Agri.

Review, 35 (2): 153 - 157, 2014 AGRICULTURAL RESEARCH COMMUNICATION CENTRE

www.arccjournals.co m
do i:10.5958/0976-0741.2014.00094.4

CHROMIUM POLLUTION: A THREAT TO ENVIRONMENT - A REVIEW

M.L. Dotaniya*, J.K. Thakur, V.D. Meena, D.K. Jajoria 1 and Gopal Rathor
Indian Institute of Soil Science, Nabi Bagh,
Berasia Road, Bhopal- 462 038, India
Received: 07-08-2013 Accepted: 10-05-2014
ABSTRACT
In recent years, contamination of the environment by chromium (Cr) has become a major concern.
It is unique among the heavy metals found in industrial waste water and sewage and sludge, as it
may exist as a trivalent cation and as anion in the hexavalent state in the pH range of agricultural
soils. It is used on a large scale in many different industries, including metallurgy, electroplating,
production of paints and pigments, tanning, wood preservation, chemical production, and pulp
and paper production. These industries are contributing larger amount of Cr, which can ultimately
have significant adverse effects on biological and ecological activities of ecosystem. Chromium enters
in the food chain through consumption of plant material. A high concentration of Cr has been found
to be harmful to vegetation. As the Cr concentration in plants increases, it adversely affects several
biological parameters and eventually renders the soil barren.

Key word: Chromium, Plant uptake, Remediation techniques

Soil and water pollution by chromium (Cr)
is a worldwide issue . All co untrie s have bee n
affected, though the area and severity of pollution
vary enormously. In Western Europe, 1400 000 sites
were affected by heavy metals, of which over 300000
were contaminated, and the estimated total number
in Europe could be much larger, as pollution problems
incre asingly o ccurre d in Ce ntral and Easte rn
European countries specially Cr pollution. In USA,
the re are 6 0 0 0 0 0 bro wn fie lds which a re
co ntaminate d with he a vy me tals and ne e d
reclamation (Bahafid et al., 2013). In India, Cr
pollution also emerged as a challenge to remediate it.
It is mainly in tannery and paint industries locations.
Heavy metals, broadly defined as a group of toxic
metals and metalloids associated with pollution and
toxicity, are elements with a density of more than 6
Mgm-3 and atomic weight that exceed that of iron.
Heavy metals are natural constituents of the Earth’s
crust. They are stable and cannot be degraded or
destroyed and therefore they tend to accumulate in
soils and sediments (Dotaniya et al., 2014b).
Chromium is one of the toxic heavy metal
for ecosystem as well as survival of human beings
*Corresponding author email: mohan30682@gmail.com
1
Directorate of Research, Maharana Pratap University of Agriculture and Technology, Udaipur – 313 001, India
on earth. It is the 21 st most abundant element in the
earth’s crust (Eliopoulos et al., 2013). It occurs in
nature in bound forms that constitute 0.1-0.3 mgkg-1
of the earth’s crust. It has several oxidation states
ranging fro m Cr (-II) to Cr (+ VI). Cr e xists
predominantly in the Cr+ 3 and Cr+ 6 oxidation states.
The most stable oxidation state of Cr is Cr (III), and
under most prevailing environmental conditions Cr
(VI) is rapidly reduced to Cr (III). The intermediate
states of + IV and + V are metastable and rarely
encountered (Lokhande et al., 2011).
