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Sabyasachi Rout, P. Supreeta, Jaspal Singh, Sanjeev Kumar & H. S. Kushwaha (2011): Risk Assessment
for Natural Uranium in Subsurface Water of Punjab State, India, Human and Ecological Risk
Assessment: An International Journal, 17:2, 381-393
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Human and Ecological Risk Assessment, 17: 381–393, 2011
Copyright C Taylor & Francis Group, LLC
ISSN: 1080-7039 print / 1549-7860 online
DOI: 10.1080/10807039.2011.552395
ABSTRACT
Traces of uranium were measured by laser fluorimeter in 235 subsurface water
samples collected from four districts of Punjab state in India. The concentration of
U in water samples ranged between <2–644 µg/L with a mean value of 73.1 µg/L.
The radiological risk was observed to be in the range of 5.55 × 10−6–1.78 × 10−3
with a mean value of 2.03 × 10−4, which is around 22% more than the maximum
acceptable level (l.67 × 10−4) as per guidelines of India’s Atomic Energy Regulatory
Board. The mean of chemical toxicity risk, expressed as life time average daily dose
(LADD) was worked out to be 5.56 µg/kg/day with a range of 0.15–48 µg/kg/day
by considering a bodyweight of 51.5 ± 8.5 kg, water ingestion rate of 4.05 L/d,
and life expectancy of 63.7 yrs for an adult Indian reference man and compared
with the reference dose (4.53 µg/kg/day). The average exposure level of U was
comparatively high and the chemical toxicity was expected to be more. The mean of
hazard quotient (LADD/ RfD) for all four districts was found to be greater than 1,
indicating that groundwater may not be suitable for consumption from a chemical
toxicity point of view.
Key Words: groundwater, uranium, laser fluorimeter, radiological risk, chemical
risk.
INTRODUCTION
Uranium is a ubiquitous element and is found mainly in the oxidation states of +3,
+4, +5, and +6. It is present in rocks, soil, natural materials, and in small quantities
in air, water, and food (USDOE 2001). Natural U and its daughter products content
in groundwater are often associated with the presence of granitic rocks (Michel
381
A. Kumar et al.
(Giblin et al. 1981). At concentrations less than 10−6M, UO2 (OH)+ is the dominant
hydrolysis species in solution, while greater than this concentration, polymeric forms
such as (UO2 )2 (OH)2 2+, (UO2 )3 (OH)4 2+, and (UO2)3 (OH)5+ are more dominant.
The biokinetics, metabolism, and chemical toxicity of U including the toxic ef-
fects of this metal on kidney functions are well established (Domingo 1995). Under
some circumstances, the chemical toxicity of soluble U can even surpass its potential
radiotoxic effects. The toxicity of U is a function of the route of exposure, parti-
cle solubility, contact time, and route of elimination (ATSDR 1999). The United
Nations Scientific Committee on Effects of Atomic Radiation (UNSCEAR 1982) es-
tablished the limits for natural U in drinking water based on its chemical toxicity for
kidney rather than on hypothetical radiological toxicity for skeletal tissues. A level of
100 µg/L of U in drinking water was chosen reasonable, based on consideration
of renal toxicity with the application of a safety factor of 50 to 150 (Wrenn et al.
1985). The chemical toxic effects of different U compounds on reproduction and
development in mammals (rats) were investigated and it was reported that quantity
of sperm DNA strand breakage increases with increase in dose of U (Zhu et al.
1994). In addition, it was also noted that U causes skeletal abnormalities in fetal
rats. In literature, the chemical effects on human kidney induced by the chronic
ingestion of U in drinking water were studied for low exposure and high exposure
with the concentration ranging from <1 µg/L–781 µg/L. The chemical toxicity
due to intake of U by considering these levels, were in the range of 0.004 to 9 µg
per kg bodyweight per day (Zamora et al. 1998).
