Environ Monit Assess
DOI 10.1007/s10661-009-1239-4
Identification of the hydrogeochemical processes
in groundwater using major ion chemistry: a case study
of Penna–Chitravathi river basins in Southern India
A. G. S. Reddy · K. Niranjan Kumar
Received: 24 May 2009 / Accepted: 29 October 2009
© Springer Science + Business Media B.V. 2009
Abstract Hydrogeochemical studies were carried
out in the Penna–Chitravathi river basins to
identify and delineate the important geochemical
processes which were responsible for the evolu-
tion of chemical composition of groundwater. The
area is underlain by peninsular gneissic complex
of Archaean age, Proterozoic meta-sediments,
and strip of river alluvium. Groundwater sam-
ples were collected covering all the major hydro-
geological environs in pre- and post-monsoon
seasons. The samples were analyzed for ma-
jor constituents such as Ca2+ , Mg2+ , Na+ , K+ ,
CO3 − , HCO3 − , Cl− , SO2 −4 , NO3 − , and F− . The
groundwater in general is of Na+ –Cl− , Na+ –
HCO3 − , Ca2+ –Mg2+ –HCO3 − , and Ca2+ –Mg2+ –
Cl− types. Na+ among cations and Cl− and/or
HCO3 − among anions dominate the water; Na+
and Ca2+ are in the transitional state with Na+
replacing Ca2+ and HCO3 − Cl− due to physio-
chemical changes in the aquifer and water–rock
interactions. The Ca2+ –Mg2+ –Cl− HCO3 − type
water in one third samples suggest that ion ex-
change and dissolution processes are responsible
A. G. S. Reddy (B)
Central Ground Water Board, SR, Hyderabad, India
e-mail: sugrive_59@rediffmail.com
K. N. Kumar
Kakatiya University, Warangal, AP, India
for its origin. Change in storage of aquifer in a
season does not influence the major geochemical
makeup of groundwater. Gibbs plots indicate that
the evolution of water chemistry is influenced
by water–rock interaction followed by evapotran-
spiration process. The aquifer material mineral-
ogy together with semiarid climate, poor drainage
system, and low precipitation factors played ma-
jor role in controlling groundwater quality of
the area.
Keywords Penna–Chitravathi rivers ·
Anantapur · Hydrogeochemstry ·
Pre- and post-monsoon · Evapotranspiration ·
Water–rock interaction
Introduction
Groundwater, being a dynamic resource, under-
goes modifications both quantitatively and quali-
tatively. Sami (1992) demonstrated that leaching
of surfacial salts; ion exchange processes, and the
residential time have caused the hydrogeochem-
ical variations of groundwater in a semiarid sed-
imentary basin in Eastern Cape, South Africa.
The groundwater chemically evolves by the in-
teraction with aquifer minerals or by the inter
mixing among the different groundwater reser-
voirs along flow path in the subsurface (Domenico
1972; Wallick and Toth 1976). The geochemical

processes are responsible for the seasonal and spa-
tial variations in groundwater quality (Matthess
1982). Hence, it is vital to study and under-
stand the different hydrogeochemical characteris-
tics of aquifers in different seasons and geological
terrains. Evaluation of the groundwater chem-
istry and delineation of various hydrogeochemical
processes that are involved in the evolution of
groundwater quality by adopting various graph-
ical methods and interpreting different indices
were attempted by many workers in the recent
past (Elango et al. 2003; Kumar et al. 2006; Singh
et al. 2006; Subbarao 2006; Raju 2007; Rashid
and Izrar 2007; Apadaca et al. 2007; Pophare
and Dewalkar 2007). Pandian and Sankar (2007)
have observed that host rocks are the main
source of dissolved solids in the groundwater of
Viappar river basin, Tamil Nadu by adopting
various methods like Gibbs plots, Kelley’s in-
dices, and chloroalkali indices (CAI). Brijraj and
Kaur (2007) have concluded that the chemical
quality of surface and groundwater of Rawalsar
Lake, Mandi district, Himachal Pradesh was con-
trolled by rock weathering, which supplied most
of the dissolved constituents to the water. Gowd
(2005) and Reddy and Prasad (2005) have stud-
ied and delineated the hydrogeochemistry of the
Peddavanka watershed and the Tadpatri area of
Anantapur district, Andhra Pradesh, India. In the
present study, an attempt has been made to clas-
sify the groundwater based on its ionic strength
and identify various geochemical reactions that
are involved in attaining the present chemical
state. Variations in chemical quality of ground-
water and its evolution processes in different sea-
sons and geological horizons were studied and
delineated to know the hydraulics controlled and
aquifer-material-related groundwater chemistry.
Study area
Anantapur is one of the most economically back-
ward districts of the Andhra Pradesh (AP) State,
India. The district falls in the semiarid tract and
rain shadow region of the state. The rainfall is
meager and erratic, the normal rain fall being
553 mm; hence, the district is declared as drought
prone (Balachendran 2004, unpublished report).
Environ Monit Assess
The study area comprises of 2,200 km2 and ex-
tends from Anantapur town in the south to the
border of Kurnool and Cuddapah districts in the
northeast and east, respectively (Fig. 1). The area
occurs between east latitudes 14◦ 30 –15◦ 30 and
north longitudes 77◦ 45 –78◦ 10 . Agriculture is the
principal occupation of the people and is the
backbone of the rural economy. A majority of
agricultural activity is dependent on groundwater,
as surface water resources are meager. Minor
irrigation projects or tanks are almost defunct
due to perennial low rainfall, and only 3% in
Khariff (monsoon) and 7% in Rabi (winter) of the
gross area sown are irrigated with surface water in
the entire study area through Tunga Badra High
Level Canal. The area irrigated by groundwater,
on the other hand, constitutes 19% in Khariff and
54% in Rabi of the gross area sown (Govt. of
Andhra Pradesh 2004). The groundwater resource
is of prime importance as most of the irrigation
and drinking water requirements are met with it.
The area mostly constitutes a pediplain, char-
acterized by a low-lying flat terrain with gen-
tle slopes and is dotted with dissected pediment
and series of denudational hills. The eastern and
northern parts of the area are prominent with
hill ranges, which strike in NW–SE and E–W
directions. The Pennar and Chitravati rivers with
their tributaries drain the area. The drainage pat-
tern is dendritic, parallel to subparallel, and the
streams are structurally controlled. All the rivers
and streams are ephemeral except Penna.
Geology and hydrogeology
The southwest part of the area is underlain by
gray granite gneiss, schists, massive granites, and
migmatities belonging to the Peninsular Gneissic
Complex of Archaean age, which at places is
traversed by younger intrusives like pink gran-
ites, pegmatites, quartz veins, and basic dykes.
The northern and eastern parts are covered by
meta-sediments belonging to the Cuddapah Super
Group and the Kurnool Group of rocks (Raju
et al. 1979). River alluvium, consisting of fine to
course sand, gravel, silt, and clay, occurs along
the major river courses to the extent of 200 to
500 m width having a thickness of 10 to 15 m, but
Environ Monit Assess

