Availability of Chromium, Nickel and Other Associated Heavy Metals of Ultramafic and Serpentine
Transcript of Availability of Chromium, Nickel and Other Associated Heavy Metals of Ultramafic and Serpentine
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Availability of Chromium, Nickel and Other Associated
Heavy Metals of Ultramafic
and Serpentine Soil /Rock and in Plants Adarsh Kumar
1, Subodh Kumar Maiti
2
1Research Scholar,
2 Professor, Environmental Science
and Engineering, Centre of Mining Environment,
Indian School of Mines, Dhanbad-826004, Jharkhand, India.
Abstract— This paper reviews the concentration of
heavy metals particularly Cr and Ni in the
serpentinised and ultramafic soil/rock throughout the
different geological regions in the world which are
produced due to anthropogenic means or due to natural
weathering. Poor nutrient content, low Ca: Mg ratio,
higher concentration of heavy metals is major reason
for the sparse vegetation on such soil. The vegetation
covers present on such area are metal tolerant and some
plants turned out to be hyperaccumulator which are
economically important and significant for extraction of
metals from it. This review further includes different
case studies of serpentine/ultramafic soil and plants
across the globe.
Keywords— Chromium, Nickel, Serpentine Soil,
Ultramafic, Hyperaccumulator
I. INTRODUCTION
Contamination of soil by trace metals is of great
concern for today’s environment. The major origin for the
release of high proportion of trace metals is dependent
upon the geochemistry of that particular region. Ultramafic
/serpentinite regions are found contaminated with
enormous amount of trace metals which includes high level
of Cr, Ni, and associated metals (Mg, Pb, Co, Zn etc.) with
other elements. Ultramafic/serpentinite is mainly composed
of serpentine soil which includes mineral groups
(Mg6Si4O10[OH]8) formed from original olivines ((Mg,Fe)2
SiO4) and pyroxenes ((Mg,Fe)2Si2O6 or Ca(Mg,Fe)Si2O6)
and contains high level of Mg, low Ca and Al and
extremely deficient in Na and K (Alexander, 2004b).
Serpentinization is a metamorphic process involving
hydrothermal processes in which low-silica mafic and
ultramafic rocks are oxidized (anaerobic oxidation of Fe2+
by the protons of water) and hydrolyzed with water into
serpentinite. It occurs as peridotite and pyroxenite rocks
and includes Fe and Mg-rich silicate minerals i.e. olivine
((Mg, Fe2+
)2[Si2O4]) and pyroxene (XY(Si,Al)2O6). Due to
the alteration by hydrothermal fluids these minerals get
detached from the subduction block and incorporated into
subduction melanges (Coleman, 1967; Gough et al., 1989;
O’Handley, 1996; Oze et al., 2004b). The serpentine group
minerals, lizardite (Mg3Si2O5(OH)4), chrysotile (Mg3Si2O5
(OH)4) and antigorite ((Mg,Fe2+
)3Si2O5(OH)4) were formed
by the hydration of pyroxene. Some of the other minerals
which are commonly associated with serpentinites include
magnetite (Fe2+
,Fe3+
2O4), Cr-rich magnetite (Fe2+
(Fe3+
,Cr)2
O4), chromite (FeCr2O4), and other mixed-composition
spinels, talc (Mg3Si4O10(OH)2), chlorite ((Mg,Fe)5
Al[(OH)8|AlSi3O10]), tremolite ([Ca2][Mg5] [(OH)2|Si8
O22]), and brucite (Mg(OH)2) (Oze et al., 2004b).
Chromium is often found in spinel minerals as chromite,
chromium magnetite, and other mixed-composition spinels
which contains enormous amount of Cr, Al, Mg, and Fe
(Oze et al., 2004b).
Chromium was discovered by the scientist Vauqueline
in the year of 1798 in Siberian red lead ore (crocoites)
(Shankera et al., 2005). Chromium exists in nature in two
stable forms: Cr (III) and Cr (VI) which is predominantly
contained in the chromite ore and is highly resistant to
weathering (Bacquer et al., 2003). Cr (III) is less toxic and
less soluble at circum–neutral pH and gets readily sorbed
onto Fe oxides; and required in a small quantity for the
proper functioning of the biological systems. In
comparison, Cr (VI) is 100-1000 times more carcinogenic,
toxic and mutagenic for human health and because of its
higher solubility in water it contaminates water bodies too
(Zayed and Terry, 2003). Weathering of these ultrabasic
rocks results in the removal of toxic trace metals and get
concentrated near the wetland water discharge areas. Since,
Ni, Mn, and Fe are more mobile in the reducing
environment rather than Cr; they get readily removed from
the ultramafic rocks (Lee et al., 2001). Due to association
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of Al, Mg, and Fe along with Cr and Ni the serpentine soil
produces enormous quantity of toxic heavy metals which
creates adverse effect on biological system. Fe, S and
organic matter are known Cr (VI) reducers whereas MnO
are considered to be the only environmentally relevant Cr
(III) oxidizers (Bartlett and James, 1979; Eary and Rai,
1987; Fendorf, 1995; Negra et al., 2005). Cr and Ni are
considered to be essential micronutrients for plants and
animals and required in less quantity, however at higher
concentrations it becomes biologically toxic and results in
carcinogenic effect primarily through respiratory pathway
(Goyer, 1996). A minimum concentration of 0.5 mg kg-1
in
water and 5 mg kg-1
of Cr in soil results in the detrimental
effect of plants (Turner and Rust, 1971).
