Geochemistry and Quality of Groundwater, and Natural

Radioactivity Measurements in Parts of Manavalakurichi:

An Active Placer Mineral Mining Site, Southern India
C.S.P. IYER, C. SREEJITH, S. SUBHA, AND SMITHA SUKUMARAN
Centre for Marine Analytical References and Standards (C–MARS)
Regional Research Laboratory (CSIR), Trivandrum–695 019

ABSTRACT
Environment and human health are closely connected. Ecological, hydrogeological, and
geochemical factors affect the physical environment in which people live. Groundwater
quality deterioration and radioactivity hazards are the major threats, where black sand
minerals are mined. A hydrogeochemical investigation and natural radiation measurements
have been carried out in parts of Manavalakurichi, southern India to assess the impact posed
by mining. The hydrochemical study provided significant information on the development of
groundwater quality in this active mining sector. The water is mostly fresh in nature, except
in coastal stretch, where saline water intrusion is there. The geochemical stressors, such as
base exchange have also influenced the quality away form the sea. The groundwater in the
vicinity of mining is affected by seawater contamination, but only to a local extent. The
distribution of natural radionuclides γ-ray activities and their monazite percentage equivalent
were determined for sand samples collected along the coast. The intensity of counts emitted
by the daughter products of natural radionuclides 232Th and 238U has also been assessed. The
area can be considered as one of the high natural background radiation area, due to the
presence of radiogenic heavy minerals.

Keywords: Groundwater, hydrogeochemistry, heavy mineral sands, natural

radioactivity, gamma-ray spectrometry, Manavalakurichi, southern India.

INTRODUCTION
The earth’s environment, where human and other organisms live in, consist of top lithosphere,
hydrosphere, atmosphere, and biosphere. The physical environment provides basic resources
and nutrients for us to survive. Water and soil in the environment are essential components of
the ecosystem and their quality is important to human health. The hydrogeological
environment, particularly in such a world of increasing population, plays an important role in
the respect of human health (Yang et. al., 1999). The interaction between human health and
the environment are complex. Each of us depends daily on geologic resources mined from
sites around the world. We use scores of metal and minerals, many of which we have never
heard of, in our lights, computers, watches, fertilizers, and cars. Mining and purifying all
these resources can have severe environmental and social consequences. The most obvious
effect of mining is often the disturbances or removal of the land surface. Farther-reaching
effects include air and water pollution. Mining changes the hydrodynamics of both surface
and groundwater systems. There is plenty of evidence from all continents that active and
abandoned mines cause severe pollution (e.g., Kempe, 1983; Hedin et. al., 1994; Banks et al.,
1997; Jarvis and Younger, 2000). Before a mining lease is awarded, the Environmental
Protection Agency (EPA) requires an Environmental Impact Assessment (EIA) report that
must be officially approved. While the EPA has a robust regime in a place for enforcing the
environmental laws of the country, many of the EIA lacks information on the hydrodynamics
of the mining areas. Even in situations, where some hydrogeological information is
presented, important aspects are often neglected in the report.

The black sand deposit of Manavalakurichi is considered to be one of the most

important placer deposits of India. Mining of these placer deposits, in large quantities, pose
serious threat to the environmental and ecological balance of the surrounding region.
Groundwater is an important source of water supply in Manavalakurichi region, Tamil Nadu.
It is mainly developed for domestic and industrial uses because there is insufficient surface
water. Large-scale groundwater abstraction in the area has resulted in adverse economic and
environmental problems, such as declining piezometric levels and deterioration in
groundwater quality. These problems will become more serious in the future. Management
of the groundwater resources requires an understanding of the main processes controlling the
geochemical evolution and origin of groundwater. The chemical characteristics of the
groundwater provide clues to its geologic history, its interference with soil or rock masses
within the hydrologic cycle (Ward, 1975; Freeze and Cherry, 1979; Fetter, 1990). Intrusion
of seawater into the inland aquifers due to the over exploitation of groundwater along the
coastal area is an environmental issue. To protect coastal groundwaters, the sources of saline
water and mechanisms of mobility need to be identified and investigated for sustainable
development of the groundwater resources.