Fig. 1 Geology with sample locations


its distribution is uneven, varying from place to
place (Reddy 2007, unpublished report). Here, the
groundwater occurs in moderately weathered and
fractured granites, meta-sediments under semi-
confined to confined condition, and in alluvium,
it occurs in the phreatic zone. The depth of
weathering is limited to 10–12 m, and the poten-
tial fractures occur between 20 and 60 m. Struc-
tural features like faults, lineaments, joints, and
dyke cuttings, located at different depths down
to 300 m, facilitate groundwater movement and
form potential aquifers in both the granite and the
sedimentary terrain (CGWB 2003, unpublished
report). Depths of water levels are quite deep
in the area; it varies from 15 to 40 m in pre-
monsoon and 6 to 12 m in post-monsoon in the
granitic terrain. In the sedimentary and alluvium
areas, however, they range between 12 and 25 m in
pre-monsoon season and 4–8 m in post-monsoon
season.
Materials and methods
Groundwater samples from the study area were
collected in pre-cleaned 1-L polyethylene bottle
following APHA (1995) method from the hand-
pump-fitted bore wells belonging to Rural Water
Supply Department of AP State Government.
In all 48 in pre-monsoon (June 2005) and 44 in
post-monsoon (November 2005), samples were
collected representing different hydrogeological
environments (Fig. 1). The sampling bottles were
rinsed thoroughly with sampled groundwater. The
water samples from bore wells were collected af-
ter pumping out water for about 10 min to remove
stagnant water from the well. Temperature, pH,
and electrical conductivity (EC) were measured
in the field at the time of sampling. The water
samples were analyzed in the Regional chemical
laboratory of Central Groundwater Board. The
temperature was measured by the normal mercury
thermometer, pH by using the Digital pH meter
of EI make (1997 model), and EC was estimated
by the EC/TDS analyzer CM 183 model (2007) of
ELICO make. The classical methods of analysis
were applied for the estimation of total hardness,
calcium, magnesium, carbonate, bicarbonate, and
chloride. Sodium and potassium were analyzed
Environ Monit Assess
by flame photometry method using CL-345 Flame
photometer of ELICO make. Sulfate was esti-
mated by the turbidity method using the Digital
Nephelo-Turbidity meter 132 model of Systronics
make. Nitrate was analyzed applying the UV-Vis
screen method using UV-visible spectropho-
tometer UV-1201 model of Shimadzu make.
Fluoride was analyzed by the ion selective elect-
rode method using Orion 290A+ model of
Thermoelectron Corporation. The total dissolved
solids (TDS) were estimated by calculation
method after Hem (1991). The obtained results
were tested for accuracy by calculating the Nor-
malized Inorganic Charge Balance (Huh et al.
1998). The analytical precision was such that the
ion charge balance was within ±5% for the major-
ity of the samples. The quality of the analysis was
ensured by standardization using blank, spike, and
duplicate samples.
Result and discussions
Groundwater chemistry: The pH varies from 7.07
to 8.75 in the pre-monsoon and from 6. 80 to
9.40 in the post-monsoon seasons, the mean pH
values indicate that the groundwater is marginally
alkaline in post-monsoon (Table 1). The mean
pH of groundwater from granites is 7.90, and in
the meta-sedimentary rocks, it is 7.86 in alluvium;
the mean pH is 8.24. The EC varied between 622
and 8,320 μS/cm in pre-monsoon and from 490
to 9,500 μS/cm in post-monsoon and the mean
EC reduced by about 50 μS/cm in post-monsoon
and is higher in the sedimentary aquifers among
different geological units. Total hardness of water
is almost static in both the seasons; it is higher in
granites (437 mg/l) than that of sedimentary rocks
(372 mg/l). The mean concentration of other ele-
ments do not vary significantly between two sea-
sons, but K+ has reduced drastically from 98 mg/l
in pre-monsoon to 21 mg/l in post-monsoon so
also NO3− which was 121 mg/l in pre-monsoon
that came down to 75 mg/l in post-monsoon. The
mean Ca2+ content is high in granite samples
being 78 mg/l, and in the sedimentary rocks, it was
only 53 mg/l, whereas the Mg2+ concentration is
similar for both these formation, being 58 mg/l.
The Na+ and K+ are higher in sedimentary rock
Environ Monit Assess

