Chin.J.Geochem.

(2011)30:490495
DOI: 10.1007/s11631-011-0533-3

A study on the mixing proportion in groundwater

samples by using Piper diagram and Phreeqc
model
Karmegam U.1, Chidambaram S.1, Prasanna M.V.2*, Sasidhar P.3, Manikandan S.1, Johnsonbabu G.1, Dheivanayaki
V.1, Paramaguru P.1, Manivannan R.1, Srinivasamoorthy K.4, and Anandhan P1
1
Department of Earth Sciences Annamalai University, Annamalai Nagar-608002
2
School of Engineering and Science, Department of Applied Geology, Curtin University, Sarawak Malaysia, CDT 250, 98009 Miri Sarawak, Malaysia
3
Safety Research Institute, Atomic Energy Regulatory Board, Indra Gandhi Center for Atomic Research, Kalpakkam-603102, India
4
Department of Earth Sciences, School of Physical, Chemical and Applied Sciences, Pondicherry University, Puducherry, India
* Corresponding author, E-mail: geoprasanna@gmail.com

Received June 29, 2010; accepted July 20, 2010

Science Press and Institute of Geochemistry, CAS and Springer-Verlag Berlin Heidelberg 2011

Abstract Piper (1944) diagram has been the basis for several important interpretations of the hydrogeochemical
data. As seen in this diagram, most natural waters contain relatively few dissolved constituents, with cations (metals
or bases) and anions (acid radicles) in chemical equilibrium with one another. Apart from the facies representation,
the composition of the mixed sample can be identified in terms of the composition of the parental solution. To bring
out this advantage of the Piper diagram, a study was conducted in the Kalpakkam region of Tamilnadu, South India.
By taking the geology and water table into consideration, two sample locations were selected as parent solution and
third one as the mixture sample. All three samples were analyzed for calcium (Ca), magnesium (Mg), sodium (Na),
potassium (K), chloride (Cl), sulphate (SO4) and phosphate (PO4) by Ion Chromatograph (Metrohm IC 861). HCO3
was determined by volumetric titration. The Piper diagram shows that parent solutions clustered towards
Na-Mg-Ca-HCO3-Cl and Na-HCO3 facies, and the mixing sample belongs to Na-Mg-HCO3 facies. Phreeqc interac-
tive (Ver 2.8) along with the original composition of the mixture sample was used to correlate the mixing proportion
identified by the Piper diagram.

Key words hydrogeochemical mixing; groundwater; Piper diagram; Phreeqc; equilibrium

1 Introduction and residence time of water (Cruz and Amaral, 2004).

The chief function of the Piper diagram is to
identify the facies of groundwater; it also can help us
to understand several geochemical processes along the
flow path of ground water. This diagram is also used
to classify the water types (Wen et al., 2005), which
are generally distinct zones that cation and anion con-
centrations are described within the defined composi-
tion categories. General distribution of thermal waters
is shown on a Piper diagram (Piper, 1953).
Mg-bearing waters have very high (Na++K+) contents
and high carbonate/sulfate ratios and carbonate-sulfate
waters have very high carbonate ratios. In most of
these waters, alkali earth elements (Ca2++Mg2+) are
higher than alkali elements (Na++K+) and weak acids
(CO3+HCO3) are higher than strong acids (Cl-+SO42-).
The chemical composition of the springs (Barut et al.,
2004) in the study area is affected by rainfall chemis-
try, climate, rock type, rock division, human activities
Similar waters are clustered in clearly defined areas,
indicating water-mixing phenomena, precipitation and
dissolution (Helena, 1998). There is no obvious
change in the chemical composition of spring water.
The water type remains as normal earth alkaline be-
fore and after recharge. The hydrochemical change in
relation to land-use in Seoul, South Korea, appears
predominantly in anion distribution, especially in Cl,
NO3, and possibly SO4. The distribution of these three
anion species is considered to reflect the recharge of
diverse pollutants directly related to land-use charac-
teristics (Byoung-Young Choi et al., 2005). Garrels
and Mackenzie (1967) pointed out that meteoric water
dissolving Na from Na-bearing silicates would pro-
duce NaHCO3 water type. Therefore, albite dissolu-
tion would also probably have produced the NaHCO3
type. The Na-Cl or Na-HCO3-Cl water type has low
conductivity, suggesting a meteoric origin. Boreholes
and mine drainage samples plot close to the top corner