The toxicity of soil is because of the presence of
chromate ions which is present in hexavalent form and
creates skin irritations (Yassi and Niober, 1988),
respiratory problems via inhalation (Whalley et al., 1999),
carcinogenic effect (Goyer, 1996; Katz and Salem, 1993;
Kortenkamp et al., 1996), weakened immune systems,
kidney and liver damage, alteration of genetic material,
lung cancer etc. The natural concentration of Cr in soil
ranges from 10 to 50 mg kg-1
depending on the parental
material whereas; ultramafic soils contain the maximum
concentration of chromium and can reach upto 125 mg kg-1
(Adriano, 1986).
II. SOURCES OF TRACE METALS IN SOIL
ENVIRONMENT
The trace metals are originated from two major sources
natural geochemical processes (weathering of ultramafic
rocks) and human activities (anthropogenic activities)
(Lazaro et al., 2006). Anthropogenic activities such as
metallurgical industries, metalliferous mining and smelting,
use of fertilizers and soil amendments in high-production
agriculture, and land disposal techniques for municipal
/solid wastes are the major source for the contamination of
trace metal in the soils (Alloway, 1995; Adriano, 2001;
Commission of the European Communities, 2002).
III. TOXICITY OF TRACE METAL IN PLANTS
Ultramafic soil is rich in Cr, Ni, Mn, Zn, Co, Pb etc.
Plants growing on such rock/ soil are highly deficient in
nutrients. However, due to these high levels of heavy
metals, plants accumulate rich level of metals such as Ni,
Zn etc., which require different mechanisms to keep ion
homeostasis and to detoxify unfavorable effects on
themselves (Clemens 2001). Increase of heavy metals
causes oxidative stress (production of reactive oxygen
species), which are directly creating adverse effect on
tissues and cellular components (Sajedi et al., 2010;
Schutzendubel and Polle, 2002).
A. Chromium toxicity in plants
Heavy metals accumulated in the different plant parts
results in the toxicity of plants. Chromium at higher
concentration becomes toxic for the plants and results in
the detrimental effect. Many trace metals such as Ni, Zn,
Mn, Cu etc. are required for the proper growth and
development of the plants. Plants have carrier molecules
for the uptake and translocation of these metals; however,
there is no specific mechanism for the uptake of chromium
since they are lacking carrier molecules for the
translocation of Cr.
Therefore, plants use same carriers for the translocation
of Cr which is non essential element for the plant
metabolism. It was reported that the maximum quantity of
element contaminant was always contained in roots and a
minimum in the vegetative and reproductive organs
(Shankar et al., 2005). The reason for the accumulation of
Cr in the plant root is immobilization of Cr in the root
vacuoles and inability to translocate from root to aerial
shoot parts.
B. Nickel toxicity in plants
Nickel is metabolically important and essential minor
element for the development of the plants but increase in
concentration results in toxicity (Fargasova, 2008). Plants
containing more than 100 mg dm–3
Ni develop symptoms
of toxicity. Different plants species have different
resistivity against nickel. While some plants are introduced
as Ni hyperaccumulators other are very sensitive and
introduced as non-accumulators (Freeman et al., 2004). In
the cytoplasm, high levels of free nickel generally avoid
removal of the metal ions to the vacuoles and the formation
of complexes with organic acids (Ernst et al., 1990). High
concentration of nickel inevitably binds organic
macromolecules and denatures them. Furthermore, nickel
can replace iron, zinc and magnesium due to the chemical
affinity with those elements, interfering with their
metabolism (Woolhouse, 1983). Ni is transported to
underground plant parts by the oxygen atoms either as
metal complexes of organic acids or as hydrated cations
(Salt et al., 2002). High Ni concentrations retard shoot and
root growth, affect branching development, deform various
plant parts, produce abnormal flower shape, decrease
biomass production, induce leaf spotting, disturb mitotic
root tips, and produce Fe deficiency that leads to chlorosis
and foliar necrosis.
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Additionally, excess Ni also affects nutrient absorption
by roots, impairs plant metabolism, inhibits photosynthesis
and transpiration, and causes ultrastructural modifications
(Ahmad and Ashraf, 2011).
TABLE 1: SOME OF THE IMPORTANT Ni AND Cr HYPER-
ACCUMULATOR PLANTS.
Metal
Hyperaccumulator
plant Family
References
Ni
Sebertia acuminata Sapotaceae Jaffre et al. (1976);
Perrier (2004)
Allysum
pintodasilvae
Allysum bertolonii
Alyssum
serpyllifolium
Brassicaceae
Garcia-Leston et al. (2007);
Barzanti et al. (2011);
Becerra-Castro et al.
(2009)
Phidiasia lindavii Acanthaceae Reeves et al. (1999)
Bornmuellera
kiyakii Brassicaceae Reeves et al. (2009)
Thalaspi goeingense
Brassicaceae Wenzel et al. (2003)
Berkheya coddii Asteraceae
Robinson et
al.(1997);
Moradi et al. (2010)
Cr
Dicoma niccolifera Asteraceae Baker and Brooks,
(1989)
Sutera fodina Scrophulariaceae Brooks (1998)
Salsola kali Amaranthaceae Gardea-Torresday et
al. (2005)
Leersia hexandra Poaceae Zhang et al. (2007)
Gynura
pseudochina Asteraceae
Mongkhonsin et al.
