EAS 44600 Groundwater Hydrology

Lecture 14: Water Chemistry 1

Dr. Pengfei Zhang

Concentration Units

Molar concentration (M) defines the number of moles of a chemical species in one liter of
solution (mol/L). One mole (mol) of a substance is its formula weight in grams. For example,
one mole of NaCl is 58.44 grams.

Molal concentration (m) defines the number of moles of a chemical species in one kilogram of
solution (mol/kg). For dilute solutions, molal concentrations are almost the same as molar
concentrations because a one-liter solution has a mass of about 1 kilogram. Notice that molal
concentrations will not change as temperature changes, whereas molar concentrations will due to
the dependence of solution density (and hence solution volume) on temperature. Therefore, in
chemical thermodynamics, molal concentrations rather than molar concentrations are used.

Mass per unit volume concentration is the most common unit for concentration. It defines the
mass of a chemical species in one liter of solution, typically reported in units such as mg/L or
g/L.

Equivalent charge concentration is the number of equivalent charges of an ion in one liter of
solution (meq/L or eq/L). The equivalent charge for an ion is equal to the number of moles of an
ion multiplied by the absolute charge of the ion. For example, with singly charged species such
as Cl
-
and Na
+
, 1 M = 1 eq/L = 1,000 meq/L, and with doubly charged species such as SO
4
2-
and
Ca
2+
, 1 M = 2 eq/L = 2,000 meq/L.

Mass per unit mass concentrations define the mass of a chemical species per total mass of the
system (mg/kg or g/kg). Older analyses often used concentration units of ppm (parts per
million) or ppb (parts per billion). These units are no longer commonly used.


Routine Water Analysis

A routine water analysis involves measuring the concentration of a standard set of constituents,
as well as pH, total dissolved solids (TDS), and specific conductance. The major constituents
reported in a routine water analysis include Ca
2+
, Na
+
, Mg
2+
, K
+
, HCO
3
-
, SO
4
2-
, Cl
-
, NO
3
-
, and
dissolved SiO
2
, and the minor constituents include Fe
2+
/Fe
3+
, Cu
2+
, F
-
, etc. Table 14-1 lists the
chemistry of some natural waters and the drinking water standards for major ions. The major
ions in most ground waters meet the drinking water standards (Table 14-1). In fact, most of the
groundwater contamination is caused by constituents in trace amounts (e.g., heavy metals and
organic compounds), not the major ions. Nevertheless, routine water analyses are necessary to
ensure the suitability of the water for human use.


14-1
Table 14-1. Major ion chemistry of natural waters and drinking water standards for the major
ions (Lee and Fetter).
Constituents
in mg/L
Precipitation
GW in
unconsolidated
deposits
GW in
Igneous
Rocks
GW in
Sedimentary
Rocks
GW in
Carbonates
Seawater
Drinking
water
standards
Na
+
0.6 47 4 20 13 10560 200
K
+
0.4 3 1 2 3 380 ---
Ca
2+
0.9 54 8 53 55 400 200
Mg
2+
0.2 15 2 19 28 1272 125
HCO
3
-
2.0 157 40 263 255 142 500
SO
4
2-
3.0 64 1 47 48 2560 250
Cl
-
0.4 21 1 12 14 18980 250
NO
3
-
0.3 0.6 n/a 2.7 n/a <1 20
SiO
2
0.1 22 19 15 n/a 1 - 4 ---
TDS 5.1 230 76 380 416 34378 500
pH 5.5 7.5 6.8 7.5 7.5 8.1-8.4 ---


Describing Chemical Data

Different graphical and statistical techniques have been developed to describe the concentration
or relative abundance of major and minor constituents and the pattern of variability in different
water samples. The most common graphical approaches to describe the abundance or relative
abundance of ions in individual water samples are the Stiff pattern diagram (Figure 14-1) and the
Piper diagram (Figure 14-2). In Stiff pattern diagrams the concentrations are expressed as
meq/L, whereas in Piper diagrams the concentrations are expressed as %meq/L.

To construct a Stiff pattern, a polygon is created from four parallel horizontal axes using the
equivalent charge concentrations (meq/L) of cations and anions. Cations are plotted on the left
of the vertical zero axis and anions are plotted on the right (Figure 14-1). Notice that in many
waters the contents of iron and carbonate are close to zero and the use of the fourth axis is
optional. Stiff diagrams are very useful in making quick comparison between waters from
different sources.

To construct the Piper diagram, the relative abundance of cations with the %meq/L of Na
+
+K
+
,
Ca
2+
, and Mg
2+
is first plotted on the cation triangle. The relative abundance of Cl
-
, SO
4
2-
, and
HCO
3
-
+CO
3
2-
is then plotted on the anion triangle. The two data points on the cation and anion
triangles are then combined into the quadrilateral field that shows the overall chemical property
of the water sample (Figure 14-2).

The Piper diagram not only shows graphically the nature of a given water sample, but also
dictates the relationship to other samples. For example, by classifying samples on the Piper
diagram, we can identify geologic units with chemically similar water, and define the evolution
in water chemistry along the flow path (Figure 14-3).

14-2
Figure 14-1. Analysis represented by Stiff patterns. The horizontal distance from the vertical
axis is based on the number of meq/L of each cation or anion (Fetter).