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Chin.J.Geochem.(2011)30:490495 491

of the diamond shape and towards the SO4 apex in the made up of charnockites, and is overlain by recent
anion field while in the cation field, the samples plot alluvium. The depth of hard rock varies from 12.9 to
almost in the middle along the Ca, Mg axis, indicating 46.0 m below the ground surface (Singh et al., 2004;
that this water type evolved from pyrite or arsenopy- Singh and Saxena, 2004). The bedrock is thin on the
rite oxidation (Benony et al., 2008). The diagram was northern and western sides and thick in the central
used by Srinivasamoorthy (2008) to discuss the varia- region. The weathered/fractured charnockite and allu-
tion facies in hard rock geochemistry. Similar studies vium form the major aquifer system. The alluvium is
were carried out by Sukhija et al. (1998), much thicker on the southern and eastern sides, and
Chidambaram et al. (2008), and Prasanna et al. (2010). lenses of clays were encountered in alluvial forma-
Apart from all these, Piper has also an advantage of tions. Sand formations vary from 3 to 12 m in thick-
identifying the mixing proportion of two water sam- ness and constitute a shallow unconfined aquifer. The
ples. Hence, an attempt has been made in this paper to rock massif consists of quartz, feldspar, biotite and
bring out the significance of this diagram in identify- pyroxene. Fractures in the charnockite rock massif
ing the mixing proportion of two water samples. This consist of fracture filling materials, which are green-
has been cross-checked by the mixing proportion ob- ish/blackish-green in colour and are predominantly
tained by USGS Software, Pheeqci (Ver 2.8) with the composed of clay minerals such as biotite, sericite and
original sample. chlorite, altered feldspar and quartz. These minerals
are resistant to weathering. Hence, the rates of reac-
2 Study area tion and transfer of solutes into groundwater are low.
Based on the borehole lithology and rock quality des-
The area proposed for the study extends from ignation (RQD), the charnockite rock massif, to a
Mahabalipuram in the north to Kuvathur in the south great extent, is classified as being excellent and
of Pondicherry State, Southern India. The study area good (Arumugham, 1994).
falls in between the geographical coordinates, 1225'
to 1237' N latitude and 8000' to 8012' E longitude
(Fig. 1). The river Palar with its tributaries flows into
the sea along the region. The study area is well known
due to the presence of the premier organization, IG-
CAR at Kalpakkam. The coastal region is entirely
composed of alluvium, which helps us with easy infil-
tration of the surface water. Geomorphic features such
as dunes and beach ridges are found along the coastal
region. Apart from its importance as a coastal region,
it is also significant to note that the natural calamities
like cyclones are frequently disturbing the normal
ecosystem. This region has been recently affected by
frequent rainfall due to the depression in the Bay of
Bengal. The aquifer behavior and its response to
Fig. 1. Map showing the study area, geological background and sam-
natural calamities in this region will help us to deci-
ple locations.
pher this sensitive region and to identify the region for
natural/artificial recharge. The average annual rainfall
in the study area is 1237 mm. The study area is com-
posed of two contracting rock types: alluvial in the
east and hard rock in the west. The water table in allu-
vial formation is shallow and becomes deeper in the
hard rock. The water table diagram (Fig. 2) shows that
there is a wide range in depth of water table from 1 to
17 m below the ground level (mbgl).