AREA OF STUDY
Location and physiography
The study area covers an area of 50 Km2, extending between latitudes 8o 04’ – 8o 14’ N and
longitudes 77o 11’ – 77o 24'E with a population of 46,928, located in the Kanyakumari district
of Tamil Nadu (Fig. 1). The climate is humid with extremely hot summers; the average
ambient day temperature varies from 25o to 38oC and is greatly influenced by the southwest
monsoon. The average annual rainfall is about 1465 mm. Physiogarphically, the study area
is almost flat with a gentle slope, generally towards the south. The drainage pattern is
subdendritic. Valliyar is the only river in the area, flowing from north and discharging into
the sea towards south.
8° 14' 51" 8° 14' 51"
77° 77°
11'
TAK
KAL 24'
AI
06"
45"
TIRUVANKOD
∋
Appatuvila
MIDALAM
NNN
HH
4477
Paracheri 77
Palayam
Midalam Neyyur Eranlel
Puduvukara
Alur
Pattarvilai
Kurundankod
yar R

Lekshmipuram
Kunnathukulam
Valli

Kolachal Vembanur
MANAVALAKURICHI
Mandakad
Chandapuram
Vellomudi Shorel ine
IRE

Road
Elluvilai
Drainage
Muttumthara

kkkkmm River
1111

LAKSHADWEEP SEA

77° 0 2.5 5 77°

11' 24'
Kilometers
45" 06"
8° 02' 36" 8° 02' 36"
Figure :: Location
Figure Location map
map of
of Manavalakurichi
Manavalakurichi

Fig. 1. Location map of Manavalakurichi

Geological and hydrogeological set up

The investigated area underlain by charnockite, leptynite (quartzo–feldspathic– garnet
gneiss), and schists of Proterozoic age (Santosh et. al., 2003). The charnockites are medium
to coarse grained and are characterized by orthoclase and plagioclase feldspar, hypersthene,
diopside, ilmenite and magnetite. Majority of the out crops observed are devoid of garnet, but
almandine garnet is seen in areas, where the charnockite incorporate metasedimentary
lithologies. The leptynites are light grey, coarse grained, consisting of quartz, plagioclase,
biotite, and garnet. Red soils derived from the weathering of parent rocks are the dominant
type. Occurrence and movement of groundwater are controlled by the degree and structure.
Groundwater aquifers in Manavalakurichi can be classified into three broad categories, (i)
shallow unconsolidated sediments and coastal alluvium, (ii) mixed laterite-hard rock horizon,
and (iii) fractured hard rock aquifers that occur in a wide range of bedrock types. The depth
of weathering ranges from 3–10 m with an average of about 6 m., while the fractures in the
rocks extend to 80 m depth, but the average depth is 50 m from the ground surface.
Groundwater in the weathered zone is under water table conditions whereas, in the fractures,
it is under semi-confined to confined conditions. Depending on the thickness of soil and/or
weathered zones, wells are fully or partly lined. The principal productive zone in this region
lies between 10 and 20 m below the land surface. Development of groundwater is through
open dug wells (shallow wells) and bore wells (deep wells).

Natural radioactivity
It has been established previously that the highest background areas in India are the coastal
plains of Kerala, Karnataka, and Tamil Nadu. This is due to the monazite deposits in these
places (Mallik et. al., 1987). Therefore, it was felt interesting to study the distribution and
enrichment of radionuclides in the southwest coast of Tamil Nadu, and assess the level of
background radiation of beach sands in the study area. Natural radioactivity in sands comes
from U and Th series and natural K. The study of the distribution of primordial radionuclides
allows the understanding of the radiological implication of these elements due to the γ-ray
exposure of the body and irradiation of lung tissue from inhalation of radon and its daughters
(Alam et. al., 1999; Singh et. al., 2005). In particular, it is also important to assess the
radiation hazards arising due to the use of soil or sand samples in the construction of
dwelling. Therefore, the assessment of gamma radiation dose from natural sources is of
particular importance as natural radiation is the largest contributor to the external dose of
world population.

METHODOLOGY
Groundwater monitoring networks and sampling techniques
The monitoring network consisted of 12 dug wells and 3 bore wells at various locations (Fig.
2). Representative water samples were collected from all the 15 wells during April 2005.
Prior to sampling, water levels were monitored in the open wells. Sample bottles were rinsed
with purge water, and then filled completely to minimize headspace. A 30 ml aliquot for
anion analysis was stored in a polyethylene bottle at 4oC until analysis. Another 30 ml aliquot
for cation analysis was passed through a 0.45 µm filter, acidified to pH 2 with ultra-pure
HNO3, and stored in a polyethylene bottle at 4oC until analysis.