Table 1 Summarized results of the Major element analysis and their ratios
Seasons/ Basic pH EC Cations Anions r1
geological statistics μS/cm TH Ca2+ Mg2+ Na+ K+ CO3 − HCO3 − Cl− SO4 2−
NO3 −
F− Na+ –Cl− /
horizons SO4 2−
mg/l mg/l meq/l
Pre- Mean 7.83 2002 378 57 57 297 98 2.31 438 323 121 121 1.24 −0.95
monsoon Min 7.07 622 100 10 1 40 ND ND 183 14 1 3 0.41 −474.15
Max 8.75 8320 1100 204 228 1404 923 60 952 2255 600 684 2.80 55.95
SD 0.35 1470 243 42 46 282 170 11 189 401 125 150 0.57 95.92
Post- Mean 7.94 1955 374 58 56 270 21 3.68 410 316 110 75 0.99 7.75
monsoon Min 6.80 490 85 8 4 35 1 ND 98 35 7 1 0.03 −7.32
Max 9.40 9500 1550 216 316 1300 422 72 897 2588 600 536 4.81 48.41
SD 0.43 1664 269 45 54 274 74 13 191 454 115 113 0.75 12.37
Granite Mean 7.90 1762 437 78 58 205 26 1.412 396 261 97 115 1.131 5.31
Min 7.07 520 180 18 1 37 ND ND 165 43 24 2 0.22 −2.32
Max 8.96 4920 1520 284 197 759 485 48 952 1021 269 684 2.90 29.07
SD 0.38 973 276 54 49 144 84 8 171 225 62 147 0.592 6.00
Sedimentary Mean 7.86 2289 372 53 58 363 110 3 458 392 156 102 1.13 −2.74
rocks Min 7.25 575 100 10 12 35 ND ND 98 14 1 3 0.38 −474.16
Max 8.75 8320 1100 216 228 1404 923 60 897 1900 600 640 2.80 46.40
SD 0.36 1782 254 42 43 332 180 13 200 466 161 146 0.60 86.96
Alluvium Mean 8.24 914 151 26 21 151 4.71 7 322 98 59 8.29 0.89 4.40
Min 7.69 490 85 12 10 71 2.00 ND 177 35 19 1.00 0.23 4.40
Max 9.40 1160 265 48 55 198 9.00 48 451 149 91 14.00 1.26 6.93
SD 0.55 218 60 13 17 40 2.29 18 102 36 24 4.92 0.35 0.98

r2 Element sum/ratios CAI-1 CAI-2

(K+ + Na+ )– Ca2+ + Na+ /Cl− Ca2+ / Mg2+ / Na+ + SO4 2− + Ca2+ Cl− −Na+ Cl− −Na+ +
− + −
Cl /SO4 2−
Mg 2+ Mg 2+ Ca2+ K HCO3 + Mg / + K+ /
2+ K+ /SO4 2− +
Na+ Cl− HCO3 − +
+ K+ CO3− + NO3 −
meq/l mg/l mg/l meq/l meq/l mg/l meq/l mg/l meq/l meq/l
Pre- Mean 5.51 115 1.31 2.22 2.08 395 9.71 0.52 −1.62 −0.51
monsoon Min −2.70 28 0.28 0.17 0.01 42 3.60 0.03 −15.95 −3.20
Max 91.39 292 6.71 70.48 5.86 1404 21.21 2.50 0.55 0.85
SD 17.69 74 1.29 13.68 1.38 364 4.80 0.59 3.19 0.73
Post- Mean 2.81 113 1.20 1.62 2.62 291 9.01 0.73 0.30 −0.89
monsoon Min −1.28 25 0.46 0.06 1.06 36 3.35 0.06 −0.80 −3.47
Max 30.74 416 2.89 22.48 23.48 1722 23.89 3.31 0.48 0.28
SD 5.00 77 0.70 5.00 5.00 334 4.79 0.71 0.36 1.08
Granite Mean 1.51 136 0.96 3.19 1.82 230 8.51 0.88 −0.54 −0.07
Min −3.80 56 0.31 0.06 0.01 38.6 3.35 0.16 −2.25 −0.45
Max 8.05 481 2.10 70.48 17.19 1244 21.21 2.73 0.53 0.79
SD 2.49 84 0.45 11.93 2.87 212 3.28 0.62 0.71 0.22
Sedemintary Mean 6.70 108 1.39 0.64 2.05 452 10.54 0.42 −1.87 −0.61
Min −1.28 28 0.36 0.20 0.49 36 3.41 0.03 −15.95 −3.20
Max 91.39 352 6.71 2.03 5.12 1421 23.89 2.02 0.27 0.45
SD 16.00 73 1.22 0.38 1.08 343 5.34 0.46 2.94 0.40
Alluvium Mean 3.74 47 1.65 1.16 1.91 156 6.49 0.33 −1.63 −0.61
Min 2.24 25 1.03 0.18 0.41 74 3.90 0.15 −2.32 −0.69
Max 4.86 71 2.11 2.43 5.66 207 8.99 0.45 −0.93 −0.52
SD 1.20 15 0.46 1.08 2.49 23 1.08 0.10 0.58 0.07
CAI-1 chloroalkali indices-1 CAI-2 chloroalkali indices-2, ND not detected
 Environ Monit Assess