3 Geological characteristics

Topography is slightly undulating with sand bars

and depressions. The regional gradient is towards the
eastern side. The altitude varies between less than 1 to
13 m (above mean sea level). Geologically, the Ar- Fig. 2. Map showing the water level contour and groundwater flow
chaean basement lies at the bottom (Fig. 1), which is direction.
492
4 Methodology
Groundwater samples were collected systemati-
cally along northern coastal tract of Kalpakkam, South
India, using clear acid washed polythene bottles. Sam-
pling was carried out during February 2008 and
analysis was done using standard procedures (APHA,
1998). Parameters such as temperature and pH were
measured in the field. Electrical conductivity and total
dissolved solids were measured in the laboratory. Na+,
K+, Ca+, Mg+, Cl-, SO4, and PO4 were determined by
ion chromatography (Metrohm IC 861). HCO3 was
determined by volumetric titration. The analytical
precision for the measurements of cations and anions
was determined by calculating the ionic balance error
that varies by about 5%10% (Domenico and
Schwartz, 1998). Phreeqc interactive (Ver 2.8) was
used to correlate the mixing proportion identified by
the Piper diagram along with the original sample. Two
different samples were identified as parent solutions to
determine the mixing proportion after studying the
water table and flow directions.
5 Results and discussion
5.1 Piper diagram
Originally the most abundant cation constituents
are alkaline earths calcium (Ca) and magnesium
(Mg), and also one alkali, sodium (Na). Potassium
(K) also occurs commonly, but ordinarily is much less
abundant than sodium. Still other cation-constituents
occur in appreciable quantities in highly concentrated
natural waters and in some water of unusual composi-
tion for the graphical methods treated in Piper (1944).
The most common anion-constituents are one weak
acid bicarbonate (HCO3), also two strong acids,
sulphate (SO4) and chloride (Cl). Less common an-
ion-constituents are summed with the major three
anions to which they are respectively related. Thus for
many of the graphical methods, a natural water is
treated substantially though it contained only three
cation-constituents and there anion-constituents. Sub-
stantially in all natural waters cations are in chemical
equilibrium with anions. Accordingly, if the several
dissolved constituents are measured in terms of per-
centage of reacting values, that this, according to their
equivalents per million expressed as a percentage of
the sum of the equivalent for the entire constituent.
The concentrations of any constituent in equivalents
per million (milligram equivalent per kilogram) are
computed by multiplying its concentrations in parts
per million by the reciprocal of the combining weight.
The subtotals of the cations and anions are necessarily
each 50 percent of the whole (Piper, 1944).
The chemical composition of 3 groundwater
Chin.J.Geochem.(2011)30:490495
samples is listed in Table 1. The EC values range from
1192 to 3273 S/cm with an average value of 2486
S/cm. The pH values of groundwater range from
7.55 to 8.09 with an average value of 7.78. This shows
that the groundwater of the study area is mainly alka-
line in nature. TDS values range from 608 to 1643
mg/L with an average value of 1250 mg/L. The geo-
chemical evolution of groundwater can be understood
by plotting the concentrations of major cations and
anions in the Piper trilinear diagram (Fig. 3). The plot
shows that the three samples, Nallur including
Na-Mg-Ca-HCO3-Cl on northern side, Velangadu
(Na-HCO3) in the central part and Nanamedu
(Na-Mg-HCO3) falling near the coast of the study area,
but all the samples have high Na concentrations.
Fig. 3. Piper plot.
To demonstrate conclusively that a certain kind
of water is a quantitative mixture of two other kinds of
water neither diluted, concentrated, nor chemically
modified after mixingone graphic criterion and one
graphic-algebra must be satisfied first, by the graphic
criterion, in all three fields of the diagram the apparent
mixture must plot on straight lines between the plots
of its two inferred components. Also the area-concen-
tration plotting in the central field must confirm to the
principle that the several concentrations of mixing is
necessary greater than the least concentration, but less
than the greatest of the several concentrations of its
components. The two sampling points: Nallur in the
north and Velangadu in the south, were considered as
the parent solutions A and B, respectively. Nanamedu
was considered as a mixture of the two parent solu-
tions. The entire sample data set along with the results
were correlated for Nallur and it was found that the
maximum correlation co-efficient of Velangadu and
Nanamedu is in the respective order than the other
samples. Now the water table at Nallur and Velangadu
was treated as parent solutions A and B and that at
Nanamedu was assumed as the mixture of the
above set of parent solution C. Now, by considering
Chin.J.Geochem.(2011)30:490495
Table 1 Chemical composition of groundwater (in mg/L) except EC and pH (EC in S/cm)
S. No. Location pH EC TDS
A Nallur 7.55 3273.00 1643.00
B Velangadu 7.71 1192.00 607.60
C Nanamedu 8.09 2992.00 1499.00
Nanamedu as an unknown sample, the composition of
the above set of samples was derived by using the
Piper diagram using the following procedure.
This graphic criterion is not decisive because it
involves only percentage reaction values and does not
involve absolute content ratios. Neither is any other
simple graphic construction on the diagram decisive.
The second decisive criterion requires satisfaction of
the following equation.
With reference to Fig. 3, Va=proportionate vol-
ume in mixture M of water having composition A;
Vb=proportionate volume of water having composi-
tion B; Ea=concentration of water A, in equivalent;
Eb=concentrations of water B, in equivalent; Em=
concentrations of the mixture, in equivalent: a=inter-
