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ABSTRACT
1. Introduction
Tannery effluents are ranked as the highest pollutant (indicates single element like chromium)
among all the industrial wastes. It is estimated that in India alone about 2000-3000 t of chromium
escapes into the environment annually from tannery industries, with chromium concentrations
ranging between 2000 and 5000 mg L-1 in the aqueous effluent compared to the recommended
permissible limits of 2 mg L-1. The tanning industries are especially large contributors of
chromium pollution in India (Manivasagam, 1987). Two types of effluents are discharged during
the tanning process: vegetable tanning, which does not contain chromium, and chrome tanning,
which contains chromium (Manivasagam, 1987). Leather processing requires large amount of
chemicals like sodium chloride, chromium sulphate, calcium salts, ammonium salts, sodium
sulphide, acids, alkalis, fat, liquor, and organic dyes. However, one of the major emerging
environmental problems in the tanning industry is the disposal of chromium contaminated sludge
produced as a by-product of wastewater treatment (Amita et al., 2005). Tannery effluents
severely affect the mitotic process and reduce seed germination in extensively cultivated pulse
crops (Thangapandian et al., 1995). At high concentrations chromium is toxic, mutagenic,
carcinogenic, and teratogenic (Luli et al., 1983). Chromium exists in oxidation states of +2, +3,
and +6. The trivalent oxidation state is the most stable form of chromium and is essential to
mammals in trace concentration and relatively immobile in the aquatic system due to its low
water solubility. The hexavalent chromium is much more toxic to many plants, animals, and
bacteria inhabiting aquatic environments (Ishibashi et al., 1990).
Currently, it has been estimated that more than 50,000 ha of productive agricultural lands have
been contaminated with Cr alone due to the disposal of tannery wastes in Tamil Nadu, where
more than 60 percent of Indian tanneries are located in Vellore district. Assessment of Cr levels
in contaminated soils in Vellore district showed that the soils surrounding tannery industries
are severely contaminated with Cr. Large amounts of Cr (16731-79865 mg kg-1) were found
in surface and subsurface soils in Vellore districts, where large number of tanneries exist
(Mahimairaja et al., 2000a). The Cr concentration in ground waters is also markedly higher
than the average background value reported in different parts of India (Mahimairaja et al.,
2000b). The accumulation of Cr in soil is of concern because of its possible phytotoxicity or
increased movement of metals into the food chain and the potential for surface and groundwater
contamination. Chromium contamination in soil and water has drastically reduced the crop yields
(25 to 40%) over the years and decreased significantly (Mahimaraja et al,. 2011).
Surface soils were collected from 0 – 15 cm depth using stainless steel spade, air dried at
25oC and passed through a 2mm sieve. The homogenized samples were stored in polythene
bags until further analysis. The moisture factor was computed and applied to express the
results on oven dry basis. The concentration of total Cr in soil was determined.
Ground water samples were collected from bore-wells that are approximately 10m deep, in one
litre polyethylene containers which were rinsed with sample water several times before filling.
After pH measurement, the water samples were acidified with concentrated HNO3 to a pH of
approximate 3.0 to stabilize the original state of heavy metals speciation. Some important
quality parameters viz., pH, EC, BOD, COD and chromium were determined. The pH and the
electrical conductivity (EC) of the water samples were measured using a combined electrode pH
meter and Conductivity Bridge, respectively (Jackson, 1973).
The dissolved oxygen (DO) content in the samples was first determined by modified Winkler’s
method following azide modification iodometric method (Anon, 1989). The chemical oxygen
demand (COD) of the water was determined by following open reflux method described by
(Anon, 1989).
The concentration of total Cr in the water sample was measured by digesting the ground
water sample with aqua-regia (HCl: HNO3 at 3:1). One gram of sample was weighed in a
acid washed 100 ml conical flask and added 15 ml of aqua-regia (HCl : HNO3 @ 3:1). One
ml of water / soil was digested with 15 ml of aqua-regia on a hot plate for 2 h. The digest was
made to 100 ml and filtered through Whatman No.1 filter paper. The total Cr present in the
solution was measured in an AAS (Varian Spectra, 2000) using air acetylene flame at 357.9
nm (USEPA. 1979a).