aquifers which are 363 and 110 mg/l, respectively,
whereas in granites, the content of these elements
were only 205(Na+ ) and 26 mg/l (K+ ). Sodic hori-
zons occurred predominantly in mid-slope and
are related to (a) fluctuations in water table,
(b) poor lateral drainage and a perched water
table, and (c) the weathering rate of feldspars
(Stocking 2006). The mean NO3 − is highest
(115 mg/l) in the granite samples among three for-
mations (Table 1). The groundwater in alluvium
is less mineralized as all the analyzed parameters
were very less when compared to those in the
other geological horizons. The standard deviation
(SD) was high for EC, TH, Na+ , Cl− for different
category of samples expressing a wide dispersion
of ionic strength from the mean. SD is low for
alluvial samples as the parameters vary in limited
range. The variation in groundwater chemistry
among the three different geological formations
in spite of hydrological continuity proves the in-
fluence of host rock environment on pore water.
The variation in ionic content of water within the
samples of a formation, as established by high
SD for some chemical constituents, could be due
to the differences in mineral makeup in aquifer
material of the geological horizon as each for-
mation contains different sub groups and types
of rocks which have contributed to the chemistry
of percolating waters. The surfaces of most ig-
neous clasts (granites and volcanics) are usually
highly altered to micaceous (“illitic”), chloritic,
and vermiculitic clays. Carbonates, such as calcite,
dolomite, and siderite, are present, particularly in
the more shallow formations. The properties of
the sediments have a clear impact on the evolution
of groundwater chemistry (Randall et al. 1996).
Ionic dominance The ionic dominance (meq/l)
pattern is in the order of Na+ > Cl− ≥ SO4 2− >
HCO3 − > Mg2+ > Ca2+ . Na+ and Cl− were in
high concentration among cations and anions, re-
spectively, in the groundwater of the study area.
The solubility limit of sodium salts can be ex-
ceeded, particularly in the inland drainage basins.
Hence, it can lead to precipitation of sodium
salts, e.g., sodium carbonate, sodium sulfate, and
sodium nitrates (Matthess 1982). No significant
seasonal variation was noticed in the ionic dom-
inance pattern. The groundwater in different ge-
ological settings showed different ionic concen-
trations. In sedimentary rock samples, K+ was in
higher concentration than that of Ca2+ whereas
in granite and alluvium, Ca2+ and Mg2+ were in
higher concentration than K+ (Table 2). Among
anions, SO4 2− replaces NO3 − in the groundwater
of sedimentary and alluvial formations when com-
pared to granites. The ionic dominance pattern
was distinct in the groundwater of alluvium as
HCO3 − dominated over Cl− when compared to
other rock types and seasons. The ionic domi-
nance pattern for the groundwater resembled that
of the leachable ions from the soils suggesting
of a lithogenic origin of minerals in groundwater
and inputs from anthropogenic sources (Kumar
et al. 2006). Variations in ionic dominance in pre-
and post-monsoon seasons could be attributed to
evapotranspiration effect and the accumulation of
certain ions in water (Reddy et al. 2008). Dilution
of NO3 − over SO4 2− in post-monsoon could be
due to fresh influx of recharge during monsoon.
Difference in the ionic dominance pattern in the
groundwater of different geological units is un-
derstandable as it is closely related to geological

Table 2 Ionic (meq/l) dominance in different seasons and terrains

Seasons/terrains Cations Anions Total ionic dominance
−
Pre-monsoon Na+ > Mg2+ Cl− = SO2− 4 Na+ > Cl− = SO2−
4 > HCO3
> Ca2+ > K+ > HCO− 3 > NO3
−
> Mg > Ca = NO3 > K+
2+ 2+ −
−
Post-monsoon Na+ > Mg2+ −
Cl = SO4 2−
Na+ > Cl− = SO2−
4 > HCO3
> Ca2+ > K+ > HCO− 3 > NO3
−
> Mg2+ > Ca2+ > NO− 3 > K +

Granite Na+ > Mg2+ Cl− > HCO3 − Na+ > Cl− > HCO− 3 > Mg 2+

> Ca2+ > K+ > NO− 3 > SO4

2−
> Ca2+ > NO− 2−
3 > SO4 > K
+
− −
Sedimentary rocks Na+ > Mg2+ −
Cl > HCO3 + −
Na > Cl > HCO3 > Mg = 2+
− 2+ > NO −
> K+ > Ca2+ > SO2−4 > NO3 SO2− +
4 > K > Ca 3
Alluvuim Na+ > Mg2+ HCO− 3 > Cl − Na+ > HCO3 − > Cl− > Mg2+
−
> Ca2+ > K+ > SO2−4 > NO3 > Ca2+ = SO2− −
4 > NO3 > K
+
Environ Monit Assess

stratification (Kumar et al. 2006). Higher content Schoeller scheme The select major ions (meq/l)
of Ca2+ and Mg2+ over K+ in the groundwater of data when plotted in Schoeller (1965) scheme
granites and post-monsoon could be due to their have indicated that there was no distinct differ-
mineralogical origin in the soils. During monsoon ence in the water quality between the two seasons
season, water percolates down to aquifer through (Fig. 2a, b). Na+ , the dominant ion, was almost
soil and the weathered mantle gaining Ca2+ and constant in its content between pre- and post-
Mg2+ . Dominance of NO3 − in granites over SO4 2− monsoons. Ca2+ and Cl− concentrations have in-
when compared with sedimentary rock aquifers creased in post-monsoon whereas HCO3 − and
could be due to higher hydraulic conductivity,
secondary porosity, and permeability in granites
than in sedimentary rocks (Reddy et al. 2009). a Premonsoon
1000
Classification of groundwater The groundwater
of different seasons and geological horizons are C
classified depending upon their ionic strength of o 100
select anions. Soltan (1998) has proposed cate- n
gorization of groundwater based on the meq/l c
content of Cl− , SO4 2− , and HCO3 − . The water e m 10
is Normal Chloride type if Cl− is <15 meq/l, n e
t q
Normal SulFate type if SO4 2− is <6 meq/l, and
r /
Normal Bicarbonate type if HCO3 − varies be- a l 1
tween 2 and 7 meq/l. Distribution of groundwater t
samples based on the Soltan’s classification has i
indicated that a majority of the samples in both o 0.1

seasons and different geological settings are of n

Normal Sulfate type, followed by Normal Chlo-
0.01
rite type and Normal Bicarbonate type (Table 3). Mg Ca Na+K Cl SO4 HCO3
Seasonal variations in concentrations of these el- Chemical Paramaters
ements were not significant, but groundwater in b
the three different formations show a remarkable Postmonsoon
variation especially with respect to SO4 2− and 1000

HCO3 − content which could be due to different

C
mineralogical make up of the country rocks. The
o 100
type and concentration of salts in natural waters n
depend on the geology, environment, and move- c
ment of water (Raghunath 1982; Gopinath and e m 10
Seralathan 2006). n e
t q
r /
1
a l
Table 3 Classification of groundwater samples
t
Seasons/ Cl− type SO4 2− type HCO−
3 type i
terrains (<15 meq/l) (<6 meq/l) (2–7 meq/l) o 0.1
% of samples n
Pre-mosoon 83 90 56
Post-monsoon 86 91 48 0.01
Mg Ca Na+K Cl SO4 HCO3
Granite 82 100 60
Sedimentary 78 78 43 Chemical Parameters
rocks
Fig. 2 a Scholler plot for pre-monsoon; b Scholler plot for
Alluvuim 100 100 71 post-monsoon
 Environ Monit Assess