Exce ssive me ta l a ccumulatio n in
contaminated soils can result in de creased soil
microbial activities, soil fertility, and overall soil
quality which may lead to reduction in yield. The
entry of toxic materials into food chain can cause
many diseases in human and animals. Very high
levels of Cr (VI) contamination (14,600 mgkg-1 in
gro und water and 25,900 mgkg -1 in soil) were
reported at the United Chrome Products site in
Corvallis, Oregon (Krishnamurthy and Wilkens,
1994). The critical concentration of chromium in
plant varies according to specie s but generally
1-2 mgkg-1 of plant biomass was found to be growth
154 AGRICULTURAL REVIEWS
limiting and maximum allowable limit in soil is 100 (CrO4 2-) and dichromate (Cr2 O7 2-) which precipitate
mgkg-1 (Purakastha and Chhonkar, 2010). readily in the presence of metal cations(especially
2+ 2+ +
Sympto ms o f Cr phyto to xicity include Ba , Pb and Ag ). Chromate and dichromate also
inhibition of seed germination, seedling development, adso rb o n so il surface s, e spe cially iro n and
re ductio n o f ro o t gro wth, le af chlo ro sis and aluminum oxides. Chromium (III) is the dominant
3+
depressed biomass (Dotaniya et al., 2014a). Many form of Cr at low pH (< 4). Cr forms solution
- - - - 2-
studies were conducted to evaluate the Cr toxicity complexes with NH3 , OH , Cl , F , CN , SO4 , and
in crop plants shows chromium significantly affects soluble organic ligands. The Cr (VI) is the more toxic
the metabolism of plants such as barley, citrullus, form of chromium and is also more mobile. However,
cauliflower, wheat and maize (Shanker et al., 2005). Cr(III) mobility is decreased by adsorption to clays
The sub-cellular localization of Cr as found by and oxide minerals below pH 5 and low solubility
electron e ne rgy lo ss spe ctro scopy (EELS) and above pH 5 due to the formatio n of Cr(OH) 3
electron spectroscopic imaging (ESI) suggested that (Chroto wski et al., 1991). Chromium mo bility
Cr is accumulate d mainly in the cell wall and depends on sorption characteristics of the soil,
vacuoles (Zou et al., 2006). including clay content, iron oxide content and the
amo unt o f o rganic matte r pre se nt. It can be
Chro mium availability in so il: The to tal Cr transported by surface runoff to surface waters in its
concentration levels in igneous and sedimentary soluble or precipitated form. Soluble and unadsorbed
rocks are usually in the range of up to about 100 chromium co mple xe s can leach fro m so il into
µgg-1 . For most of soils the Cr concentration is in the groundwater. The leachability of Cr(VI) increases
range of 15 to 100 µgg-1 soil and increase with the as soil pH increases. Most of Cr released into natural
proportion in clay (Baize, 1997). However, soil wate rs is particle asso ciated and is ultimately
derived from serpentine may contain several percent deposited into the sediment (Andjelkovic et al.,
of Cr. Soil Cr is largely unavailable to plants because 2012).
it occurs in relatively insoluble compounds such as
chromite FeCr2 O4 in mixed oxides of Cr, Al and Fe, Plant uptake: In general, plants have a low capacity
or in silicate lattice. In addition Cr3+ binds tenaciously to absorb and translocate Cr. Different vegetable
to negatively charged sites on clays and organic crops vary in their ability to accumulate Cr in tissues
matter. For this reason the translocation of Cr from (Zayed et al., 1998). In plants grown on soils after
soils into plants is generally insignificant (Juste and long-term application of sewage sludge containing
Mench, 1992). Chromates (hexavalent Cr) in soils Cr, its level in leaves seldom exceeded a few µgg-1
are relatively rare and only stable in alkaline oxidizing dry weight (DW). Even in plants adapted to Cr-rich
conditions. It is supported that Cr3+ and CrO4 2- are serpentine soils, the mean Cr content does not
taken up by two different mechanisms. The uptake exceed 45 µgg-1 DW (Juste and Mench, 1992).
of CrO4 2- is depressed by SO4 2- (Shenbagavalli and Chromium hyperaccumulator like Leptospermum
Mahimairaja, 2012). scoparium reported to accumulate 20,000 mgkg-1
-1
Chromium chemistry: Chromium is one of the less and B. juncea accumulated 1,400 mgkg but some
common elements and does not occur naturally in of agricultural crops also accumulated less amount
elemental form, but only in compounds. It is mined of Cr from soil .