Survey was undertaken to delineate the ‘Hot-spot’ of Cr in Vellore district. Surface soil (0-15
cm of agriculture land) and groundwater samples from bore wells / open wells were collected
and Cr concentration was determined. The soil and water samples were analysed for total Cr
content and presented in Table 1.
Table 1: Chromium content of soils and ground waters collected from Vellore district
Total Cr in Soil Total Cr in Water
S. No Village Name -1
(mg kg ) (mg L-1)
I WALAJAPET
1 V.C.Mottur 458 13.5
2 Keel Pudhu pettai 610 Bdl
3 Dhanvandhiri nagar 349 Bdl
4 Mel Pudhupettai-1 881 Bdl
5 Melpudupettai-2* 1 17.3
6 Melpudupettai-3* Bdl 7.6
7 Amananthangal 598 Bdl
8 Devadhanam 492 Bdl
9 Lalapettai 341 8.02
VII GUDIYATHAM
53 Thiruvalam 414 Bdl
54 Sevur 415 Bdl
55 Karanampattu 338 Bdl
56 Alinjikuppam 853 Bdl
57 Sokkarishipuram 812 Bdl
58 Keelpattu 315 4.5
59 Keel Samuththiram 175 Bdl
60 Sundharakuttai 1646 Bdl
61 Kakkathoppu 840 Bdl
62 Melmottur 443 Bdl
63 Kalmadugu 492 Bdl
64 Melalaththur 92 3.4
65 Rajakkal* 239 Bdl
*Sampled from a place near the Palar river basin, Bdl: Below detectable limit
The Cr content in soils examined showed wide variations and varied from trace to 1646 mg
kg-1. In general, about 74 percent of samples exceeded the concentration of
200 mg kg-1 and 16 percent of samples had Cr content more than 600 mg kg-1. About
five percent of sample exceeded the concentration of 1000 mg kg-1. Except in Ambur block,
all blocks in Vellore districts have shown high concentration of soil Cr, mostly exceeding the
permissible (threshold) limit prescribed by the Environmental Protection Agencies (EPA) in
different countries.
Table 2: Threshold levels of Cr permissible in soils (mg kg-1) of some developed countries
New
Metals Australiaa UKc Canadad USEPAe Germanyf
Zealandb
50 (Total
Cr (III) 600 600 250 1500 200
Cr)
Cr (VI) 10 25 8
The 65 locations sampled in Vellore district have shown wide variation in soil Cr content. At
all locations, the Cr content showed no definite pattern in soil, but tended to accumulate in
disproportionate amounts in soil. The variation may possibly be due to the varying texture of
soil and hydrological features of sampling sites which may have influenced the mobility of Cr,
resulting in differential amount of Cr in surface and subsurface soil. The different chemical
composition of tannery effluent and sludge may also have contributed to the variation in Cr
accumulation.
The data clearly showed that the soil close to tannery industries is severely contaminated with
Cr. However, the nature and speciation of Cr is not determined. In nature, Cr can occur both
as trivalent Cr (III) and as hexavalent Cr (VI), depending on the nature of soil environment.
Since Cr2(SO4)3 is predominantly used in tanning process, the tannery effluent and sludge are
rich in Cr III and therefore, large accumulation of Cr (III) in soil is expected (Mahimairaja et
al., 2000). The results corroborate with the findings of (Sundar et al., 2010) who recently
have reported severe contamination of soil due to Cr from tannery wastes in Vellore. Sundar
and co workers reported that soil contaminated with chromium and isolated effective
bacterial strains at Ranipet area. Present study deals with whole district of Vellore that
contaminated with chromium in both soil as well as water. No one found the chromium
concentration at different location.
In groundwater, the Cr concentration ranged from trace (below detectable level) to 36.7 mg
L-1. About 67.6 percent of the groundwater samples had only traces of Cr or the concentration
below the detectable level. However, 27.7 percent of the samples had relatively higher
concentration of Cr, exceeding the safer limit of drinking water
-1 -1
(0.05 mg L ) and irrigation water (2 mg L ), prescribed by the World Health Organization and
Food and Agricultural Organization, respectively. Water samples from SIPCOT areas in
Walajapet and from Palar river basins had relatively higher concentration of Cr. A high
concentration of Cr in groundwater sampled from wells located approximately 2 km away from
the effluent outlet of tannery at Melpudupettai in Walajapet and Arcot, clearly indicates the extent
of Cr pollution in groundwater. The most disturbing fact about this contamination is that these
waters are currently in use for potable purposes. Given that many of these villages do not have
any other source of potable water, continued consumption of Cr-contaminated water can pose
greater risks to both animals and humans living in these areas.