(2011)
Spartina
argentinensis Poaceae
Redondo-Gomez et.
al.,(2011)
Typha latifolia
Carex lurida
Typhaceae
Cyperaceae Zazo et al. (2008)
IV. PLANT, SOIL AND HEAVY METALS
A. Plant-Soil Interaction
Interaction of plant and soil involves many physical,
chemical and or biochemical processes which include
microbial and other living organism’s interaction with
environment. Thus, these living organisms by soil mineral
weathering increases soil sustainability and terrestrial
ecosystem productivity (Adriano, 2001; Balogh-Brunstad
et al., 2008). The heavy metals are present in the depth of
rocks which releases out due to weathering and get
accumulated in the soil. The plants which are able to
sustain themselves on these contaminated soils are able to
tolerate the toxicity and create interaction with the soil. X -
ray diffraction and X–ray fluorescence of the clay fraction
(>0.2mm) of rhizospheric soil has indicated that the
hyperaccumulator plants growing on the serpentine soil are
containing high level of Ni-rich ferromagnesium minerals
due to weathering. Same results were found, when a
hyperaccumulator species A. serpyllifolium subsp.
lusitanicum was compaired with non-accumulating species
Dactylis glomerata growing on the same geographical area.
Moreover, chlorite and serpentine are the dominant
clayminerals in the rhizosphere of both species but the
presence of smectite was only observed in the rhizosphere
of the Ni hyperaccumulator. Smectite has been identified as
weathering product of serpentine (Wildman et al., 1968;
Rabenhorst et al., 1982; Graham et al., 1990). The nutrient
availability of the ultramafic soil is very low. Ultramafic
soil is deficient in N, P, K, Ca, Cation Exchange Capacity
etc. Due to unfavorable soil properties and high level of
trace metals in the serpentine soil the roots are not properly
developed and they compel the plant roots to modify soil
conditions in the rhizosphere in order to promote nutrient
availability.
B. Plant-Heavy metal Interaction (Translocation of Cr and
Ni from Root to shoot)
Non-hyperaccumulating plants retain the heavy metals in
there root cells and detoxify them by chelating in the
cytoplasm or by storing them into vacuoles. Contrastingly,
hyperaccumulators rapidly and efficiently translocate them
into the leaf vacuoles via xylem (Rascio et al., 2011). The
pathway involved in the transport of Cr (VI) includes active
mechanism.
FIGURE 1: SCHEMATIC REPRESENTATION OF TRANSLOCATION
OF Cr AND Ni FROM ROOT TO LEAF.
The carriers involved in such transport mechanism are
sulphate (Cervantes et al., 2001). Fe, S and P are also
known to compete with Cr for carrier binding (Wallace et
al., 1976). Heavy metals Cr (III) and Cr (VI) present in the
soil get attached to the root surface and passes through the
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plasma membrane. Cr (VI) directly and in presence of SO4
(II) and Fe (III) moves into the plasma membrane and gets
reduced to Cr (III), enters into the vacuole and increases the
heavy metal concentration in the root vacuole. In hyper
accumulators these heavy metals get less accumulated in
the root vacuole and translocate into the aerial part (leaves)
through xylem. Skeffington et. al. (1976) has done a
experiment and by using radioactive tracers 51
Cr reported
that Cr mainly moved in the xylem of the plant. It is well
studied that Cr is maximum accumulated in root parts
rather than shoot. The main reason for the high
accumulation of Cr in roots could be because Cr is
immobilized in the vacuoles of the root cells, thus
rendering it less toxic, which may be a natural toxicity
response of the plant (Shanker et al., 2004a).Similar
translocation mechanism is involved for Ni. The main role
in heavy metal accumulation is played by free amino acid
such as histidine (His) and nicotinamine, which forms
stable complexes with the bivalent cations. Free histadine
(His) is considered as the most important ligand in the
hyperaccumulation of Ni (Callahan et al., 2006).
Presence of high concentration of His in the roots of
Thlaspi species which is Ni hyperaccumulators, suggest the
same mode of operation of amino acid in other
hyperaccumulators (Assuncao et al., 2003). Because of the
presence of carrier for the transport of Ni in plants, heavy
metal get absorbed from the soil easily, crosses the cell
wall and plasma membrane of the root and through xylem
gets accumulated in the leaf vacuole.
The root to shoot translocation in hyperaccumultor
plants relies on enhanced xylem loading by constitutive
overexpression of genes coding for transport system
common to non-hyperaccumulators (Rascio et al., 2011).
Moreover, Heavy Metal Accumulation (HMAs) plays a
vital role in metal homeostasis and tolerance (Axelsen and
Palmgren, 1988). The MATE (Multidrug And Toxin
Efflux) family of small organic molecule transporter seems
to be another transport protein that is active in translocation
of heavy metals in hyperaccumulation plants (Rascio et al.,
2011).
V. SIGNIFICANCE OF THE HYPERACCUMULATION
PROCESS
Phytoremediation is an emerging technology used by
different countries that uses plants to clean up pollutants
from the environment. It includes: Hyperaccumulation
process involves both ecological and physiological interest.