Table 4 Types of groundwater as per Soltan classification

SO4 2− concentrations were steady in both the
seasons. The water quality type was similar within Seasons/terrains r1 < 1 r1 > 1 r2 < 1 r2 > 1
the season which can be classified as Na+ –Ca2+ – Type of GW> Na+ – Na+ – Deep Shallow
SO2− HCO− meteoric meteoric
Cl− type with few samples having low Na+ can 4 3
type type
be designated as Ca2+ –Cl− HCO3 − type which
% of samples
indicated that the sources were closer to recharge
Pre-monsoon 27 73 25 75
areas (Kumar et al. 2006).
Post-monsoon 23 77 45 55
Granite 18 82 49 51
Base exchange indices The Base Exchange in- Sedimentary 24 76 24 76
dices (Soltan 1999) determined by using the fol- rocks
lowing Eq. 1 which could be applied for the Alluvuim 14 86 0 100
further classification of groundwater.
  
r1 = Na+ − Cl− SO42− meq l (1)
percentage of samples belonging to Na+ –HCO3 −
The groundwater can be grouped as Na+ –HCO3 −
type had increased marginally in post-monsoon
type if r1 > 1 and Na+ –SO4 2− type with r1 <
when compared to pre-monsoon. Whereas in sedi-
1. Majority of samples in both the seasons and
mentary aquifers, they have decreased when com-
in all the formations were of Na+ –HCO3 − type
pared with those of granites and alluvium.
(Fig. 3a, b) and variations in the groundwater type
The groundwater source can be determined
with reference to r1 were minor in two seasons
based on meteoric genesis index, which is com-
and different geological formations (Table 4). The
puted applying Soltan (1999) Eq. 2.
    
r2 = K+ + Na+ − Cl− SO2−
4 meq l (2)

a Premonsoon Postmonsoon The value of r2 < 1 indicates that the ground-

25
water is of deep meteoric percolation type and >1
20 express the water is of shallow meteoric percola-
15 tion type. The groundwater in different seasons
-Index

10
and formations of the area was of mixed type,
but in general, more than half of the analyzed
r1

5
samples showed that it was of shallow meteoric
0
water percolation type (Fig. 4a, b). Significant sea-
-5 sonal and temporal (geological) variations were
0 10 20 30 40 50 60
Sample Nos
noticed within this category. The groundwater in
post-monsoon was more (45%) of deep meteoric
b Granites Sedimentary rocks Alluvium
percolation type than that of pre-monsoon (25%),
20 and the same could also be seen between those
of granite (49%) and sedimentary aquifer (24%);
15
evidently, all of alluvium water is of shallow me-
-Index

10 teoric percolation type (Table 4). Low rainfall

conditions leading to continuous exploitation of
5
r1

groundwater resulting in steep fall in water levels

0 might have led to more of deep meteoric per-
-5 colation type of water in post-monsoon period.
0 10 20 30 40 Potential deep fracture system in granites could
Sample Nos
be one of the reasons for more disparity in the
Fig. 3 a Base Exchange Index (r1) plot; b Base Exchange groundwater type between granite and sedimen-
Index (r1) plot tary rocks (Reddy et al. 2008).
Environ Monit Assess

a Premonsoon Postmonsoon ing to different water types (Table 5, Fig. 5b), but
25
for the variations in the number of samples, the
20 groundwater in general was of Na+ –Cl− , Na+ –
15 HCO3 − , Ca2+ –Mg2+ –HCO3 − , and Ca2+ –Mg2+ –
-Index

Cl− types in a decreasing order. Few samples

10
(one in each) fall in two or three sub-blocks of
r2

5 the diagram. It can be inferred from plots that

0 the groundwater was of mixed type with multiple
-5
processes involved in its evolution. The modified
0 10 20 30 40 50 60 piper plots further strengthen that the mineralogy
Sample Nos of the aquifer material played an important role
in determining the water chemistry. The plots
b Granites Sedimentary rocks Alluvium
also suggest that among cations Na+ and anions
20
Cl− and/or HCO3 − dominate the ionic concen-
tration in groundwater. Na+ was the dominat-
15

10 ing cation, and its concentration was relatively

-Index

5 higher in pre-monsoon season, which may be

attributed to negative index of Base Exchange
r2

0
-5
-10
0 10 20
Sample Nos
Fig. 4 a Meteoric genesis Index (r2) plot; b Meteoric
genesis Index (r2) plot
Modified piper diagram The groundwater is fur-
ther evaluated to determine its facies by plotting
the percentages of select chemical constituents
in Modified Piper diagram (Chadha 1999). The
plots for pre- and post-monsoon season indicated
scattered distribution with minor or negligible var-
iations in their chemical characteristics between
two seasons (Table 5, Fig. 5a). The groundwater
samples of different geological terrains show sig-
nificant changes in percentage of samples belong-
(Pophare and Dewalkar 2007). Na+ and Ca2+
are in transitional state with Na+ replacing Ca2+
and HCO3 − Cl− due to physiochemical changes in
30 40
the aquifer and the water–rock interactions. Due
to cation exchange process, Na+ –HCO3 − , Ca2+ –
Cl− , and Na+ –SO4 2− , the groundwater types
may form according to cation exchange capac-
ity of the matrix; this is a vice versa reaction
(Elango and Kannan 2007). The mechanism is
an exchange of calcium and magnesium ions in
aqueous solution with sodium ions on the clay
minerals of the shales. This cationic exchange is
the principal source of sodium in the groundwater.
Aquifer parameters seem to play minimum role
in the determination of the water facies as no
seasonal changes were evident. Change in stor-
age of aquifer between seasons did not influence
the major geochemical makeup of groundwater
quality.