In 1991, the U.S. Environmental Protection Agency (USEPA) classified U as a
confirmed human carcinogen (group A) and has suggested that zero tolerance
only is a safe acceptable limit for the carcinogenic risk. At present, the USEPA
has proposed a realistic regulation level as maximum contaminant level (MCL)
of 30 µg/L (USEPA 1999b). Canada has proposed interim maximum acceptable
concentration (IMAC) of 20 µg/L. The World Health Organization (WHO 2004)
has strictly recommended a reference level of 15 µg/L, considered, being protective
for subclinical renal effects. The reference level is derived from epidemiological
studies, based on the assumption of a 60 kg adult consuming 2 liters of drinking
water per day and 80% allocation of the Tolerable Daily Intake (TDI) to drinking
water. The WHO has also established a TDI for U of 0.6 µg/kg bodyweight/day
(WHO 1998, 2003), which is based on adverse effects observed on kidneys of rats at
uptake of 60 µg U per kg per day (Gilman 1998).
ter containing 1 mL of HNO3 (70% pure). The blank sample containing the same
amount of fluorescing reagent was also measured for U concentration. Five per-
cent phosphoric acid in ultra pure water was used as fluorescence reagent. All the
reagents used for experimental work were of ultrapure/analytical grade (Merck,
Mumbai, India).
where U level (Bq/L) = a measured value (µg/L) × conversion factor (0.025 Bq/
µg).
(HDR India 2009), and 51.5 ± 8.5 kg for bodyweight (Dang et al. 1994). The hazard
quotient (HQ) and chemical toxicity risk (LADD) were calculated through ingestion
of groundwater by the following formulas
LADD
HQ = (3)
RfD
LADD (UG/KG/DAY) = [Ci × IR × EF × LE]/[BW × AT] (4)
Uncertainty Analysis
To analyze the uncertainty on estimation of excess cancer risk and lifetime average
daily dose (LADD), the input distributions on exposure frequency and bodyweight
were assumed as triangular distribution and normal distribution, respectively. Nor-
mality testing for U (concentration) distribution in all the four districts of Punjab
was tested by the Shapiro-Wilk statistical method as well as by box-and-whiskers plots.
Since mean and median values are significantly different, the U distribution cannot
be assumed as a normal distribution. Ingestion rate of drinking water, total exposure
duration, and averaging time were considered as constant input values as given in
Table 1. Finally, the 5th, 50th, and 95th percentiles of the output distribution were
forecasted for excess cancer risk and LADD.
Statistical Methods
To study the distribution characteristics of U concentrations in subsurface water
of all the four districts in Punjab, normality testing was performed by two statistical
methods: the Shapiro-Wilk “W” test and the box-and-whiskers plot (Origin Software,
Version 8.1). The Shapiro-Wilk W statistical method is a semi-nonparametric analysis
of variance that detects a broad range of different types of normality in a sample of
data. The null hypothesis for this test is that “the data follows a normal distribution.”
At the significant level of 0.05, if the calculated probability value (W) is greater than
a tabulated value, then the null hypothesis is rejected (i.e., the data do not follow
a normal distribution). The second statistical method applied to data was box-and-
whiskers plot (a nonparametric analysis), which is a powerful graphical summary of
distribution characteristics of data. The box (in the graph plot) covers the middle
half of the data and whiskers show the range of the data. Since mean and median
values obtained from the above methods were significantly different, therefore the
U concentration distribution cannot be assumed a normal distribution.
Table 2. Uranium concentrations of subsurface water in four districts (Bathinda, Mansa, Faridkot, and Firojpur)
of Punjab state in India (all data in µg/L.
Districts Mean IQR
(No. of samples) concentration of U Median P5 P95 P25 P75 (P75 -P25 ) Minimum Maximum
Bhatinda (80) 80.83 ± 5.3 56.02 4.5 164.225 28.50 108.67 80.17 2 644
Mansa (80) 75.83 ± 6.7 47.25 5 216.95 25.15 104.65 79.50 < 0.2 498
Faridkot (30) 68.56 ± 8.3 38.35 3.25 242.9 16.50 81.70 65.20 16.5 473.5
Firozpur (45) 62.12 ± 7.3 54.8 3.4 142.5 27.40 95.70 68.30 2.8 184.4
P5 = 5th Percentile; P25 = 25th Percentile; P75 = 75th Percentile; P95 = 95th Percentile.
IQR: Inter quartile Range.
387
A. Kumar et al.
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types, soil texture, different rocks, rocks weathering, or different levels of surface
mineralization. Depicted in Figure 2 is the graphical representation of mean con-
centrations of U in all subsurface water at different depths ranges in the Bathinda,
Mansa, Faridkot, and Firozpur districts of Punjab state. From the data, it is obvious
that as the depth increases, the concentration of U decreases. It was also observed
that, up to the depth of 200 ft, all districts showed higher mean concentration of U
except the Firozpur district, which may be due to leaching through soil by heavy use
of fertilizers in the fields and/or due to wastes released from thermal power plants,
fertilizer factories, chemical factories, or cement factories.