Apart from this it has some other applications such as:
potential application in phytomining and in genetic
engineering. Chaney et al. (1983) is the first to have
proposed the exploitation of heavy metal hyperaccumulator
plants to clean up polluted sites. It was found by different
researchers that Thlaspi and Allysum species are the well
known hyperaccumulators. Thlaspi can accumulate more
than one metal. However, there are many plants which can
accumulate only one type of metal. Apart from this they
can be used in their natural habitats only, and, above all,
have small biomass, shallow root systems and slow growth
rates, which limit the speed of metal removal (Cunningham
et al. 1995; Ebbs et al.1997). Apart from phytoremediation
phytoming is another excellent approach for the extraction
of metals from the plant parts.
Phytomining is another significant application which is
being used to extract the metals from the hyperaccumulator
plants. A pioneer phytomining study has been carried out
using the Ni hyperaccumulator S. polygaloides (Nicks and
Chambers, 1998) with a yield of 100 kg ha−1
of sulphur-
free Ni could be obtained after moderate application of
fertilizers. The removal of Ni from soil using phytomining
is viable in principle, since there are many
hyperaccumulator plants, such as Alyssum spp. and B.
coddii, fulfilling the criterion of achieving shoot Ni
concentrations higher than 10 g kg−1
on a dry matter basis
and producing more than 10,000 kg ha −1
year−1
(Brooks et
al., 1998). A. bertolonii can also accumulate 10 mg Ni g−1
dry matters from serpentine soil (Minguzzi et al., 1948).
Phytomining is also being used now days for the extraction
of other metals such as Au, Cu, Mn etc.
VI. STUDY OF THE SERPENTINE AND
ULTRAMAFIC REGION ACROSS THE WORLD
Different case studies were studied and evaluated to
understand the natural behavior and interaction of soil and
plant for the proper revegetation of the region.
A. Southeastern Quebec, Canada
Moore and Zimmermann (1977) conducted the experiment
on flat topped and slopping asbestos mine dumps to assess
factors which inhibited the plant growth and to find
solutions that can be used to improve plant growth. Nine
experimental plots of 4 x 4 m, divided into two subplots of
2 x 4 m, were established on the asbestos dumps and
addition of organic and inorganic fertilizer were used to
access the growth of the plant in the contaminated soil. A
combination of agricultural fertilizer containing ammonium
nitrate, potassium sulphate and super phosphate were added
to the mine waste at 0, 0.1, 0.25, 0.5 and 1 kg m-2
. Cow
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TABLE 2: ACCUMULATION OF Ni AND Cr (mg kg-1
) IN DIFFERENT PARTS OF THE PLANT BELONGING TO THE DIFFERENT GEOLOGICAL
REGION IN THE WORLD.
Location Plant Family Plant part Ni
(mg kg-1
)
Cr
(mg kg-1
) References
Anarak, Central Iran Aegopordon berardioides Asteraceae - 20.0 11.5 Ghaderian
and Baker.,
2007. Nain, Central Iran Cleome heratensis Capparaceae - 21.0 1.2
Pingarela, North–East of
Portugal
A. serpyllifolium Brassicaceae A 38105 129.2 Freitas et al.,
2004. L. spartea (L.) Scrophulariaceae A 492.0 706.6
Tras-os-Montes, NE
Portugal
A. serpyllifolium Brassicaceae L 670-31200 5-27
Lazaro et al.,
2006 Cistus ladanifer Cistaceae L 3-50 1.8-128
Plantago subulata subsp.
radicata Plantaginaceae L 46.4-267 7.7-80.5
Northern Apennines,
Italy
Silene armeria
Caryophyllaceae
- 2540 3503
Lombini et
al., 1998.
Cerastium arvense - 2685 3636
Minuartia laricifolia - 2629 3874
Dianthus sylvestris - 2501 3848
Biscutella laevigata Brassicaceae
- 2399 4470
Alyssum bertolonii - 2594 3351
Central Ridge and Costal
Range in Eastern Taiwan Brassica juncea Brassicaceae
R 18 42 Hsiao et al.,
2007. S 9 35
Santa Elena peninsula,
Costa Rica
Cynanchum schlechtendalii Asclepiadaceae - 235 1.7
Reeves et al.,
2007
Macroptilium gracile Fab./Papilionaceae - 114 16.4
Hyptis suaveolens Lamiaceae - 175 26.6
Oxalis frutescens Oxalidaceae - 106 15.7
Paspalum pectinatum Poaceae - 170 25
Diodia teres Rubiaceae - 246 38.7
Buchnera pusilla Scrophulariaceae
- 185 7.5
Russelia sarmentosa - 130 6.8
dung obtained from farmyard was applied at 1 and 4 kg m-
2. The mixture was evenly added to the upper top layer of
the mine dumps and seeded with a mixture of common
agricultural grasses and legumes at an amount of 20 g m-2
.
The experiment was conducted on native plants which are
growing in the pocket of the soil, overburden or waste rock
and were used by distributing there seeds evenly into the
plots. Addition of 1 kg m-2
of aluminum sulphate
significantly lowers the pH from 9.2 to 8.5. Deficiency
symptoms were seen in the plants especially on the
fertilizer plots only. Decrease in the nutrient was seen after
one season and capacity of regrowth was low after 1 year.
Germination of seeds was more on untreated soil but it
decreases after two months. Decrease in the pH results in
the leaching of heavy metals and does not help much in
revegetation. It was found that plots receiving 1 kg m-2
fertilizer or 1 kg m-2
fertilizer plus 4 kg m-2
manure had
more than 90% ground cover at the end of the first growing
season (September 1973).
Other experiment was conducted in 1974 on the slopes
using fertilizer and manure/saw dust. The plots treated with
only fertilizer shows only 10% cover whereas 90% of the
cover was seen using both fertilizer and saw dust/manure.
