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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) 256 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 1 Research Scholar, 2 Professor, Environmental Science and Engineering, Centre of Mining Environment, Indian School of Mines, Dhanbad-826004, Jharkhand, India. AbstractThis 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. KeywordsChromium, 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 (Mg 6 Si 4 O 10 [OH] 8 ) formed from original olivines ((Mg,Fe) 2 SiO 4 ) and pyroxenes ((Mg,Fe) 2 Si 2 O 6 or Ca(Mg,Fe)Si 2 O 6 ) 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 Fe 2+ 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, Fe 2+ ) 2 [Si 2 O 4 ]) and pyroxene (XY(Si,Al) 2 O 6 ). 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 (Mg 3 Si 2 O 5 (OH) 4 ), chrysotile (Mg 3 Si 2 O 5 (OH) 4 ) and antigorite ((Mg,Fe 2+ )3Si 2 O 5 (OH) 4 ) were formed by the hydration of pyroxene. Some of the other minerals which are commonly associated with serpentinites include magnetite (Fe 2+ ,Fe 3+ 2 O 4 ), Cr-rich magnetite (Fe 2+ (Fe 3+ ,Cr) 2 O 4 ), chromite (FeCr 2 O 4 ), and other mixed-composition spinels, talc (Mg 3 Si 4 O 10 (OH) 2 ), chlorite ((Mg,Fe) 5 Al[(OH) 8 |AlSi 3 O 10 ]), tremolite ([Ca 2 ][Mg 5 ] [(OH) 2 |Si 8 O 22 ]), 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 circumneutral 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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Page 1: Availability of Chromium, Nickel and Other Associated Heavy Metals of Ultramafic and Serpentine

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)

256

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

Page 2: Availability of Chromium, Nickel and Other Associated Heavy Metals of Ultramafic and Serpentine

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)

257

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.

Page 3: Availability of Chromium, Nickel and Other Associated Heavy Metals of Ultramafic and Serpentine

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)

258

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

Page 4: Availability of Chromium, Nickel and Other Associated Heavy Metals of Ultramafic and Serpentine

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)

259

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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International Journal of Emerging Technology and Advanced Engineering

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260

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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261

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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262

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.

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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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International Journal of Emerging Technology and Advanced Engineering

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266

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Page 12: Availability of Chromium, Nickel and Other Associated Heavy Metals of Ultramafic and Serpentine

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

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d

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, 200

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al.,

2004

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al.,

2006

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.,

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al.

,

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.,

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al.

,

2009

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Page 13: Availability of Chromium, Nickel and Other Associated Heavy Metals of Ultramafic and Serpentine

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

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mb

ini

et a

l.,

1998

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ico e

t al

.,

2008

.

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ader

ian

and

Bak

er, 200

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