100
Bhatinda 100 Mansa
Mean Uranium Conc. (µg/L)
80
80
60 60
40 40
20 20
0 0
<100 ft. 100–200 ft. 200–300 ft. >300 ft. <100 ft. 100–200 ft. 200–300 ft. >300 ft.
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80
240
Mean Uranium Conc. (µg/L)
70
210
Faridkot 60 Firozpur
180
50
150
40
120
30
90
60 20
30 10
0 0
<100 ft. 100–200 ft. 200–300 ft. >300 ft. <100 ft. 100–200 ft. 200–300 ft. >300 ft.
Depth range (ft.) Depth range (ft.)
Figure 2. Graphical representation of mean concentration of uranium in all sub-
surface water at different depths range of Bathinda, Mansa, Faridkot,
and Firozpur districts in Punjab state.
390
Table 3. Excess cancer risk with different percentile (5th–95th) due to ingestion of uranium in subsurface water
of four districts of Punjab.
Point Median
Districts estimate (mean) (50th percentile) P5 P95 P25 P75
−4 −4 −4 −4 −4
Bhatinda 2.26 × 10 1.56 × 10 1.26 × 10 4.6 × 10 0.79 × 10 3.05 × 10−4
Mansa 2.12 × 10−4 1.32 × 10−4 1.40 × 10−4 6.1 × 10−4 0.70 × 10−4 2.93 × 10−4
Faridkot 1.92 × 10−4 1.07 × 10−4 0.91 × 10−4 6.8 × 10−4 0.46 × 10−4 2.30 × 10−4
Firozpur 1.74 × 10−4 1.54 × 10−4 0.95 × 10−4 4.0 × 10−4 0.77 × 10−4 2.68 × 10−4
P5 = 5th Percentile; P25 = 25th Percentile; P75 = 75th Percentile; P95 = 95th Percentile.
Risk Assessment for Natural Uranium
Table 4. Chemical toxicity risk (LADD1 and HQ) with different percentile
(5th–95th) due to ingestion of uranium in subsurface water of four
districts of Punjab.
Point
estimate
(mean) Median P5 P95 P25 P75
1
Expressed as µg kg−1 day−1
P5 = 5th Percentile; P25 = 25th Percentile; P75 = 75th Percentile; P95 = 95th Percentile.
LADD: Life Time Average daily Dose, HQ: Hazard Quotient.
The mean of hazard quotient (LADD/RfD) was also found to be greater than 1 for
all the areas, which may not be acceptable from the chemical toxicity point of view.
However, in the case of the median of hazard quotient or LADD, all areas showed
less than acceptable limits indicating that subsurface water is fit for consumption
from a chemical toxicity point of view. In the worst case based on very conservative
assumptions, at the 95th percentile, the average exposure dose was determined to be
14.10 µgkg−1day−1, which is 5–6 times greater than the RfD. The LADD was observed
to be highest in Faridkot and Mansa at the 95th percentile. The average exposure
level of U was comparatively high and the chemical toxicity in turn is also presumed
to be greater. Therefore groundwater in those areas may not be considered safe for
drinking purposes. It is also suggested that periodic monitoring of water quality and
management are needed for those areas where U was detected in high concentra-
tions. Chemical toxicity risks (LADD1 and HQ) with different percentiles (5th–95th)
due to ingestion of U in subsurface water of the four districts of Punjab are given in
Table 4.
CONCLUSIONS
At the 5th percentile, no statistically significant radiological risk was found among
all districts but in the case of the 95th percentile, the Mansa and Faridkot dis-
tricts showed the greater radiological risk (about 6–7 per 10,000 people) than the
Bhatinda and Firozpur districts (4–5 per 10,000). The mean hazard quotient for all
districts was also found to be greater than 1. However, in the case of the median
hazard quotient or LADD, all districts showed less than the permissible limits. In
the worst case, based on a very conservative assumption (at 95th percentile), the
average exposure dose was determined to be 5–6 times greater than the RfD. The
LADD was observed to be greater in the Faridkot and Mansa districts at the 95th
percentile than the Bhatinda and Firozpur districts. It was also observed that, up to
a depth of 200 ft, all districts showed greater mean concentration of U except the
Firozpur district, which may be due to leaching through soil by farmers’ heavy of use
of fertilizers on the fields. Over a lifetime consumption of groundwater at an aver-
age 4.05 L/day with present U levels, the mean excess cancer risk in all districts was
found to be 2.03 × 10−4 (about 2 per 10,000 people) whereas at the 95th percentile
(worst case) it rose to 5 × 10−4 (about 5 per 10,000). At the 50th percentile (me-
dian), both radiological risk (carcinogenicity) and chemical risk (non-carcinogenic
toxicity for kidney toxicity), were observed to be well within acceptable limits. It is
suggested that a periodic monitoring of water quality and proper management of
water supplies by installing reverse osmosis units in villages should occur where U is
detected in high concentrations.