cept between the plots of A and M, measured in any of
the three fields of the diagram and on any convenient
scale; and b=intercept between the plots of B and M
and can be shown as:
(a/b) = (vb.Eb/Va.Ea)
(Va/Vb) = (b.Eb/a.Ea)
Em= [Ea.Eb (a+b)]/(a.Ea+b.Eb)
Va = b.Eb/(a.Ea +b.Eb) and
Vb=a.Ea/(a.Ea+b.Eb)
Furthermore, with respect to any particular
chemical constituent, let: Ca=concentrations in com-
ponent water A, in equivalent or part per million as
desired; Cb=concentrations B; and Cm=concentrations
in the mixture. Then
Cm= (Ca.Va) + (Cb.Vb)
Natural water may be concentrated progressively
until it becomes saturated with respect to the con-
stituents, which are separated out in the solid phase.
Until a saturation- point is reached, the chemical
characteristics of concentrating of the water are repre-
sented by the single fixed point in the three fields of
the diagram. If the material separated in the solid
phase is of constant composition, then, as evaporation
continues, the characteristics of the water will be
traced on the respective fields by strength-line vectors
493
Ca Mg Na K Cl HCO3 PO4 SO4
110.00 90.00 72.20 4.50 175.00 489.00 0.30 22.50
36.00 52.80 154.80 23.90 177.20 427.00 0.30 6.00
44.00 48.00 46.60 4.50 120.00 402.60 0.40 7.30
directed away from the point that represents the com-
position of the separating solid. If the solid phase is a
simple component consisting of one cation and one
anion, the vector in the central field will be directed
away from one of the apexes of that field, each of
which represents a particular simple salt or a group of
salts.
Certain changes in the chemical properties of the
water are caused by chemical reactions which in effect
substitute one cation or one anion for another, mole-
cule for molecule. Thus, reduction of the sulfate
(Roger, 1941) is equivalent to substitution of bicar-
bonate (HCO3) for an equivalent amount of sulphate
(SO4): natural softening by reaction with base-ex-
change minerals (Renick, 1925), to substitute sodium
and potassium (Na, K) for calcium and magnesium
(Ca, Mg). These two chemical changes are traced on
the diagram by straight-line vectors parallel to the
bases of the central field.
(1) 5.2 Phreeqc mixing
(2)
In mixing, each solution is multiplied by its mix-
(3) ing fraction and a new solution is calculated by sum-
ming over all of the fractional solutions. In the exam-
ple data block, if the moles of sodium in solutions A,
(4) B, and C were 0.1, 0.2 and 0.3, the moles of sodium in
the mixture would be 0.11.1+0.20.5+0.30.3=0.3.
The moles of all elements are multiplied by the solu-
tion's mixing fraction, including hydrogen and oxygen.
Thus, the mass of water is effectively multiplied by
the same fraction. In the example data block, if all
solutions have 1 kg of water, the total mass of water in
the mixture will be 1.1+0.5+0.3=1.9 kg and the con-
centrations of sodium would be approximately 0.16
(5) mol/kgw (0.3/1.9). The charge imbalance of each so-
lution is multiplied by the mixing fraction and all the
imbalances are then summed to calculate the charge
imbalance of the mixture. The temperature of the
mixture is approximated by multiplying each solution
temperature by its mixing fraction, summing these
numbers, and divided by the sum of the mixing frac-
tions. Other intensive properties of the mixture are
calculated in the same way as temperature. This ap-
proach for calculating the temperature of mixtures is
an approximation because enthalpies of reaction are
ignored. For example, heat generated by mixing a
494
strong acid with a strong base is not considered.
This formulation of mixing can be used to ap-
proximate constant volume processes if the sum of the
mixing fractions is 1.0 and all of the solutions have
the same mass of water. The calculations are only ap-
proximate in terms of mixing volumes because the
summation is made in terms of moles (or mass) and
no consideration is given to the partial molar volumes
of solutes.
The two parent solutions A and B are considered
for different mixing proportions from 10% to 90% of
both the samples by using patch reaction. The results
obtained by the mixing proportion in the software
were expressed in molar concentration and further
converted to (epm) and compared with the original
composition of the Nanamedu sample. It was found
that 10% of solution A, 90% of solution B matched
almost perfectly the composition of the Nanamedu
sample (C) (Table 2). Spatially the distance between
mixture and the parent solution 2 is lesser then that of
solution1 hence was found that the proportion of solu-
tion 2 is more.
Table 2 Mixing proportions of Piper and Phreeqci
values in epm values
Original composition Piper value Phreeqci
Ca 1 1.126076 2.0339
Mg 4.166667 1.991012 8.439
Na 11.17391 10.61585571 11.16
K 0.615385 0.1914653 0.616
Cl 0.998592 1.8179788 1.994
HCO3 2.2 3.0075934 3.93111
SO4 0.027083 0.05750893 0.05420
6 Conclusions
The hydrogeochemical analysis of the study area
reveals that the groundwater is alkaline in nature. The
abundances of major cations and anions follow the
order of Na >Ca >Mg >K=HCO3 >Cl >SO4. The alka-
lis (Na and K) exceed the alkaline earth elements (Ca
and Mg) and HCO3 exceeds other anions. The Piper
diagram was used for classifying ground waters of
different origins; moreover it can also be used to iden-
tify geochemical processes involving the evolution of
the efficient composition. The present study helps to
calculate the mixing percentage of the concentrations
of different ions in a sample mixing from two parent
solutions. This study reveals that 10% of parent solu-
tion A (Nallur) and 90% of parent solution B (Velan-
gadu) matched almost perfectly the composition of
mixing solution C (Nanamedu). Hence, the proportion
of solution B is more in mixture solution C, due to the
lesser spatial distance between mixture solution C and
parent solution B.
Chin.J.Geochem.(2011)30:490495
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