.19

0.00
8.00
Cd

the river sediment can be further understood by

comparing the same with Shivnath river sediment
–1.28
–0.87
5892.73
1188.59
7600.00
3144.72

1199.70
8549.70

studied by us (Pandey, Nair, Bhui, & Pandey,

Cu

2004). Compared elements show (Fig. 3) a nega-

tive enrichment in Banjar river at Malanjkhand
2.77
0.09
2.70
0.25

0.90
2.50
3.20
–0.17

compared to the Shivnath sediment in Durg-

pH

Rajnandgaon region.
Standard deviation

Toxic metal mobilization is taking place at a

big scale at Malanjkhand, which can be evidenced
Standard error

by the water quality analysis of the surface water

Maximum
Minimum
Skewness

sources (Table 7). Correlation study of surface

Kurtosis
Median
Mean

water shown that strong correlation between Cu

and Fe (0.86), result presented in Table 8. The

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Table 4 Correlation analysis of AMD impacted water

pH Cu Cd Zn Ni Cr Fe Mn Mo Pb Ag Ca Mg Na K As SO4

pH 1.00
Cu 0.32 1.00
Cd 0.02 0.42 1.00
Zn –0.32 –0.69 –0.58 1.00
Ni –0.28 –0.60 –0.86 0.90 1.00
Cr –0.09 –0.44 0.58 –0.08 –0.36 1.00
Fe 0.66 –0.19 0.21 –0.12 –0.27 0.44 1.00
Mn 0.17 –0.13 0.38 0.30 –0.03 0.36 0.61 1.00
Mo 0.13 –0.79 –0.18 0.28 0.19 0.55 0.71 0.31 1.00
Pb 0.55 –0.36 –0.18 –0.22 –0.13 0.32 0.61 –0.21 0.70 1.00
Ag 0.52 –0.22 0.11 –0.08 –0.15 0.40 0.92 0.58 0.70 0.51 1.00
Ca 0.38 0.24 0.78 –0.33 –0.61 0.56 0.68 0.78 0.17 0.00 0.64 1.00
Mg 0.20 0.06 0.84 –0.35 –0.68 0.77 0.40 0.39 0.14 0.18 0.17 0.70 1.00
Na 0.28 0.40 0.52 –0.11 –0.39 –0.02 0.17 0.47 –0.28 –0.26 –0.13 0.45 0.56 1.00
K 0.33 0.73 0.21 –0.75 –0.58 –0.45 0.11 –0.18 –0.31 0.03 0.09 0.13 –0.12 0.22 1.00
As 0.28 0.36 0.28 –0.65 –0.56 –0.06 0.47 0.09 0.17 0.25 0.50 0.36 0.02 0.07 0.85 1.00
SO4 0.17 –0.61 –0.33 0.59 0.42 0.06 0.51 0.47 0.66 0.32 0.34 0.02 0.02 0.29 –0.25 0.00 1.00

Table 5 Statistical analysis of sediments. (Units in ppm unless shown otherwise)

Cu Cd Zn Ni Cr Fe (%)

Mean 2459.94 4.45 1403.92 694 154 1.82

Standard error 237.3 0.25 69.34 16.31 4.30 0.13
Median 2099.7 4.5 1400 690 155 1.85
Standard deviation 530.57 0.57 155.0511 36.47 9.618 0.28
Sample variance 281504 0.32 24040.83 1330 92.5 0.08
Kurtosis –3.25 –2.50 –0.80 1.63 –0.022 0.18
Skewness 0.62 –0.23 –0.08 0.75 –0.59 0.57
Maximum 3080 5 1599.6 750 165 2.24