The Cr concentration in groundwater was much higher than the normal average background
value of 4 to 7 µg Cr L-1 reported in various parts of India (Handa, 1978).
A high concentration in groundwater has been reported by several workers (Omole and
Longe 2008 & Longe and Balogun, 2010). Forstner and Wittman (1983) reported a mean
value of 10 mg Cr L-1 in groundwater of Tokyo. They suggested 0.5 µg Cr L-1 as the
background concentration of Cr in surface water. Drinking water standards have been set at
50 µg total Cr L-1, because of the toxic effect of Cr (VI) and the possibility that Cr III will
oxidize to toxic Cr VI (USEPA, 1976).
A comparison was made between the current data on soil and water Cr and that of data
obtained during 2000 (Mahimairaja et al., 2000a). The results (Figure 2) have shown that the
concentration of Cr in soils at five selected locations ranged from 1875 to 25664 mg kg-1
during 2000 (Mahimairaja et al., 2000 & Sundar et al., 2010). The current study has revealed
that the Cr concentrations in soils at the same villages were found drastically reduced. In the
same villages the Cr concentration in groundwater ranged between 51 and 996 µg L-1 during
2000; whereas the concentration were found markedly increased during 2012. The reduction
in soil Cr might be due to oxidation of Cr III to Cr VI, which dissolved in water leached
down in the soil profile and reached the groundwater, over a period of more than ten years.
Substantial increase in the concentration of Cr in the groundwater further confirmed this. In
many villages the concentrations of Cr in water were only traces or below the detectable limit.
This could be attributed to adsorption of Cr VI on aquifer minerals, as adsorption was found
to be an important mechanism for removing Cr VI from solution (Stollenwerk and Grove,
1985). It was also possible that part of Cr VI might have reduced (microbially or chemically)
to Cr III and adsorbed on sediments / aquifer minerals and reduced the concentration of Cr.
Rainfall and subsequent run off also might have reduced the soil Cr content.
Figure : 2 A comparison of soil and water Cr measured during the year 2000 (Mahimairaja et al.,
2000) and 2012 (current study)
About 52 per cent of samples had pH more than 8.5, indicating sodicity (sodium hazard) in
soil (Table 3). However, the EC, an index of salt loading, was found to be lesser (<1.0 dSm-1)
in most (96 %) of the soils examined, probably due to leaching of salts. Only 18 per cent of
the samples have shown higher pH (>8.2) and remaining 82 per cent samples had the pH
ranged between 7 and 8.2. Forty eight per cent of groundwater samples examined had an EC
ranging from 1 to 3 dSm-1, about 51 per cent of samples were found to have an EC values
more than 3 dSm-1. The EC values were very high (> 5 dSm-1) in 28 per cent of the
groundwater samples.
EC BOD COD
S. No Village name pH
(dS m ) (mg L ) (mg L-1)
-1 -1
EC BOD COD
S. No Village name pH
(dS m-1) (mg L ) (mg L-1)
-1
4. Conclusion
Most (>90%) of the soil samples collected from 65 locations in Vellore district had high
concentration of Cr (>200 mg kg-1) which exceeding the permissible (threshold) limit
prescribed by the Environmental Protection Agencies (EPA) in different countries especially
fixed the concentration by India. In ground water, the Cr concentration ranged from trace
(below detectable level) to 36.7 mg L-1. About 67.6 per cent of the groundwater samples had
only traces of Cr or the concentration below the detectable level. Twenty eight per cent of the
samples had relatively higher concentration of Cr, exceeding the safer limit of drinking water
(0.05 mg L-1) and irrigation water (2 mg L-1), prescribed by the WHO and FAO, respectively.
The most disturbing fact about this contamination is that these waters are currently in use for
potable purpose. The soil chromium concentration was decreased at the same time water
chromium was increased due to leaching process. The chromium was leached from upper
layer of soil to deeper layer of aquifer. Most of the Cr contaminated ground water exhibited
greater risk in terms of both salinity and sodicity hazards and were found unsuitable for both
human consumption and irrigation purpose.
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