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ACKNOWLEDGMENTS
The authors sincerely acknowledge the guidance and help provided by Dr. P.K.
Sarkar, Head, Health Physics Division, BARC, Trombay, Mumbai, and Dr A.G. Hegde,
Head, Evironmental Studies Section, BARC, Mumbai. The authors thank Professor
B.S. Bajwa, HOD, Department of Physics, Guru Nanak Dev University (GNDU), Am-
ritsar, Prof. Lakhwant Singh, Department of Physics, GNDU, Amritsar, for providing
necessary facilities, good hospitalities, help in sampling, and for encouragement.
The authors are also grateful for financial support given by the Board of Research
in Nuclear Science (BRNS), Mumbai, under the memorandum of understanding
(MOU) between GNDU, Amritsar, Punjab and the Bhabha Atomic Research Centre,
Trombay, Mumbai.
REFERENCES
Abdelouas A, Lutze W, and Nuttall E. 1998. Chemical reactions of uranium in ground water
at a mill tailings site. J Contaminant Hydrol 34(4):343–61
AERB, DAE (Atomic Energy Regulatory Board, Department of Atomic Energy). 2004. Drink-
ing Water Specifications in India. Atomic Energy Regulatory Board, Mumbai, India
ATSDR (Agency for Toxic Substances and Diseases Registry). 1999. Toxicological Profile for
Uranium. US Department of Health and Human Services, US Public Health Services,
Atlanta, GA, USA
Cantaluppi C and Degetto S. 2000. Civilian and military uses of depleted uranium: Environ-
ment and health problem. Ann Chim 90:665–76
Dang HS, Jaiswal DD, Parmeshwran M, et al. 1994. Physical, Anatomical, Physiological and
Metabolic Data for Reference Indian Man-A Proposal. BARC/1994/E/03. Board of Re-
search in Nuclear Sciences, Mumbai, India
Domingo JL. 1995. Prevention by chelating agents of metal-induced development toxicity.
Reprod Toxicol 9:105–13
Drever JL. 1997. The Geochemistry of Natural Waters–Surface and Groundwater Environ-
ments, 3rd edit, pp 436. Prentice Hall Publishing, New Jersey, USA
Giblin AM, Batts BD, and Swaine DJ. 1981. Laboratory simulation studies of uranium mobility
in natural waters. Geochim Cosmochim Acta 45:699–709
Gilman AP, Villeneuve DC, Secours VE, et al. 1998. Uranyl nitrate: 28-day and 91-day toxicity
studies in the Sprague-Dawley rat. Toxicol Sci 41:117–28
HDR (Human Development Report). 2009. National Resource Centre for Urban Poverty and
All India Institute of Local Self Government. Mumbai, India
Health Canada. 1999a. Uranium in Drinking Water. Document for Public Comment Prepared
by Federal Provincial Subcommittee on Drinking Water. Ottawa, ON, Canada
Health Canada. 1999b. Summary of Guidelines for Canadian Drinking Water Quality. Pre-
pared by Federal- Provincial Subcommittee on Drinking Water of the Federal-Provincial-
Territorial Committee on Environmental and Occupational Health. Ottawa, ON, Canada
Jain SC, Mehta SC, Kumar B, et al. 1995. Formulation of the reference Indian adult anatomic
and physiological data. Health Physics 68(4):509–22
Michel J. 1991. Relationship of radium and radon with geological formations. In: Richard
Cothern CR and Rebers PA (eds), Radon, Radium and Uranium in Drinking Water, 2nd
edit, pp 83–96. Lewis Publishers, Boca Raton, FL, USA
Ortega X, Valles I, and Serrano I. 1996. Natural radioactivity in drinking water in Catalonia
Downloaded by [Bhabha Atomic Research Centre] at 04:37 27 July 2011