Table 6 Enrichment factor for trace metals in Malanjkhand The most obvious casualty in case of AMD is
Toxic Average Threshold effect Enrichment the surface water and to some extent the ground-
metals (ppm) levels (ppm) for factor water that is essentially two separate identities of
freshwater sedimentsa the single underlying media. The water quality of
Cu 2460 35.7 68.9 river Banjar upstream of the Malanjkhand area
Cd 4.45 0.6 7.41 and after the addition of metal drainages shows a
Cr 154 37.3 4.12 significant change (Fig. 4). High enrichment SO4
Fe 1.84% 20% 0.092 (761.3), Cu (634), Fe (422) and Cl (134) are the
Zn 1404 123.1 11.4
Ni 694 18 38.5 main impact of the mining activities.
a
(Environment Canada, 1994)
Impact on aquatic ecodiversity
groundwater contamination levels of the loca-
tions, which were mainly located in the upper Metal cycling via physical and chemical weath-
reaches of the studied site, are presented ering of discrete sources (copper mines) and
(Table 9). This contamination level is expected regional (non-point) sources (sulphide-rich shale)
to be high in the watershed area. Correlation is evaluated by chemistry of weathering products.
analysis of ground water had shown that Cu The elements in copper mine waste, secondary
moderate to strongly correlate to other studied minerals, stream sediments, and waters that are
water parameters (Table 10). most likely to have negative impacts on aquatic

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Environ Geochem Health (2007) 29:237–248 245

Fig. 3 Comparative 100000

heavy metal analysis of
10000
sediments of Shivnath
river and Banjar river in 1000
Malanjkhand mine site 100
10
1
0.1 Cu Cd Cr Fe

Shivnath Malanjkhand % Enrichment in Malanjkhand

Table 7 Surface water quality parameters study

Location PH SO4 Cu Zn Fe Cl

SF 1 (Interstate border) 7.00 5.00 0.20 0.12 0.80 12.90

SF 2 (Banjar river) 7.10 10.00 0.30 0.07 0.30 17.00
SF 3 (Banjar river) 6.90 7.00 0.25 0.06 0.40 0.00
SF 4 (Banjar river) 6.80 9.00 0.26 0.00 0.30 0.00
SF 5 (Banjar river) 5.30 28.00 0.60 0.04 1.30 0.00
Drinking water 7.50 20.00 0.00 0.08 0.10 0.00
Cd, Cr, Ni, Mn, Hg are absent in above water sample

Table 8 Correlation analysis of surface water secondary weathering products also. Both of these
are impacting aquatic ecosystems.
pH SO4 Cu Zn Fe Cl
Mine drainage is a complex mixture of ele-
pH 1.00 ments that interact to cause a variety of effects on
SO4 –0.34 1.00 aquatic life that are difficult to separate into
Cu –0.13 0.40 1.00
Zn –0.35 0.66 –0.42 1.00 individual components. Toxicity is dependent on
Fe –0.15 0.42 0.86 –0.24 1.00 discharge volume, pH, total acidity, and concen-
Cl 0.38 –0.43 0.09 –0.51 0.09 1.00 tration of dissolved metals. The pH is most
critical component, as the lower pH will have
severe potential impacts on aquatic life. The
ecosystems are aluminium, copper, zinc, and overall effect of mine drainage is also dependent
arsenic because these elements locally exceed on the flow (dilution rate), pH, and alkalinity or
toxicity guidelines for surface waters or for stream buffering capacity of the receiving stream. The
sediments. The formation of AMD in the studied higher the concentration of bicarbonate and
location with high rainfall and the long dry carbonate ions in the receiving stream, the
spells provide ideal venues for development of higher the buffering capacity and the greater the

Table 9 Ground water quality of adjoining area of Malanjkhand

Location PH SO4 Cu Zn Fe Cl

GW (Birja) 6.00 20.00 0.20 0.40 1.20 37.00

GW (Chorsole) 6.50 15.00 0.00 0.30 0.30 26.00
GW (Bhimjeri) 6.80 10.00 0.00 0.25 0.40 17.00
GW (Birja) 6.20 15.00 0.00 0.20 0.50 12.00
GW (Damoh) 7.00 21.00 0.25 3.60 0.30 38.90
GW (Salghat) 6.50 25.00 0.30 0.20 0.80 38.90
Cd, Cr, Ni, Mn, Hg are absent in above sample