Fig. 2. Location of the representative groundwater sample point

The samples were analysed for the major ion chemistry, employing the standard methods
(APHA, 1992). Hydrogen ion concentration (pH) and specific electrical conductivity (SEC)
were measured, using pH and SEC meters. Carbonate (CO32–) and bicarbonate (HCO3–) were
estimated by titrating with HCl. Total hardness (TH) as CaCO3, and calcium (Ca2+) were
analysed titrimetrically, using standard EDTA. Magnesium (Mg2+) was calculated from TH
and Ca2+. Sodium (Na+) and potassium (K+) were measured by a flame photometer. Chloride
(Cl–) was estimated by standard AgNO3 titration. Sulphate (SO42–), nitrite (NO2–), nitrate
(NO3–), and phosphate (PO43–) were analysed using PerkinElmer UV–Visible
spectrophotometer, Lambda 25. All the parameters are expressed in milligrams per litre
(mg/l) and millimoles per litre (mmol/l), except pH (units).

Radiometric analysis
The sand samples containing heavy minerals were collected from the Manavalakurichi placer
deposit by the core sampling technique. About 1 kg of the sand samples was collected from
each location. In the laboratory, the samples were cleaned with warm water and dried. The
gamma-ray spectrometric analysis was carried out using a Minim Based Gamma Ray
Spectrometer Nucleonix–GR 611M. The detector was placed in a 6 cm shield of lead bricks
to reduce background radiation originating from building materials and cosmic rays. An ideal
measuring geometry of cylindrical source (homogeneously distributed activity with constant
volume and distance) was placed coaxially with the detector for sample measurements.
Energy calibration was performed in the energy range from 0.5 to 3 meV. The following
photon emissions, observed as single or double peaks, were used: 57Co (0.123 meV), 133Ba
(0.36 meV), 22Na (0.511 and 1.280 meV), 137Cs (0.662 meV), 54Mn (0.84 meV), and 60Co
(1.17 and 1.33 meV). Natural radionuclides of relevance for this work are mainly gamma-ray
emitting nuclei in the decay series of 232Th and 238U. It is possible to measure gamma-rays
emissions of these elements only by observing their decay products, as 232Th and 238U are not
directly gamma-ray emitters. Decay series of 238U (214Pb: 0.295 and 0.911 meV; and 214Bi:
0.609 meV) and 232Th (228Ac: 0.209, 0.338, and 0.911 meV; 212Pb: 0.239 meV; and 212Bi:
0.727 meV) were used by assuming the decay series to be in secular equilibrium (Firestone
and Shirley, 1998).

RESULTS AND DISCUSSION

Groundwater quality
Summary of the results of the chemical analysis of groundwater are presented in Table 1, and
is compared with the Indian Standards (BIS 10500, 1991) and WHO (1993). The pH of
groundwater varied from 4.60 to 7.31. The alkaline pH of 7.30 is recorded in well no. 2,
situated in the mining site.

Table. 1. Summary of the chemical composition of groundwater and their comparison

with drinking water standards, Indian (BIS 10500, 1991) and WHO (1993)
Range Indian WHO
Parameters
Minimum Maximum Standards Limits
pH 4.60 7.31 6.5–8.5 7.0–8.0
Specific Electrical Conductivity µS/Cm 120 3,010 – –
Total dissolved solids (mg/l) 80 2,040 – –
Total hardness as CaCO3 28.80 470.40 300 –
Bicarbonate (mg/l) 15.15 202 – –
Chloride (mg/l) 27.55 688.70 250 250
Sulphate (mg/l) 2.17 278.04 200 250
Phosphate (mg/l) 0.009 17.40 – –
Calcium (mg/l) 10.01 210.17 75 75
Magnesium (mg/l) 4.39 260.23 30 30
Sodium (mg/l) 1.86 162.42 – 200
Potassium (mg/l) 0.50 55.00 – –
The pH records a low value of 4.60 in well no. 1, which is the mineral processing site, 500
meters away from the mining site. This indicates that the acidic discharges from the mineral
processing have contributed to the lowering of pH. The variation in pH at a small spatial
interval infers the impact of mining or processing operation does not extend to a wide region.
The well water from no. 3, very near the fresh water lake, Periyakulam, records a pH of 7.31.
Otherwise, the water in the wells in the study area is slightly on the acidic side, in the range of
5.50–6.83. This is also true of the water from the bore wells, numbered 11 and 12. However,
in the bore well water of no. 14 is neutral.