as a primary ore product in the form of the mineral Adhikari and Singh (2007) reported that Cr
chro mite , FeCr2 O4 . The Cr(VI) is the form o f application at more than 75 mg Cr (VI) kg-1 soil for
chromium commonly found at contaminated sites. maize totally inhibited the growth after germination,
It can also o ccur in the + III o xidatio n state , whe re as 25 mg Cr (VI) kg -1 so il hinde re d the
depending on pH and redox conditions. Cr (VI) is germination of spinach crop. Initial symptoms of Cr
the dominant form of Cr in shallow aquifers where (VI) appeared as severe wilting of the tops of treated
aerobic conditions exist. Cr (VI) can be reduced to plants. Maize plants suffering from severe Cr (VI)
Cr(III) by soil organic matter, S2- and Fe 2+ ions under toxicity had smaller roots and narrow brownish red
anaerobic conditions often encountered in deeper leaves covered with small necrotic spots. In spinach,
groundwater. Major Cr (VI) species include chromate severe chlorosis was observed in leaves. Higher
 Vol. 35, No. 2, 2014
levels of Cr (VI) inhibited the growth and dry matter
yield of the crops. However, application of city
compost alleviated the toxic effect of Cr (VI). The
concentration of Cr (VI) in plant part increased when
Cr (VI) wa s applie d a lo ne but de cre ase d
considerably when used in combination with city
compost. There is evidence of an antagonistic effect
of Cr (VI) on other heavy metals (Mn, Cu, Zn and
Fe) concentration in plant. At 25 mg Cr (VI) kg-1 soil,
yield of maize was reduced to 41% of control plants,
whereas in spinach, 10 mg Cr (VI) kg-1 soil caused
33% yield reduction. The maize top (cereal) is less
effective in accumulating Cr (VI) than spinach (leafy
vegetables). Chromium is involved in numerous
physiological functions as a component of several plant
enzymes, with minimum requirements generally in the
range of 1–5 µgg-1 in plant tissue depending on the
species (Shanker et al., 2005). Various interactions
can occur when plants are exposed to unfavorable
concentrations of Cr. Chromium promotes the uptake
o f Zn in Am aranthus viridis L. Barce ló and
Poschenrieder (1997) observed that when bean plant
grown in Cr(VI) nutrient solution, translocation of Cu,
Zn and Fe in plant was inhibited. Chromium
accumulation levels in A. viridis were as follows: leaf >
ro o t > ste m. Whe re as co ntaminate d so il
approximately11 times more accumulation of Cr was
reported than those growing at the uncontaminated site.
Factors affecting bio-mobilization of chromium:
A number of soil processes and factors may affect
the form and bio-mobilization potential of Cr. It is
present in soils mostly as insoluble Cr(OH)3 or as
Cr(III) adsorbed to soil components, which prevents
Cr leaching into groundwater or its uptake by plants.
The Cr (VI) is readily transformed to Cr (III) as a
result of reduction by Fe (II) in solution and at mineral
surfaces by sulfur compounds, or by soil organic
matter under most soil conditions. Chromium(III)
has be e n fo und to be re adily abso rbe d by
macromolecular clay compounds; also, humic acids
co ntain do no r gro ups fo rming stable Cr(III)
complexes, especially when they produce chelate
rings, and adsorption of Cr(III) to humic acids
re nders it insoluble, immobile and unre active.
Although Cr (III) can oxidize to Cr (VI), especially in
the presence of manganese oxides, oxidation usually
occurs only in moist conditions, and not appreciably
in dry soils. Cr (III) can thus expect to be the
predominant form. The Cr (III) largely exists in soil
155
as relatively unavailable, insoluble oxides of Cr
(Naidu and Kookana, 2000). However, Cr(VI) is the
most mobile, reactive, and toxic Cr form, and it
would be the only existing form if all chromium were
to be in the rmo dynamic e quilibrium with the
atmosphere. The hexavalent form of Cr (CrO4 -2 )
being most active in soils is of particular concern
because this form has been demonstrated to be toxic
at low concentrations to both plant and animals.
The Cr(VI) is a strong oxidizer and as a result exists
only in oxygenated species that are soluble and pH
dependent and occurs as an anion in aqueous
solution
Effe c ts o f c h ro mium o n hu ma n he a lth :
Chromium is used in metal alloys and pigments for
paints, cement, paper, rubber, and other materials.
Low level exposure can irritate the skin and cause
ulceration. Long term exposure can cause kidney
and liver damage and damage too circulatory and
nerve tissue. It often accumulates in aquatic life,
adding to the danger of eating fish that may have
been exposed to high levels of chromium. However,
human activitie s have drastically alte re d the
biochemical and geochemical cycles and balance
of some heavy metals. The principal manmade
sources of Cr are industrial point sources, i.e. mines,
foundries and smelters, and diffuse sources such as
combustion by-products and traffic etc.
Remediation techniques: The Cr contamination
is steeply increasing in the environment. It can be
remediated by chemical, physical and biological
appro ache s. In bio lo gical appro ach it can be
separated into phytoremediation as well as bio-
re me diatio n (micro o rganism). Amo ng the all
re me diation te chnologies, phyto remediatio n is
cheaper and eco-friendly in nature (Dotaniya and
Lata, 2012).