The poor growth rate of the plants was due to the less water
retention capacity of the slopes, washing off of the seeds
and fertilizer from the slope. Better result was seen on the
flat tops than slopes. After conducting the whole
experiment it was found that the most successful grasses
which can grow easily on the tailings are L. perenne, Poa
pratensis, Elymusjunceus and Bromus inermus. Poa
palustris and Hordeum jubatum were the most successful
of the locally-occurring species and Medicago sativa,
Trifolium hybridum and Melilotus alba were the most
successful legumes. The only plant whose root growth
exceeds 10 cm of length is Elymus junceus. Most of the
root growth in the plants is confined in the amended region.
The study of southern Quebec case study highlights the fact
that the tailing is nutrient deficient and requires amendment
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for the proper growth of the grasses and plants. Some
mines dumps are 60 years old and have limited vegetation.
To decrease the soil erosion and heavy metal contamination
revegetation of such dumps are required. Elymus junceus
can be easily establishment on asbestos tailing and can be
used significantly for revegetation of asbestos waste dump.
B. Nelson Region, New Zealand
Robinson et al. (1996) had studied and performed
detailed study on Ultramafic (serpentine) soils from the
Nelson Region which contains low total levels of calcium,
potassium, phosphate and high total levels of nickel,
chromium, cobalt, iron, manganese and magnesium. The
concentration of Ni, Cr and Mn are 6090, 7850 and 2780
mg kg-1
respectively. The growth of stress-tolerant plants
such as Cyathodes juniperina, Leptospermum scoparium
and Pteridium esculentum on the waste material from the
United Mine is strong evidence of its infertility. However,
the total abundance and solubility of the element is
unrelated and lower amount of these heavy metals were
observed in the extracts.
Different extracting agents were used in the
experiments with varying pH and the samples were eluted
through it. It was found that the concentration of Cr and Co
were low at the serpentine pH. This was because of the
lower mobility or leaching capacity of the Cr and Co
whereas high concentration of Ni and Mg was seen in
ultramafic soils seems likely to account for the observed
vegetation change. Only extractable manganese and iron
could be predicted by their total concentration. In an
experiment, the serpentine-endemic Italian crucifer
Alyssum bertolonii was grown for three months in
serpentine soil from the Dun Mountain Complex.
The plants had been sown in a tray containing 3.46 kg
of soil and extracted 0.019 g of nickel however the Ni
concentration in the soil is 6090 ug g.-1
. The pH of soils
under Beech forest was significantly lower than that under
serpentine vegetation and was probably a result of humic
decay of forest litter. From the study it was conclude that
the Nickel availability increases with decreasing pH.
Extractions in the range pH 1-9 were performed on a bulk
quantity of serpentine soil collected from near the United
Mine The magnesium/calcium quotient decreased from pH
1 to pH 4 then increased from pH 4 to pH 7. The pH of this
area satisfies the high concentration of Mg in the soil. With
decrease in pH the extractabilities of Ni, Mn, Co, Cr and
Zn was increased exponentially.
Lower concentration of extractable Cr, Co and Mn and
presence of very stunted serpentine vegetation in the
United Valley and Cobb Asbestos Mine clearly justifies
that these elements are not the limiting factor for
controlling of vegetation on ultramafic soils. The
concentrations of total soil nickel, chromium, manganese
and cobalt all showed significant increase with distance
into the ultramafics across an ecotone near the Dun saddle.
It was concluded from the experiment that the most
significant edaphic factors correlated with the distribution
of the serpentine vegetation are an excess of available
nickel and magnesium and/or an iron deficiency. This
effect is not limiting on nickel-poor sedimentary soils, but
the increased nickel availability at lower pH on serpentine
soils may prohibit forest colonisation of this ultramafic
environment. This hypothesis is supported by the
observation that isolated Nothofagus and Pinus radiate
have colonised humus-deficient ultramafics at Hackett
Creek and the Cobb asbestos.
C. Sukinda, India
The study performed by Rout et al. (2000) on the
metalliferous overburden around chromite mines at
Sukinda shows the tailing contains low level of nutrients.
The pH of the spoil is slightly acidic where as the low
percentage of organic carbon, phosphorus, potassium,
calcium and high level of magnesium was observed. The
ratio of the Ca/Mg is 0.22 with low field capacity.
Echinochloa colona the most abudantly growing grass on
the chromite minewaste dump was used for the experiment.
The tolerance of populations of a grass, Echinochloa
colona, growing abundantly on chromite mine waste
dumps, was tested in two separate experiments. Seed-based
experiments indicate that the seeds collected from the Ni
and Cr contaminated soil are having higher percentage of
seed germination than the uncontaminated site. At lower
concentration of Cr (1.25 mg/L) germination of seeds
derived from mine waste dump and control site
(uncontaminated site) was 96.4 and 78.45% respectively.
With doubling of Cr concentration, percentage of seed
germination was hindered /declined by 13%. Low
percentage of seed germination was observed when Cr and
Ni were applied together. Population of Echinochloa
colona occurring naturally on chromite mine spoil,
therefore, appear to have developed metal tolerance. The
suitable growth of Echinochloa colona was due to the
adaptability of the plant and natural selection by the nature.
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Echinochloa colona reduces soil erosion and can be
used for the restoration of such mine waste dump sites.