Concentration of total dissolved solids (TDS), a measure of quality, ranged from 80

to 2,040 mg/l with a mean of 420. Except two samples, no. 2 from the mining site and no.
14– a bore well which have TDS>500 mg/l, all the others are within the permissible limit of
TDS for drinking (BIS, 1991; WHO, 1993). According to the standards TDS classification
(Fetter, 1990), most of the groundwaters fall under fresh water category (TDS<1,000 mg/l),
except sample no. 2, which coming under the brackish type (TDS>1,000 mg/l).

The total hardness (TH) varies from 29 to 470 mg/l. This indicates that the
groundwater vary from soft (<75 mg/l), as in the case of most samples; moderately hard (75–
150 mg/l), as in samples 9 and 10; hard (150–300 mg/l), as in sample no. 1, 8, and 14; to very
hard (>300 mg/l), as in sample no. 2, as per the TH classification of Swayer and McCarty
(1967). TH with more than 300 mg/l is not suitable for drinking (BIS 10500, 1991).

Major ion chemistry

Among the cations, the concentration of Ca2+, Mg2+, Na+, and K+ ions ranged from 10 to 210,
4 to 260, 2 to 162, and 0.50 to 55 mg/l with a mean of 54, 27, 56, and 14 mg/l respectively.
The order of ionic abundance is Na+ > Ca2+ > Mg2+ > K+. The dissolved anions, CO32–, HCO3–
, Cl–, and SO42– ions lie in between 10 and 101, 15 and 202, 27 and 688, and 2 and 278, mg/l
with a mean of 23, 44, 110, and 57 mg/l respectively. The order of their abundance is Cl– >
(CO32– + HCO3–) > SO4–. A comparison of the concentrations of Ca2+, Mg2+, and Cl– with the
recommended limits (Table. 1) for drinking suggests that the concentration of Ca2+ exceeds in
samples 1, 2, and 14, Mg2+ in samples 1 and 2, and Cl– in sample no. 2.

The ionic ratio Ca2+: Mg2+, which is widely used for assessing the impact of seawater
on the aquifer chemistry (Revelle, 1941; Hem, 1959), were computed from the analysed
chemical constituents. The groundwater samples 2, 4, 7, and 8 appear to be contaminated by
seawater. However, regarding the sample no. 8, which is located at moderate topography
away from the sea may not support any influence of seawater into the inland aquifer-water.
In this case the brackish nature of the water is not due to the influence of seawater, but is
caused by hydrogeochemical processes. For example, feldspar in the country rock mainly
contributes Ca2+ and Na2+ to the groundwaters, whereas ferromagnesium content in the parent
rock is major source of Mg2+ in the groundwaters. Base exchange appears to be responsible
for the occurrence of brackish waters, as the area is associated with clayey horizon at the
intermediate zone.

Radiation measurements
The measured counts per 10 seconds for samples from Midalam, Mandakkad, and
Manavalakurichi respectively are 867, 1349, and 90 for the 212Pb (daughter product of 232Th)
and 307, 472, and 44 for the 214Pb (product of 238U disintegration). The monazite percentage
equivalent for these samples is 1.54, 0.17, and 2.9. The distribution of radioactivity with
respect to monazite percentage is depicted in figure no. 3. The study indicates that the
sources of enhanced level of natural radioactivity in the beach sands are found chiefly in
monazite sands. Based on the high natural radioactivity, this region can be considered as a
high background radiation area.
 Fig. 3. Map showing radioactive mineral distribution along the beach

CONCLUSION
In this study we have reported the hydrochemistry of groundwaters in an active placer mineral
mining area, Manavalakurichi. Groundwater in this region occurs in three main aquifer units.
These are the unconsolidated sediments, forming the unconfined aquifer of top layers,
weathered horizon under the water table condition, and the fractures under semi-confined to
confined conditions. The study provides significant information on the development of
groundwater quality in parts of Manavalakurichi, which is the major fresh water source for
this coastal region. Most of the waters are in fresh water side. However, some locations
show saline water intrusion and quality deterioration, to a limited extent, may be due to the
mineral mining and processing. Hydrogeochemical processes also caused for the brackish
nature in one location. Long term monitoring of water levels are required for assessment of
ongoing local and regional impacts on groundwater quality in this basin. Validated baseline
quality data are sparse. A major effort is needed to collect reliable hydrochemical
information and to make the data accessible both to the regular and the environmental
community. Study of natural radioactivity is of considerable importance with respect to such
as in future exploitation of nuclear energy, nuclear waste management problems, radiation
exposure in natural high background areas, processing of radioactive materials, and also in
radiological research programmes. Monazite percentage equivalent rates of the beach placers
indicate the good prospect of monazite in Midalam beach apart from the Manavalakurichi,
which is an active mining site at present. The natural radioactivity in these sites may be
correlated with the presence of heavy-mineral deposits in the beach sands. The information
regarding the gamma-ray dose can be transferred to the local people to avoid the use of these
soil or sand in the construction of dwellings.