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Table 10 Ground water correlation study cause a reduction in the diversity and total
pH SO4 Cu Zn Fe Cl
numbers, or abundance, of macro invertebrates
and changes in community structure, such as a
pH 1.00 lower percentage of EPT taxa.
SO4 –0.10 1.00
Our assessment shows a considerable lowering
Cu 0.10 0.93 1.00
Zn 0.64 0.31 0.44 1.00 of the density, richness and EPT taxa in the
Fe –0.73 0.47 0.47 –0.36 1.00 Banjar river stream compared to the reference
Cl 0.11 0.85 0.91 0.46 0.42 1.00 point, which was chosen upstream. Though the
reference point also showed average macro
invertebrate matrices, the impacted stream has
protection of aquatic life from adverse effects of shown a very poor assessment (Table 11).
AMD (Kimmel, 1983). AMD with elevated met-
als concentrations discharging into headwater Impact of metal enrichment on land based
streams or lightly buffered streams can have a flora
devastating effect on the aquatic life. Secondary
effects such as increased carbon dioxide tensions, Element, such as Cu, Mo, Zn, Mg, Mn, P and S are
oxygen reduction by the oxidation of metals, essential micro-nutrients that the plants require
increased osmotic pressure from high concentra- for their proper growth. The essential micronutri-
tions of mineral salts, and synergistic effects of ents are readily taken up by plants, provided the
metal ions also contribute to toxicity (Parsons, concentration in the soil substrate does not exceed
1957). In addition to chemical effects of mine a certain critical level. This critical level is species
drainage, physical effects such as increased tur- dependent. However, there are non-essential ele-
bidity from soil erosion, accumulation of coal ments, which, if dissolved in nutrient solution,
fines, and smothering of the stream substrate enter into a plant’s dynamic system by passive
from precipitated metal compounds may also uptake (Berry, 1986). The availability of mineral
occur (Parsons, 1968). nutrients in the root environment influences the
Benthic (bottom-dwelling) macro invertebrates metal content of a plant. With the increase in
are often used as indicators of water quality concentration of an element, the normal function-
because of their limited mobility, relatively long ing of a plant is hampered and plants may develop
residence times, and varying degrees of sensitivity symptoms of toxicity such as dwarfism, chlorosis
to pollutants. Unaffected streams generally have and necrosis (Berry & Wallace, 1981). In extreme
a variety of species with representatives of all cases (with lethal levels of concentration) a plant
insect orders, including a high diversity of insects may restrict the inflow of toxic metals through its
classed in the taxonomic orders of Ephemerop- roots or may simply fail to grow due to the death
tera (mayflies), Plecoptera (stoneflies), and Tri- of the root. Some plants may take up metal
choptera (caddisflies) (EPT taxa). Like many passively and deposit it in senescent organs such as
other potential pollutants, mine drainage can leaves and needles. The senescent parts are

Fig. 4 Comparative 1000

water quality parameters
and enrichment study of 100
upstream and impacted
stream 10

1
pH SO4 Cu Zn Fe Cl
0.1

0.01
Upstream Impacted stream % Enrichment

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Environ Geochem Health (2007) 29:237–248 247