Further experiment on plant-heavy metal uptake,
translocation and bioaccumulation factor can make
Echinochloa colona more effective in heavy metals
extraction from dump sites.
D. New South Wales, Australia
Pot culture studies on Hordeum vulgare L.cv weeds
were conducted by Meyer (1980) on chrysotile asbestos
mine tailings of Barraba, New South Wales, Australia
which showed the residues to be deficient in nitrogen,
phosphorus, potassium and calcium. The basal fertilizer
were added consisting of K2SO4 (95.4 mg/pot), H3PO4 (3.8
g/pot) and Na2MoO4.2H2O (0.1mg/pot). Nitrogen was
applied as Ca(NO3).4H2O. Five treatments were made
using three levels of superphosphate. All fertilizers were
mixed thoroughly in 500g of tailings containing pot.
Another experiment was conducted using fertilizer of
superphosphate 1.098 g/pot and gypsum 6.106 g/pot, and
mixed thoroughly Nitrogen was applied as Ca(NO3).4H2O.
Treatments (expressed as kg ha-1
with milligram’s per pot
in parentheses) consisted of a control treatment of K2SO4 -
250 (95.4), H3BO3 -10 (3.8), CuSO4.4H20 -10 (3.8),
ZnSO4.7H20 -10 (3.8), MnSO4.4H20 -10 (3.8) and
Na2MoO4.2H2O -0.25 (0.1) and six other treatments, each
omitting one of the compounds in turn. A further treatment
doubling the level of K2SO4 was included, giving a total of
eight treatments in three randomised blocks.
The chemical analysis of the asbestos tailing shows the
deficiency of major elements and Ca. High level of Cr, Ni,
Zn and Mn were found. The pH of the tailing was 9.85 (1:5
Soil: Water) were as low salinity was observed in the
solution. Further, high Mg content clears the serpentine
nature of the soil.
From the pot experiment it was found that Barley grew
normally only when superphosphate and gypsum were
applied at rates equivalent to 5 and 16 t ha-1
respectively,
together with the application of 'normal' rates of nitrogen
and potassium. Although gypsum increased the level of
calcium in the 'soil' solution, most of the calcium from the
gypsum treatments was retained by the tailings, displacing
magnesium and substantially increasing the level of the
latter element in the soil solution. In spite of this exchange,
gypsum was the most significant source of calcium and by
lowering the pH of the tailings increased the availability of
calcium provided by the superphosphate. Lime, by
comparison, made no measurable contribution to calcium
supply or plant growth. Low level of heavy metals was
recorded in soil solution due to high pH but concentration
can increase if the pH lowers below 8.
E. North–East of Portugal
Freitas et al. (2004) had conducted the experiment in
north–east of Portugal consisting serpentinized area of
about 8000 ha with a characteristic geology and flora. One
hundred and thirty five plant species belonging to 39
families and respective soils have been analyzed for total
Co, Cr, Cu, Fe, Mn, Ni, Pb and Zn. High concentration of
Cr and Ni was observed in the serpentinised soil of this
region bearing variety of vegetation. Apart from Cr and Ni,
adequate amount of Fe and Mn were also detected. The
concentration of Ni, Cr, Co were very high and are present
in the order of Cr>Ni>Mn> Co. The concentration of
exchangeable Ca/Mg ratio is very low which signifies the
serpentine nature of the soil. The plant samples were
collected and digested to access the variability of heavy
metal accumulation in different parts. Substantial amounts
of Ni, Cr, Co and Mn were detected in plant tissues which
are listed below: Ni (mg kg-1
): Alyssum serpyllifolium (38
105); Bromus hordeaceus (1467); Linaria spartea (492);
Plantago radicata (140); Cr (mg kg-1
): L. spartea (706.7);
Ulmus procera (173.4); A. serpyllifolium (129.3); Cistus
ladanifer (40.8); L. stoechas (29.5); P. radicata (27.81);
Setariopsis verticillata (25.7); Plantago lanceolata (24);
Digitalis purpurea (23.4); Co: A. serpyllifolium (145.1); L.
spartea (63.2); Mn: A. serpyllifolium (830); L. spartea
(339).
The significance of serpentine flora, need for
conservation of these fragile and environmentally
invaluable plant resources for possible use for in situ
remediation of metalliferous substrates were found to be of
great importance.
F. Tras-os-Montes region, NE Portugal
Lazaro et al. (2006) has performed the chemical and
heavy metal analysis of the serpentine, ultrabasic and other
type of soil of Tra´s-os-Montes region, NE Portugal. pH of
the serpentine soil was found to be slightly acidic. The
concentration of Ca/Mg is below 1 and nutrient availability
was low. Due to high concentration of Ni, Cr and Mg the
growth of the plants were retarded. The concentration of
Ni, Cr and Mg were 4384, 1574 and 2451 mg kg-1
respectively were relatively higher than other type of soil.
Also, significant amount of heavy metals were found in
EDTA extracted soil. It was found that the Ca
concentration was not insufficient and it was not
considered as the limiting factor for the vegetation growth.
International Journal of Emerging Technology and Advanced Engineering
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263
Serpentine areas were proved valuable sources of metal
accumulating plants.