Table 5 Types of Type of GW> Na+ –Cl− Na+ – Ca2+ –Mg2+ – Ca2+ –Mg2+ – Other
groundwater as per
HCO− 3 HCO− 3 Cl− sub-blocks
Modified Piper diagram
Sub-Div. No.> 7 8 5 6 1 to 4
Seasons/terrains % of samples
Pre-mosoon 40 32 12 10 2+2+2
Post-monsoon 32 32 18 14 2+2
Granite 23 26 20 26 3+3
Sedimentary rocks 43 30 14 4 3+3+3
Alluvuim Nil 60 Nil Nil 20 + 20
 Environ Monit Assess

a Premonsoon Postmonsoon as proven in the plots of Na+ /Cl− versus EC where

100 the samples were plotted in a horizontal line
parallel to x-axis (Fig. 6a, b). Na+ /Cl− ratio would
not alter when no mineral species is precipitated
50
(CO3+HCO)-(Cl+SO4) %

if evaporation process is dominant (Jankowski

and Acworth 1997). Salinization and sodification
0 are often associated with irrigated areas where
-100 -50 0 50 100 low rainfall, high evapotranspiration rates or soil
textural characteristics impede the washing of
-50 salts out of the soil, which subsequently build up
in the surface layers (SoCo 2009). Na+ /Cl− molar
ratio will be 1 if halite dissolution is responsible
-100 for sodium dominance in groundwater and
(Ca+Mg)-(Na+K) %
>1 if Na+ is released from silicate weathering
process (Meybeck 1987). The Na+ /Cl− molar ratio
b Granites Sedimentary rocks Alluvium
(Fig. 7a, b; Table 6) is >1 in many samples of
100

50
(CO3+HCO)-(Cl+SO4) %

a Premonsoon Postmonsoon
8
0
7
-100 -50 0 50 100
6
Na/Cl ratio (mg/l)

-50 5

3
-100
(Ca+Mg)-(Na+K) % 2

Fig. 5 a Modified Piper Diagram; b Modified Piper 1

Diagram 0
0 2000 4000 6000 8000 10000
EC ( µ S/cm )

Hydrogeochemical evaluation Concentration b Granites Sedimentary rocks Alluvium

8
of different major elements and their inter-
relationship was studied to understand and 7

illustrate the hydrogeochemical processes that 6

Na/Cl ratio (mg/l)

were involved in aquifer domain during the 5

evolution of different groundwater facies. Major 4
ion chemistry of groundwater provides basis to
3
investigate the weathering reactions in the basin
(Brijraj and Kaur 2007). High sodium content 2

among cations in the groundwater for different 1

seasons and geological formations (Table 1) 0
could be due to weathering of silicate rocks 0 2000 4000 6000 8000 10000
EC (µ S/cm)
such as granite gneisses, schists, shales, slates,
and phyllites, which was further enhanced by Fig. 6 a Plot of Na+ /Cl− ratio versus EC; b Plot of
evaporation and/or evapotranspiration processes Na+ /Cl− ratio versus EC
Environ Monit Assess

Premonsoon Postmonsoon water can only evolve to brine rich in NaCl if

a
80 it encounters highly soluble chloride minerals,
70 typically associated with evaporative deposits
60 (evaporates, Gosselin et al. 2003). Different
Na (meq/l)

50 geochemical processes are involved in enrichment

40 of an element in different environments. Shallow
30 water levels in post-monsoon resulted in more salt
20 dissolution from the soil and weathered mantle
10 leading to enhancement of Cl− and reduction of
0 Na+ in exchange (Kumar et al. 2006). The Na+
0 10 20 30 40 50 60 70 80
vs Cl− plot indicates a majority of samples fall
Cl (meq/l)
along or above the equiline, reflecting silicate
weathering. Few samples, occupying along and
b Granites Sedimentary rocks Alluvium
below equiline, could be due to the fact that
70
halite dissolution was responsible for high Cl− as
60
the low annual normal rainfall (<600 mm) was
50 making it possible for availability of free halite for
Na (meq/l)

40 dissolution in the soil zone (Elango and Kannan

30
20
10
0
0 10 20 30 40
Cl (meq/l)
Fig. 7 a Na+ versus Cl− plot; b Na+ versus Cl− plot
pre-monsoon season, sedimentary and alluvium
terrains indicating that silicate weathering was
the primary process responsible for the release
of Na+ into the groundwater (Stallard and
Edmond 1983; Pophare and Dewalkar 2007). In
post-monsoon and granite terrain, the Na+ /Cl−
ratio is <1 in most of the groundwater samples
where the ion exchange and/or evaporation
were/was dominant process resulting in the
addition of Cl− in the groundwater. Ground-
2007).
The study of Ca2+ /Mg2+ ratio also revealed
that the dissolution of silicate minerals was
one of the prime processes involved in at-
50 60 70 taining the present chemical makeup of the
groundwater. The Ca2+ /Mg2+ ratio of 1 indicated
dissolution of dolomite and of >2 reflected an
effect of silicate minerals on the groundwater
chemistry; it also suggested calcite dissolution for
Ca2+ –Mg2+ concentration in groundwater (May
and Loucks 1995). Majority of the samples in
both the seasons and different geological terrains
have Ca2+ /Mg2+ ratio between 1 and <2, indi-
cating dolomite dissolution responsible for Ca2+ –
Mg2+ contribution (Fig. 8a, b). The groundwater
in granite and alluvium has 17% and 28% of
samples, respectively, with >2 Ca2+ /Mg2+ ratio
where calcite dissolution and effect of silicate
minerals were evident for the Ca2+ –Mg2+ con-
tent (Table 6). The scatter diagram of Ca2+ +