Phytore me diatio n: It also referred as botanical
bioremediation which involves the use of green plants
to decontaminate soils, water and air. It is an
emerging technology that can be applied to both
organic and inorganic pollutants present in the soil,
water or air. It employs plants and their associated
root bound microbial community to remove, degrade
or render environmental contaminants harmless. At
present, there are about 400 species of known
terre strial plants that hype raccumulate o ne o r
more metal(loid)s. It helps in reducing heavy metal
156 AGRICULTURAL REVIEWS
pollution. It has the advantage of relatively low cost becoming incorporated into the plant tissues. Plant
and wide public acceptance. It can be less than a enzymes have be en identified that breakdo wn
quarter of the cost of excavation or insitu fixation. ammunition wastes, chlorinated solvents such as
Phyto re me diatio n has the disadvantage o f TCE (Trichloroethane).
taking lo nge r time to acco mplish than o the r (3) Rhizo filtration: It is a similar in concept to
tre atme nt. The re are diffe re nt cate go rie s phyto e xtractio n but is co nce rne d with the
o f phyto re me dia tio n i.e . phyto e xtra ctio n, remediation of contaminated groundwater rather
phytodegradation, rhizofiltration, rhizodegradation than the re me diatio n o f po llute d so ils. The
and phyto stabiliza tio n, de pe nding o n the contaminants are either adsorbed onto the root
mechanisms of remediation. surface or are absorbed by the plant roots. Plants
(1)Phyto extraction: It is the name given to the used for rhizofiltration are not planted directly in situ
pro ce ss whe re plant ro o ts take up the me tal but are acclimated to the pollutant first. Plants are
contaminant from the soil and translocate them to hydroponically grown in clean water rather than soil,
their above ground plant tissues. Once the plants until a large root system has developed. Once a large
have grown and absorbed the metal pollutants, they root system is in place the water supply is substituted
are harvested and disposed off safely. This process for a polluted water supply to acclimatize the plant.
is repeated several times to reduce Cr contamination After the plants become acclimatized they are planted
to acceptable levels. Hyper accumulator plant in the polluted area where the roots uptake the
species are used on many sites due to their tolerance polluted water and the contaminants along with it.
o f re la tive ly e xtre me le ve ls o f po llutio n. As the roots become saturated they are harvested
Phytoextraction offers an efficient, cost-effective, and and disposed of safely.
environmentally friendly way to clean up heavy metal (4) Rhizo de gradatio n: It also called enhanced
co ntaminatio n. The re are two type s o f rhizosphere biodegradation, phytostimulation, and
phyto e xtractio n. The y a re (1 ) Natural plant assisted bioremediation, in which breakdown
phytoextraction and (2) Induced phytoextraction. of organic contaminants in the soil by soil dwelling
(a) Natural phytoextraction: It is usually conducted microbes which is enhanced by the rhizosphere’s
by planting se le cte d plant spe cie s in the presence . Plant ro ot exudates such as sugars,
contaminated soil. These plants are grown under alcohols, and organic acids act as carbon sources
normal farming conditions until they reach their for the soil microflora and enhance microbial growth
maximum size. The aboveground parts of the plants and activity. The plant roots also loosen the soil and
containing the contaminants are then harvested and transport water to the rhizosphere thus additionally
disposed off appropriately. enhancing microbial activity.
(b) Ind uc e d p h y t o e xt ra c tio n : In no n (5) Phyto stabilisatio n: Phytostabilisation is the
hyperaccumulato rs plants, factors limiting their process in which plants are used to immobilize soil
potential for phytoextraction include small root and water contaminants. This technique can also
uptake and little root-shoot translocation of metals. be used to re-establish a plant community on sites
Throughout the growth period, amendments are that have been denuded due to the high levels of
added to the soil to increase availability of metals to metal contamination. Once a community of tolerant
the plants. The most commonly used agents for species has been established the potential for wind
induced phytoextraction are: EDTA, DTPA, CDTA e ro sio n is re duce d and le aching o f the so il
and citric acid etc. contaminants is also reduced. It involves three
(2) Phytodegradatio n: Phytodegradation is the processes which include: humification, lignification
degradation or breakdown of organic contaminants and irreversible binding.
by internal and external metabolic processes driven CONCLUSION
by the plant. Some contaminants can be absorbed Chromium pollution attracting the mind of
by the plant and are then broken down by plant research to control its contamination in water bodies
enzymes. These smaller pollutant molecules may then as well as in ecosystem across the globe. So many
be used as metabolites by the plant as it grows, thus chemical, physical and biological technologies are
 Vol. 35, No. 2, 2014 157
in practice no w a day; cheaper and e ffective use. As countries around the world are struggling to
technologies are needed to protect the precious natural arrive at an effective regulatory regime to control the
resources and biological lives. Use of Cr containing discharge of industrial effluents into their ecosystems,
farm inputs should contain less amount of Cr. Effluent use of modern and traditional approaches can diverse
for cultivation of vegetables should be treated prior to our land use system in new horizon.