In this study heavy metal accumulation was
determined in the flora associated with ultramafic and non-
ultramafic soils of the Tras-os-Montes region of NE
Portugal. Study sites were selected to represent a wide
range of soil-forming rocks (serpentinized (S), ultrabasic
(UB), basic (B) and acid (migmatite, M and schists, SC)
rocks) and plant metal accumulation was related to soil
metal bioavailability. Nine plant species (representing 7
families) were sampled including the Ni hyperaccumulator
Alyssum serpyllifolium subsp. lusitanicum. The greatest
metal accumulation, transport (leaf[metal]:root[metal]) and
bioaccumulation (leaf[metal]/soil[metal]) was found in four
of the non metal-hyperaccumulating species: Cistus
ladanifer, Lavandula stoechas, Plantago subulata subsp.
radicata and Thymus mastichina. Metal accumulation
depended on both the plant species and the edaphic
conditions at its provenance. While P. subulata is of less
interest due to its low biomass the remaining three species
could be of use in phytoremediation technologies such as
phytoextraction, and particularly in soils contaminated with
Cr, Mn and Zn. These three species are also of economic
interest due to their oil and fragrance producing biomass.
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Website: www.ijetae.com (ISSN 2250-2459, ISO 9001:2008 Certified Journal, Volume 3, Issue 2, February 2013)
266
TA
BL
E 3
: C
ON
CE
NT
RA
TIO
N O
F N
i, C
r A
ND
OT
HE
R A
SS
PC
IAT
ED
HE
AV
Y M
ET
AL
S I
N S
OIL
/ R
OC
K I
N D
IFF
ER
EN
T G
EO
LO
GIC
AL
RE
GIO
N O
F T
HE
WO
RL
D.
Ref
eren
ces
Gar
nie
r et
al., 2
006
Mo
rris
on
et a
l., 200
9
Go
ldh
aber
et a
l.,
2009
.
DeG
roo
d
et a
l., 200
5
Oze
et
al.,
2004
.
Oze
et
al.,
2008
Moo
re A
nd
Zim
mer
man
n,
1977
M
eyer
, 1980
Ree
ves
et
al., 2
007
Qu
anti
n e
t
al., 2
008
Mo
raet
is e
t
al., 2
012
Gid
arak
os
et a
l.,
2008
.
Al
(%)
2.0
4
- 7.9
-
0.2
-
0.8
1.0
2-
1.3
1.4
7-
1.7
4
-
100
1.8
-
3.6
1.1
6-
3.9
0
- -
Fe
(%)
35.4
-
4.2
5
0.0
0
1
3.0
3
-7.1
9.3
2
-11
4.8
-
7.6
8
- -
10.2
-16
4.6
-
7.5
- -
Cu
(mg k
g-1
)
- -
5-3
088
0.6
3
-
19-2
4
17-2
1
-
200
48-7
2
- -
<10
Zn
(mg k
g-1
)
- -
18-3
350
0.3
5
-
74-7
8
44-6
0
-
6400
- - -
<10
-22
Mn
(mg k
g-1
)
6667
-
48-4
430
7.0
5
155
-800
1615
-
2030
1095
-
1385
-
1300
1450
-
2600
938
-138
7
- -
Cr
(mg k
g-1
)
5107
-
7410
1700
-
10000
12-5
910
>0.1
580
-228
0
1650
-
2090
797
-158
5
3000
3400
1400
-
3640
637
-188
0
-
43-3
70
Ni
(mg k
g-1
)
2330
-45
77
1300
-39
00
6-4
955
18.7
1
1545
-33
21
3160
-39
40
1295
-26
60
2000
1900
3240
-72
20
515
-142
1
567
100
-177
0
pH
(H2O
)
5-7
- -
7.0
5
-
6.5
-
7.0
-
9.2
9.8
5
-
5.8
-
7.1
8.1
7.7
-
7.9
Dep
th
(cm
)
0-2
0
0-1
5
0-1
5
10
-
0-2
0
- - -
0-1
0
Ho
rizo
n-A
-
0-3
0
Ty
pe
of
Soil
/Ro
ck
Ult
ram
afic
(ri
ch i
n I
ron
oxid
es, sp
inel
s an
d
quar
tz)
Ser
pen
tine
and
Spin
al
Ser
pen
tine
and
Spin
al
Ser
pen
tine
Ser
pen
tine,
Ch
lori
te, T
alc,
and
Spin
els
Ser
pen
tine
Gra
ssla
nd
Ser
pen
tine
Ch
apar
ral
Ser
pen
tine-
Asb
esto
s
Ch
ryso
tile
asb
esto
s
Per
ido
tite
, cu
t by m
afic
dykes
Ser
pen
tine,
Mag
nes
ium
-
bea
ring
oli
vin
e
Ser
pen
tine
Asb
esto
s, U
ltra
maf
ic
Lo
cati
on
Niq
uel
and
ia, B
razi
l
No
rth
ern C
alif
orn
ia, U
SA
No
rth
ern C
alif
orn
ia, U
SA
Co
ast
Ran
ge,
cen
tral
Cal
ifo
rnia
, U
SA
San
ta C
ruz
Mo
unta
ins,
Jasp
er r
idge,
Cal
ifo
rnia
Cen
tral
Coas
t R
ange
of
Cal
ifo
rnia
Sou
thea
ster
n Q
ueb
ec,
Can
ada
Bar
rab
a, N
ew S
outh
wal
es,
Au
stra
lia
San
ta E
len
a
pen
insu
la,C
ost
a R
ica
Cze
ch R
epubli
c
No
rth
-Eas
tern
Att
ica,
Gre
ece
Ko
zani,
No
rther
n G
reec
e
International Journal of Emerging Technology and Advanced Engineering
Website: www.ijetae.com (ISSN 2250-2459, ISO 9001:2008 Certified Journal, Volume 3, Issue 2, February 2013)
267
Gh
asem
i an
d
Gh
ader
ian
, 200
9
Fre
itas
et
al.,
2004
.