Table 6 Hydrogeo- Seasons/terrains Na+ /Cl− mg/l Ca2+ /Mg2+ meq/l Mg2+ /Ca2+ meq/l
chemical evaluation of
Groundwater (meq/l) >1 <1 1 to 2 >2 <1 >1
% of samples
Pre-monsoon 51 82 8 10 21 79
Post-monsoon 45 76 11 13 25 75
Granite 34 62 21 17 41 59
Sedimentary rocks 58 89 8 3 10 90
Alluvuim 100 58 14 28 43 57
 Environ Monit Assess

a3 Premonsoon Postmonsoon
a Premonsoon Postmonsoon
30
Ca/Mg (molar ratio)
25
2

Ca+Mg (meq/l)
20

15
1
10

0 5
0 20 40 60
0
Samples Numbers
0 10 20 30
SO4+HCO3 (meq/l)
b3 Granites Sedimentary rocks Alluvium
b 25 Granites Sedimentary rocks Alluvium
Ca/Mg (molar ratio)

20

2 15

Ca+Mg
10

5
1
0
0 5 10 15 20 25
SO4+HCO3
0
0 10 20 30 40
Samples Numbers Fig. 9 a Plot of Ca2+ + Mg2+ and SO4 + HCO3 ; b Plot of
Ca2+ + Mg2+ and SO4 + HCO3
Fig. 8 a Plot of Ca2+ /Mg2+ molar ratio; b plot of
Ca2+ /Mg2+ molar ratio

Mg2+ vs HCO3 − + SO4 2− (Fig. 9a, b) shows

that majority samples in both the seasons and
different geological terrain fall below the equi-
line, indicating that silicate weathering was the
primary process involved in the evolution of
groundwater (Datta and Tyagi 1996). If bicar-
bonate and sulfate are dominating than calcium
and magnesium, it reflects that silicate weath-
ering was dominating and, therefore, was re-
sponsible for the increase in the concentra-
tion of HCO3 − in groundwater (Elango et al.
2003; Elango and Kannan 2007). The plot of
Ca2+ + Mg2+ against HCO3 − + SO4 2− further
proves the influence of dolomite dissolution
on Ca2+ –Mg2+ contribution in the groundwater
(Fig. 9a, b). The Ca2+ and Mg2+ could be traced
to the dissolution of carbonates in the aquifer
materials and also from the weathering of the
accessory pyroxenes and amphiboles (Sami 1992).
If the points are below the median line in the
plot, ion exchange was the active reaction lead-
ing to SO4 2− HCO3 − accumulation in ground-
water (Cerling et al. 1989; Fisher and Mulican
1997). In both the plots of pre–post-monsoon
(Fig. 9a) and granite-sedimentary-alluvium ter-
rain (Fig. 9b), a majority of samples (90%) oc-
cur below the median line and close to x-axis,
indicating that ion exchange was responsible for
the higher HCO3 − SO4 2− concentration in ground-
water. Few samples (10%) falling above median
reflect reverse ion exchange for the dominance of
Ca2+ + Mg2+ over SO4 2− HCO3 − , which was more
conspicuous in the groundwater samples of gran-
ite and post-monsoon season. Na+ vs Ca2+ scatter
plot (Fig. 10a, b) shows that Na+ was dominating
over Ca2+ , which indicates that Ca2+ /Na+ ion ex-
change process had led to increase in Na+ content
in groundwater. The dominant cation in Gabriola
groundwater is calcium (Ca++), which is gradually
replaced at depth by sodium (Na+ ) released from
sodium-rich feldspar (albite) as it weathers (Doe
and Windecker 2005). Smectitic clays with high
amounts of exchangeable sodium are particularly
likely to disperse into groundwater if the ionic
strength of the pore water substantially decreases
(King and Olsen 1999). The Na+ vs HCO3 − plot
Environ Monit Assess

a Premonsoon Postmonsoon the reduction of Na+ in the groundwater. Sulfate

70 vs chloride scatter plot (Fig. 13a, b) suggests low
60 sulfate content in the groundwater, which could be
50 due to reduction process (Datta and Tyagi 1996;
Ca (meq/l)

Lavitt et al. 1997). Lack of natural sources for

40
sulfate in aquifer material could also be one of the
30 reasons for low SO4 2− .
20
10 Gibbs plots The chemical reactions involved in
the evolution of groundwater chemistry were de-
0
0 10 20 30 40 50 60 70 pendent on the aquifer material or the country
Na (meq/l) rock mineralogy with which the groundwater was
associated. The chemical composition of ground-
b Granites Sedimentary rocks Alluvium water implies rock–water interaction and the
70 chemical process involved; thus, the groundwater
60 chemistry can be used to identify these processes
(Elango and Kannan 2007). Gibbs (1970) plots,
50
in which TDS vs Na+ /(Na+ + Ca2+ ) for cations
Ca (meq/l)

40 and TDS vs Cl− /(Cl− + HCO3 − ) for anion were

plotted to illustrate the groundwater evolution
30

20

10 a Premonsoon Postmonsoon
70
0 60
0 10 20 30 40 50 60 70
50
HCO 3 (meq/l)

Na (meq/l)
40
Fig. 10 a Na+ versus Ca2+ plot; b Na+ versus Ca2+ plot
30
20
−
(Fig. 11a, b) further proved that HCO3 was the 10
resultant of silicate weathering (Eq. 3). 0
0 10 20 30 40 50 60 70
2NaAlSi3 O8 + 2H2 CO3 + 9H2 O> Na (meq/l)
Albite

<Al2 SiO5 (HO)4 + 2Na+ + 4H4 SiO4 +2HCO3 b Granites Sedimentary rocks Alluvium
Kaolinite (Silicate weathering).
70
60
(3)
50
HCO3 (meq/l)

The cation contribution to groundwater by sili- 40

cate weathering can also be assessed by the (Na+ )
30
versus total cation index (Stallard and Edmond
1983; Sarin et al. 1989). The plot for the aquifers 20
of two seasons and three different formations 10
(Fig. 12a, b) shows that samples fall along the 0
equiline suggesting that the cations in groundwa- 0 10 20 30 40 50 60 70
Na (meq/l)
ter might have been derived from silicate weath-
ering. Few points falling below the equiline could Fig. 11 a Na+ versus HCO3 − plot; b Na+ versus HCO3 −
be due to Ca2+ /Na+ exchange process resulting in plot
 Environ Monit Assess

a Premonsoon Postmonsoon anions (CAI-2). It is imperative to understand

110
100
the modifications in water chemistry during its
90 movement and residency time for better evalua-
Cations (meq/l)