REFERENCES
Adhikari, T. and Singh, M. V. (2007). Sorption characteristic of chromium and its phytotoxic effect with and without city
compost on maize and spinach in a Vertisol of central India. Communi. Soil Sci. Plant Ana. 38 (11&12): 1503-
1518.
Andjelkovic, D.H., Andjelkoviæ , T. D., Nikolic, R. S., Purenovi, M. M., Blagojeviæ, S. D., Bojiæ , A. L. and Ristiæ, M.
M. (2012). Leaching of chromium from chromium contaminated soil – a speciation study and geochemical
modelling. J. Serb. Chem. Soc. 77 (1) 119–129.
Bahafid, W., Joutey, N. T., Sayel, H., Boularab, I. and Ghachtouli, N. (2013). Bioaugmentation of chromium-polluted
soil microcosms with Candida tropicalis diminishes phyto-available chromium. J. Appl. Microbiol. doi: 10.1111/
jam.12282.
Baize, D. (1997). Total Contents of Metallic Trace Elements in Soils. INRA Paris.
Barceló, J. and Poschenrieder, C. (1997). Chromium in plants. In: Canali , S., Tittarelli, Sequi, P. (eds.) Chromium
environmental issues, Franco Angeli Publ, Milano pp 101–129.
Chrotowski, P., Durda, J.L. and Edelman, K.G. (1991). The Use of natural processes for the control of chromium
migration. Remed. 2: 341-351.
Dotaniya M. L., Das, H. and Meena, V. D. (2014a). Assessment of chromium efficacy on germination, root elongation,
and coleoptile growth of wheat (Triticum aestivum L.) at different growth periods. Environ. Monit. Assess.
186:2957-2963.
Dotaniya, M. L. and Lata M. (2012).Cleaning soils with phytoremediation. GeoGraphy You. 12 (73): 18-21.
Dotaniya, M. L., Saha J. K., Meena, V. D., Rajendiran, S., Coumar, M. V., Kundu, S. and Rao, A. Subba (2014b).
Impact of tannery effluent irrigation on heavy metal build up in soil and ground water in Kanpur. Agrotechnol.
2(4):77.
Eliopoulos, E. M., Megremi, I., Cathy, A., Theodoratou, C. and Vasilatos, C. (2013). Spatial evolution of the chromium
contamination in soils from the Assopos to Thiva Basin and C. Evia (Greece) and potential source(s):
Anthropogenic versus natural processes. Geosci. 3(2): 140-158.
Juste, C. and Mench, M. (1992). Long-term application of sewage sludge and its effects on metal uptake by crops. In:
Adriano DC (eds.) Biogeochemistry of trace metals, Lewis Publishers, Boca Raton, pp 159–193.
Krishnamurthy, S. and Wilkens, M. M. (1994). Environmental chemistry of Cr. Northeastern Geol. 16: 14–17.
Lokhande, R. S., Singare, P. U. and Pimple, D. S. (2011). Toxicity study of heavy metals pollutants in waste water
effluent samples collected from Taloja industrial estate of Mumbai, India. Resources Environ. 1(1):13-19.
Naidu, R. and Kookana, R. S. (2000). Chemistry of chromium in soils: an overview. In: Towards better management of
soils contaminated with tannery wastes. AICAR Public. 88: 43-54.
Purakastha, T. J. and Chhonkar, P. (2010). Phytoremediation of heavy metal contaminated soils. Soil Biol. 19: 389-429.
Shanker, A. K., Cervantes, C. Tavera, H. L. and Avudainayagam, S. (2005). Chromium toxicity in plants. Environ. Int.
31:739-753.
Shenbagavalli, S. and Mahimairaja, S. (2012). Biotransformation and bioavailability of chromium contaminated soil
and the effect of poultry manure and pseudomonas. Int. J. Plant, Animal Environ. Sci. 2 (1):190-196.
Zayed, A., Lytle, C. M., Qian, J. H. and Terry, N. (1998). Chromium accumulation, translocation and chemical
speciation in vegetable crops. Planta. 206: 293–299.
Zou, J., Wang, M., Jiang, W. and Liu, D. (2006). Chromium accumulation and its effects on other mineral elements in
Amaranthus viridis L. Acta Biol Cracoviensia Series Bot. 48 (1): 7–12.