Laz
aro
et
al.,
2006
Alv
es e
t al
.,
2011
Bal
kw
ill
et a
l.,
2011
.
Nin
gth
ouja
m e
t
al., 2
012
Rou
t et
al.
,
2000
.
Kie
rcza
k e
t al
.,
2008
Bar
bea
u e
t al
.,
1985
Hsi
ao e
t al
.,
2007
.
Mir
and
a et
al.
,
2009
.
Rob
inso
n e
t al
.,
1996
.
- - - -
4-4
.8
- - - -
0.3
8
0.1
0.5
2
- -
1.5
3
- - - -
10-
12.2
13.4
2
- 5.7
-
4.0
9
4.2
5
1.0
1
- -
23.4
2
-
30.8
–
225
150
53
29-3
3
-
24.2
0-
115.7
1
-
25.3
8
12
<6
63
2.3
7–
79.6
100
-
63–24
2
88
72
73-1
18
-
64.2
9-
275.0
0
-
108
39
65
65
124
-
140
-
1007–
1853
2451
1857
2700
-
2300
- - - -
870
303
457
- -
2780
-
200–6
822
4384
1277
2800
-42
00
4500
557.6
9-
1384
.00
2950
2671
2015
497
854
3100
10.0
–116
2
7850
1600
102–2
348
1574
963
2800
-38
00
4800
1290
.82
-
2670
.02
1830
1329
3075
425
265
3400
5.9
1–940
6090
7.7
-
6.5
6.0
6.4
8-
7.5
3
7.0
5
- -
7.2
- - -
6.5
4.6
0–
5.8
2
6.6
15
10-3
0
0-1
5
0-1
5
0-1
5
0-1
0
0-1
5
0-1
0
Ho
riz
on -
A
- - -
0-5
0-1
0
Ser
pen
tine
Ser
pen
tine
Ser
pen
tine
Ult
rabas
ic
Ser
pen
tine
(chlo
rite
)
Asb
esto
s
Ser
pen
tiniz
ed
Ult
ram
afic
cu
mu
late
and
Per
idoti
te
Ch
rom
ite
Hy
per
eutr
ic
mag
nes
ic s
ilti
c
Cam
bis
ol
der
ived
from
ult
rab
asic
ro
ck
Ch
ryso
tile
A
sbes
tos
Ser
pen
tine
Ser
pen
tine
Ser
pen
tine
Mar
ivan
, W
este
rn I
ran
Pin
gar
ela,
No
rth
–E
ast
of
Po
rtug
al
Tra
s-os-
Mon
tes,
NE
Po
rtu
gal
Tra
s-os-
Mon
tes,
Po
rtu
gal
Kaa
pse
ho
op
Sta
r
Min
e, S
A
Ind
o-M
yan
mar
subdu
ctio
n z
on
e,
No
rth
east
India
Suk
ind
a, I
nd
ia
Szk
lary
Mas
sif,
SW
Pola
nd
Qu
ebec
(Je
ffre
y
min
e)
Qu
ebec
(Bel
l m
ine)
Qu
ebec
(Car
ey
Can
adia
n m
ine)
Cen
tral
Rid
ge
and
Cost
al R
ang
e in
Eas
tern
Tai
wan
Gal
icia
, N
W S
pai
n
Nel
son
reg
ion
, N
ew
Zea
land
International Journal of Emerging Technology and Advanced Engineering
Website: www.ijetae.com (ISSN 2250-2459, ISO 9001:2008 Certified Journal, Volume 3, Issue 2, February 2013)
268
Rob
inso
n e
t al
.,
1996
.
Shti
za e
t al
, 20
05
Lo
mb
ini
et a
l.,
1998
Dam
ico e
t al
.,
2008
.
Gh
ader
ian
and
Bak
er, 200
7.
0.6
0.1
0.0
5
0.2
9
0.0
6
2.8
-6.1
- - -
22.6
13
4.9
21.5
29.0
6.2
-
12.3
- -
4.5
0
59
29
11
3101
107
23-
840
17
5.2
-
108
55
14
56
76
73-
843
56
- -
1844
1708
395
624
3126
- - -
800
892
3151
536
456
589
843
-
3385
2231
1400
300
2490
1505
2682
827
4713
1553
-34
50
2466
342
1500
6.9
7.4
7.7
6.0
7.5
7.1
-7.8
- 4.7
7.5
-7.9
0-1
0
0-1
0
0-2
0
Ho
rizo
n
- A
E
0-1
0
Ult
ram
afic
soil
Ser
pen
tine
Ser
pen
tinit
e
Ser
pen
tinit
e
Per
ido
tite
(ser
pen
tiniz
ed t
o
som
e d
egre
e)
Du
n M
ou
nta
in, N
ew Z
eala
nd
Du
n S
add
le, N
ew Z
eala
nd
Cobb
Min
e, N
ew Z
eala
nd
Un
ited
Min
e, N
ew Z
eala
nd
Un
ited
Val
ley
, N
ew z
eala
nd
Bu
rrel
, A
lban
ia
No
rth
ern A
pen
nin
es,
Ital
y
Ao
sta
Val
ley
, It
aly
Cen
tral
Ira
n