80 tion of the hydrochemistry of any area more so

70
when different geological formation are involved
60
50 in a water shed or river basin (Johnson 1979;
40 Sastry 1994). CAI-1 [Cl− − (Na+ + K+ )]Cl− and
30 CAI-2 [Cl− − (Na+ + K+ )/(SO4 2− + HCO3 − +
20
10
CO3 − + NO− 3 )], developed by Schoeller (1967),
0 relate the ion exchange process between ground-
0 10 20 30 40 50 60 70 80 90 100 110 water and aquifer material. The CAI-1 and CAI-
Na+K (meq/l) 2 are negative in a majority (77% to 92%) of
the samples indicating the ion exchange be-
b Granites Sedimentary rocks Alluvium tween Na+ –K+ in water and Ca2+ –Mg2+ in rocks
100 (McIntosh and Walter 2006). The groundwater
90 in granite has positive CAI value for 23% of
80
the samples, where instead of Base Exchange,
Cations (meq/l)

70
60
cation–anion exchange reaction has taken place
50 (Tables 1 and 7). Base-exchange process is sim-
40 ilar in pre- and post-monsoon seasons, but in
30
20
10
0 a Premonsoon Postmonsoon
0 10 20 30 40 50 60 70 80 90 100 80
Na+K (meq/l) 70
Fig. 12 a Na+ + K+
versus total cations plot; b Na+ + K+ 60
Cl (meq/l)

versus total cations plot 50

40
30

process and the influence of host rock on ground- 20

water chemistry indicated that the samples, by and 10
large, occupied the rock dominance to evapora- 0
0 5 10 15
tion dominance fields (Fig. 14a–d). In accordance
SO4 (meq/l)
with the earlier conclusions, the water–rock inter-
action and aquifer material played major role in
the evolution of water chemistry, which was partly b Granites Sedimentary rocks Alluvium
70
influenced by evaporation. Geological location is
60
one of the most important factors affecting the
groundwater quality (Beck et al. 1985). In pre- 50
Cl (meq/l)

monsoon, evaporation and water–rock interaction 40

played an equally active role in deciding the hy- 30
drochemistry as the samples fall in the transition
20
zone.
10

Chloroalkali indices The role of aquifer ma- 0

0 5 10 15
terial in the evolution of groundwater chem- SO4 (meq/l)
ical composition can be further probed by
determining the CAI for cations (CAI-1) and for Fig. 13 a SO4 –2 versus Cl− plot; b SO4 –2 versus Cl− plot
Environ Monit Assess

a c
10000 10000 Granites Sedimentary rocks Alluvium

1000 1000
TDS (meq/l)

TDS (meq/l)
100 Rock-dominance 100
Rock-dominance

10 10

Premonsoon Postmonsoon

1 1
0 5 10 15 0 5 10 15 20
Na+K:(Na+K+Ca) Na+K:(Na+K+Ca)
b 10000 d
10000 Granites Sedimentary rocks Alluvium

1000
1000
TDS (meq/l)

TDS (meq/l)

100 Rock-dominance 100

Rock-dominance

10 10

Premonsoon Postmonsoon

1 1
0 5 10 15 20 0 5 10 15 20
Cl:(Cl+HCO3) Cl:(Cl+HCO3)

Fig. 14 a–d Gibbs plots (four numbers)

relation to host rock environment, significant Table 7 Classification of water as per Chloroalkali Index
variation was noticed in groundwater occur- Seasons/terrains CAI-1 CAI-2
ring in different rock types. Seasonal deviations + − + −
were found in the chloroalkaline indices of the % of samples
Peddavanka watershed (Gowd 2005). Same set Pre-monsoon 13 87 13 87
of samples in two seasons and three different Post-monsoon 16 84 16 84
formations have either positive or negative CAI- Granite 23 77 23 77
1 and CAI-2 values indicating a uniform reaction Sedimentary rocks 8 92 8 92
pattern with Na+ + K+ − Cl− and other anions. Alluvuim 0 100 0 0

Conclusions
The groundwater in Penna–Chitrvati river sub-
basins exhibited marginal variations in its chem-
ical parameters between pre- and post-monsoon,
but distinct change in water chemistry was no-
ticed in different hydrogeological environments.
Na+ among cations and Cl− among anions are
dominant ions in the groundwater; there was no
seasonal change in ionic dominance, but SO4 2−
dominates NO3 − in sedimentary rocks. High
sodium content could be due to the weather-
ing of silicate rocks which was further enhanced
by evapotranspiration, whereas ion exchange
and/or evaporation were dominant process re-
sulting in the addition of Cl− in groundwater.
Dolomite dissolution might have been responsi-
ble for Ca2+ –Mg2+ contribution and ion exchange
process for higher SO4 2− –HCO3 − content in the
groundwater. The groundwater is of Na+ –Cl− ,
Na+ –HCO3 − , Ca2+ –Mg2+ –HCO3 − , and Ca2+ –
Mg2+ –Cl− types, and the Base Exchange indices
also indicated that majority of samples in both
the seasons and all the formations were of Na+ –
HCO3 − type. The groundwater in different sea-
sons and in different geological environs of the
area was of mixed type, but in general, more than
half of samples showed that it is of shallow mete-
oric water percolation type. Significant variations
in hydrochemistry of different rock types are re-
lated to host rock environment. The groundwater
chemistry is influenced by water–rock interaction
and aquifer material mineralogy, where as the
aquifer hydraulics play limited role in hydrogeo-
chemical processes.
Acknowledgements The authors wish to place on the
record the help rendered by Prof. V. Madhavan in prepa-
ration of the Paper and carrying out many corrections in a
short span time with lot of interest.
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