ACKNOWLEDGEMENTS
Financial support to CSP under an EIA by the CMRI, Govt. of India is gratefully
acknowledged. We are grateful to the Director Atomic Minerals Directorate, Trivandrum unit
for his help in radiometric analysis. Also our sincere thanks to Mr. C. Sandeep, Ceramic
Technology Division, RRL, for his kind help and keen interest taken during the Flame
Photometric analysis. CS would like to thank Council for Scientific and Industrial Research
(CSIR), Govt. of India for the fellowship in the form Research Intern awarded to him.

REFERENCES
Alam, M.N., Chowdhury, M.I., Kamal, M., Ghose, S., Islam, M.N., Mustafa, M.N., Miah,
M.M.H., and Ansary, M.M., 1999. The 226Ra, 232Th, and 40K activities in beach sand
 minerals and beach soils of Cox’s Bazar, Banagaladesh. Jour. Environ. Radioact.,
v.46, pp.243–250.

APHA, 1992. Standard Methods for the Examination of Water and Waste Water. 16th Ed.,
American Public Health Association, Washington DC. 1268p.

Banks, D., Younger, P.L., Arnesen, R.T., Iversen, E.R., and Banks, S.B., 1997. Mine water
chemistry: the good, the bad, and the ugly. Environ. Geol., v.32, pp.157–174.

BIS 10500, 1991. Indian Standard Drinking Water–Specification. Bureau of Indian

Standards, First Revision, pp. 1–8.

Fetter, C.W., 1990. Applied Hydrogeology. Mirril Publ. Co., USA.

Firestone, R.B. and Shirley, V.S., 1998. Table of Isotopes. 8th Ed., John Wiley, New York.

Freeze, W.H. and Cherry, J.A., 1979. Groundwater. Prentice–Hall, Inc., USA.

Hedin, R.S., Nairn, R.W., Kleinmann, R.L.P., 1994. Passive treatment of coal mine drainage.
US Bureau of Mines Information Circular 9389. US Deptt. of the Interior. Pittsburgh
(PA), Bureau of Mines, 35p.

Hem, J.D., 1959. Study and interpretation of the chemical characteristics of natural waters.
US Geol. Surv. Water Supply, 1473.

Jarvis, A.P. and Younger, P.L., 2000. Broadening the scope of mine water environmental
impact assessment: a UK perspective. EIA Rev., v.20, pp.27–58.

Kempe, J.D., 1983. Review of water pollution problems and control strategies in the south
African mining industry. Water Sci. Technol., v.15, pp.27–58.

Mallik, T.K., Vasudevan, V., Aby Verghese, P., and Terry Machado, 1987. The black sand
placer deposits of Kerala beach, southwest India. Mar. Geol., v.77, Pages 129-150.

Revelle, R., 1941. Criteria for recognition of seawater in groundwaters. Trans. Amer.
Geophys. Union, v.22, pp.593–597.

Santosh, M., Tagawa, M., Taguchi, S., and Yoshida, S., 2003. The Nagercoil Granulite
Block, southern India: petrology, fluid inclusion, and exhumation history. Jour.
Asian Earth Sci., v.22, pp.131–155.

Singh, S., Rani, A., and Mahajan, R.K., 2005. 226Ra, 232th, and 40K analysis in soil samples
from areas of Punjab and Himachal Pradesh, India using gamma ray spectrometry.
Radiat. Meas., v.39, pp.431–439.

Ward, R.C., 1975. Principles of Hydrology. McGraw–Hill Publ. Co. Ltd., London.

WHO, 1993. Guidelines for Drinking Water Quality. 2nd Ed., World Health Organisation,
v.1, 188p.

Yang, Y.S., Lin, X.Y., and Kalin, R.M., 1999. Water management under the impact of urban
development in developing country. Environ. Manage. Health, v.10, pp.18–30.