Figure 14-2. Plotting chemical data on a Piper diagram.

14-3


Figure 14-3. A Piper diagram shows how samples can be classified according to setting, e.g.,
limestone, alluvial fans and basin fills, and the salt flats. The evolutionary pathway is defined by
groundwater moving from the limestone, through the alluvium fan to the salt flats.


Chemical Activity

The chemical activity (a) of an ion is equal to the molal concentration multiplied by the activity
coefficient ():

m a = (14-1)

The activity coefficient of an individual species can be computed from the ionic strength (I) of
the solution. The ionic strength of a mixture of electrolytes is given by

=
2
2
1
i i
z m I (14-2)

where m
i
is the molal concentration of i
th
ion and z
i
is the absolute charge of i
th
ion.
For a dilute solution (I 10
-3
), the activity coefficient can be calculated from the Debye-Hckel
equation:

I Az
i i
2
log = (14-3)

where A is a constant.

14-4

At higher ionic strengths (10
-3
< I 0.1), equation 14-3 can be modified to take account for the
finite size of the ions, giving the extended Debye-Hckel equation:

I Ba
I Az
o
i
i
+

=
1
log
2
(14-4)

where B is a constant and a
o
is the hydrated radius of the particular ion. The values of A, B, and
a
o
for various ions are listed in Table 14-2. Note in Table 14-2 that the product Ba
o
has a
numerical value of about 1. Furthermore, the a
o
values for many ions have not been measured
experimentally. Therefore, a common alternative form of equation 14-4, the so-called
Gntelberg equation, is used:

I
I Az
i
i
+

=
1
log
2
(14-5)

Table 14-2 Parameters for the Debye-Hckel equation at 1 atmosphere pressure.
T (C) A B (10
8
) Ion a
o
(10
-8
)
0 0.4883 0.3241 Ca
2+
5.0
5 0.4921 0.3249 Mg
2+
5.5
10 0.4960 0.3258 Na
+
4.0
15 0.5000 0.3262 K
+
, Cl
-
3.5
20 0.5042 0.3273 SO
4
2-
5.0
25 0.5085 0.3281 HCO
3
-
, CO
3
2-
5.4
30 0.5130 0.3290 NH
4
+
2.5
40 0.5221 0.3305 Sr
2+
, Ba
2+
5.0
50 0.5319 0.3321 Fe
2+
, Mn
2+
, Li
+
6.0
60 0.5425 0.3338











H
+
, Al
3+
, Fe
3+
9.0


At ionic strengths greater than 0.1, equations 14-4 and 14-5 can be modified to the Davies
equation by adding a further term:
I
I Ba
I Az
o
i
i
3 . 0
1
log
2
+
+

= (14-6)
or

I
I
I Az
i
i
3 . 0
1
log
2
+
+

= (14-7)


Equilibrium Reactions

Consider the following reaction, where species A and B react to produce species C and D:

14-5

dD cC bB aA + + (14-8)

where a, b, c, and d representing the number of moles of these constituents. At chemical
equilibrium, the equilibrium distribution of mass between reactants and products can be
expressed as:
b a
d c
B A
D C
K
] [ ] [
] [ ] [
= (14-9)

where K is the equilibrium constant, and [A], [B], [C], and [D] are the activities for reactants and
products at equilibrium. Equation 14-9 is referred to as the Law of Mass Action. Depending
on the reaction, the equilibrium constant K may represent a solubility constant in dissolution
reactions, a dissociation constant in acid-based reactions, or a complexation constant in
complexation reactions.

Notice that for a dilute solution, the activity coefficient for an ion is close to 1 and the activity is
almost equal to the molality (or molarity). This is generally true for groundwater systems. Since
most of the water chemistry analyses use molarity, we may use molarity rather than activity
or molality in our calculations.


Deviations from Equilibrium

In a groundwater system, some reactions may not be at equilibrium (e.g., dissolution or
precipitation reactions). The departure of a reaction from equilibrium is often described using
the ratio of the ion activity product (IAP) to the equilibrium constant, IAP/K. Given a
groundwater with known activities of [A], [B], [C], and [D], the activity product of equation 14-
8 is:


b a
d c
B A
D C
IAP
] [ ] [
] [ ] [
= (14-10)

At disequilibrium, the activity product will not be equal to K. If IAP/K > 1, the reaction will tend
to go to the left; if IAP/K < 1, the reaction will tend to go to the right.

A closely related term is saturation index (SI), which is defined as log (IAP/K) for a dissolution
reaction. A negative SI value indicates undersaturation of a particular solid phase, whereas a
positive SI indicates supersaturation.


pH

Water undergoes the following dissociation reaction to form H
+
and OH
-
ions:

+
+ OH H O H
2
(14-11)

14-6

The equilibrium constant for water is:
] [
] ][ [
2
O H
OH H
K
+
= (14-12)

where [X] is the activity of species X. The activity of water is 1, and the equilibrium constant for
water is 10
-14
at about 25 C.

The pH is the negative log of the activity of the hydrogen ion in a solution:

] log[
+
= H pH (14-13)

For a neutral solution, [ , and the pH is 7. An acidic solution has a pH value
of less than 7, whereas a basic solution has a pH value of greater than 7.
7
10 ] [ ]
+
= = H H

14-7