Table 11 Macro invertebrates matrices from Malanjk-
hand area
Parameters Banjar river Reference
(Malanjkhand) point upstream
Density 25 >300
Richness 13 >30
EPT 9.5 >18
Assessment Very poor Average
subsequently deposited in such a manner that the
normal metabolism process continues unhindered.
Metal concentrations in plants depend not only on
the total soil concentration, but also on the
chemical speciation of metals in soil and soil
solution (Spasito & Page, 1984). After being
dislodged from an ore body by ground water
action and indirectly by the chemical reaction of
the plant themselves, metal ions may remain in
solution and migrate away from their source or
may precipitate out of solution. They may be
scavenged and may become adsorbed on ion
exchange sites of hydroxides of Fe and Mn,
depending on the ionisation potential of that
metal relative to Fe and Mn. Humic compounds
and the surfaces of clay particles may also absorb
active metal cations due to their higher surface
negativity. It is commonly believed that a plant
species found growing in the vicinity of, or over a
substrate having anomalous metal values may
have anomalous concentrations of metals in one
or more plant parts. But normally a genetically
fixed mechanism controls the nutrient uptake
potential for different mineral nutrients (Berry,
1986). The toxic effect (Berry, 1986) may genet-
ically modify a species producing an ‘‘ecotype’’ or
‘‘metallophyllic ecotype of finding an anomaly in
plant organs may reveal the plant’s nature (i.e.,
hyper-accumulator or effective indicator).
With the above objective we analysed the
metal concentrations in the land-based flora of
the region. The results present an interesting
feature (Table 12). The results show a consider-
able enrichment of the metal levels in various
plant species commonly found in the area. The
results further confirm that some species viz. S.
Urens, H. Suavenolens are hyper accumulators of
metals and particularly of copper. This result
confirms a previous report (Pal & Sindhupe,
2004) in the regard and hence these species can
also be considered as geo-indicator plants. Chem-
ical analysis also shows a significant correlation
between Cu, Ni, Cr and Cd and a negative
correlation with Fe (Tables 13 and 14).
Based on the geology and the water chemistry
it can be seen that AMD at the present site is
principally caused by the oxidation of pyrite and
pyrrhotite and the subsequent ferric iron induced
dissolution of chalocopyrites, etc. The oxidation
rate is depending on many factors, which define
the environment within the waste-rock pile,
including pH, temperature, oxygen concentration,
chemical composition of the contacting water,
and also the microbial population. The overall
oxidations are causing the ultimate drainage
water with high levels of major ions, and trace
elements but with near-neutral pH values. Exten-
sive damage to the flora and fauna is visible in the
receiving waters. The extent of damages to the
overall environment is so high that it can be
termed as criminal negligence on the part of the
concerned.

Table 12 Metal concentration in the land flora of Malanjkhand area

Name of vegetation Cu Cd Zn Ni Cr Fe (%)

Calotropis procera (Aak) 139.7 0 1100.2 26.6 0 0.13

Syzygium cumini (Jamun) 63.2 0 210.4 53.4 0 0.21
Azadirecta indica (Neem) 85.6 8 140 11 8 3.6
Sterculia urens (Kurlu tree) 1250 7 920 168 10 0.45
Hyptis suavenolens (Jangli Tulsi) 390 5 800 140 5 0.37
Pimpinella heynreana (Jangli Dhania) 150 4.5 750 120 8 0.38
Dalbergia paniculata (Dhobnin) 270 6 375 145 5 0.25
Adina cordifolia (Hardool) 280 3.7 180 120 7 0.28

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Table 13 Descriptive statistical analysis of metal concentration in land based flora

Cu Cd Zn Ni Cr Fe (%)

Mean 328.56 4.28 559.45 98.00 5.38 0.71

Standard error 137.30 1.05 133.12 20.92 1.31 0.41
Median 210.00 4.75 562.50 120.00 6.00 0.33
Standard deviation 388.33 2.97 376.52 59.16 3.70 1.17
Sample variance 150801.60 8.82 141765.54 3499.60 13.70 1.38
Kurtosis 6.13 –0.82 –1.92 –1.55 –0.83 7.82
Skewness 2.40 –0.57 0.17 –0.52 –0.64 2.79
Range 1186.80 8.00 960.20 157.00 10.00 3.47
Minimum 63.20 0.00 140.00 11.00 0.00 0.13
Maximum 1250.00 8.00 1100.20 168.00 10.00 3.60
Sum 2628.50 34.20 4475.60 784.00 43.00 5.67
Count 8.00 8.00 8.00 8.00 8.00 8.00
Confidence level (95.0%) 324.65 2.48 314.78 49.46 3.09 0.98

Table 14 Correlation analysis of metal concentration in Kimmel, W. G. (1983). The impact of acid mine drainage
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Cu Cd Zn Ni Cr Fe (%) technology and utilization (pp. 424–437). The Pa.
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Cu 1.00 NEERI (National Environmental Engineering Research
Cd 0.43 1.00 Institute) (1977). Technical Digest 54.
Zn 0.42 –0.16 1.00 Pal, A. P., & Sindhupe, G. L. (2004). A preliminary study
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Cr 0.55 0.87 –0.06 0.51 1.00 Malanjkhand granitoid. Journal of Geological Survey
Fe (%) –0.19 0.57 –0.43 –0.53 0.36 1.00 of India, 64, 146.
Pandey, P. K., Nair, S., Bhui, A., & Pandey M. (2004).
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