Groundwater Geochemistry

(Hydrogeochemistry)

Wan Zuhairi Wan Yaacob (PhD, Assoc. Prof)

Program Geologi, UKM

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 Geochemistry
• Water / rock interactions in
unsaturated/saturated zones

• Geochemistry is important to groundwater

studies:-
– Characterizing the natural system (or
groundwater composition)
– Understanding contaminant migration
– Designing remediation programs

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 Simple geochemical model
• Aqueous geochemistry
– Water/rock
interactions
– To control the
groundwater
composition and the
movement of dissolved
constituents

Deutch WJ. 1997. Groundwater Chemistry. CRC Press

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 Fresh water without any Reactions that dissolve
dissolved constituents gases and minerals and
(disequilibrium) changes the solution
composition

Dynamic geochemical
system consisting
(i) Solid phase
(ii) Gas phase
(iii) Aqueous
solution phase

disequilibrium

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 Groundwater solution
• Definitions and concentration units

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 • Concentration of solute in solution
• Milligram per liter (mg/L)
• Part per million (ppm)

mg/L  ppm mg/L ppm

mg/L
------- = solution density (g/cc) – TDS (g/cc)
ppm

Solution density = 1.008 g/cc

TDS = 10,000 mg/L (0.01 g/cc)

Then, 1 ppm = 0.998 mg/L (0.2 % difference!)

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• Groundwater solutes
– Major Ions (concentration > 1 mg/L)
– Minor ions (concentration < 1 mg/L)

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• Converting measured concentration (mg/L or ppm) to
electrical equivalent unit (meq)

= 4.6 meq / L

(1000 miliequivalents = 1 equivalent)

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 • Conversion to meq
• Electrical balance

Electrical balance:

Electrical balance for Table 1-2 = +0.5%

+ (excess cations; insufficient anions)
- (excess anions; insufficient cations)
Reasonable
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 Several possible reasons that create an
electrical imbalance in the data
1. The design of the sampling program neglected a
major dissolved species
2. Laboratory error
3. Using unfiltered water samples
4. Precipitation of a mineral in the sample
5. In certain cases, the dissolved species may not
correspond to the typical species used in the
making the ion balance calculation

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 Groundwater types
• Classify groundwater based on dominant
cations and anions
• Ca-HCO3 type (dominant with Ca and HCO3)
• Displayed graphically by several methods
– Bar graph
– Circular diagram
– Stiff diagram
– Trilinear or Piper diagram
– Durov diagrams

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 Bar Diagram Circular Diagram

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Stiff Diagram Piper Diagram

Durov Diagram

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 STIFF DIAGRAM
1. Ion concentrations in meq L-1 are plotted on the
horizontal axis.
2. Cations are plotted to the left, anions to the right, of a
vertical axis.
3. The data are plotted in four rows and the points are
connected to form a polygon.
4. Advantage: each water type produces a distinct shape.
5. Disadvantage: each analysis requires its own plot; only a
limited number of data can be shown on a single plot.

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n e C re e k , C D A V a l l e y , I d a h oAn example of a Stiff diagram drawn for
M ine W at er s
mine waters from the Pine Creek district,
Cat io ns m eq/ l Anio n s Coeur d’Alene Valley, ID. The anions are
1 5 1 0 5 5 1 0 1 5
mostly dominated by sulfate, with lesser
N a + K C l bicarbonate, whereas the cations are
C a AD0 0 2 H CO 3 + CO 3 dominated by calcium and magnesium.
M g S O 4
N a + K C l

C a AD0H0C4O 3 + CO 3

M g S O 4
N a + K C l

C a AD0 0H5C O 3 + CO 3

M g S O 4
N a + K C l

C a AD0 0 7H C O 3 + CO 3

M g S O 4
N a + K C l

C a S97 - 3 H CO 3 + CO 3

M g S O 4
N a + K C l

C a SP0 0 2 H CO 3 + CO 3

M g S O 4
N a + K C l

SPNEW
C a H CO 3 + CO 3
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M g S O 4
 Stiff pattern

Stiff pattern are centered

over locations of wells

Isocon of TDS

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 PIPER DIAGRAMS
1. Consists of two triangles (one for cations and one for
anions), and a central diamond-shaped figure.
2. Cations are plotted on the Ca-Mg-(Na + K) triangle as
percentages.
3. Anions are plotted on the HCO3--SO42--Cl- triangle as
percentages.
4. Concentrations are in meq L-1.
5. Points on the anion and cation diagrams are projected
upward to where they intersect on the diamond.
6. Many water analyses can be plotted on the same
diagram and can be used to classify waters.

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 Percentage of cations and anions as percentage of the total
(Step 2 and 3)

Cations meq/L % of Anions meq/L % of

total total
Ca2+ 1.15 36 Cl - 0.27 9
Mg2+ 0.39 12 SO4 2- 0.02 1
Na+ + K+ 1.64 52 CO3 2- + 2.80 90
HCO3 -
Total 3.18 Total 3.09

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 Figure 1-6 from
Kehew (2001). Water
analyses plotted on a
Piper diagram. Cation
percentages in meq L-1
plotted on the left
triangle, and anion
percentages in meq L-1
plotted on the right
triangle.

Ca = 22.3 %
Mg = 13.7 %
Na+K = 64 %
HCO3 = 31.3 %
SO4 = 54.5 %
Cl = 14.2 %

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 Figure 1-7 from
Kehew (2001).
Classification of
hydrochemical facies
using the Piper plot.

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 Pin e Cr e e k , CDA Va le y , I d ah o

l)
An example of a Piper

(C
M in e W at er s

e
diagram drawn for mine

d
ri
waters from the Pine

lo
AD002

8
Creek district, Coeur

C
C

0
AD004

8
)+

a
d’Alene Valley, ID. These

lc
AD005

iu
O

0
may be characterized as

0
AD007

m
6
(S

(C
S97- 3 Ca-Mg sulfate-
te

a
0
a

0
SP002
lf

)+
4 bicarbonate-type

)
3
u

M
SPNEW

O
S

waters.

a
0

C
0

g
2

(H
n
e

te
s
iu
a
n
m
o

(M
rb
M g S O
4
2

a
)

g
2

ic
g

)
(M

B
2

8
)+
S
0

0
4
0

0
m

0
8

2
0
o

3
4
iu

O
iu
s

S
4

6
(C
e

6
0

0
m
0

u
0
0
n
6

4
te

lf
6
(N
g

a
a

te
a
6

4
n
M

0
0

8
)+
0

0
o

(S
6
0
4

rb
8
P

O
o

a
8

4
ta
0

0
C
0

)
2

8
s
s
iu
m

C a 8 0 6 0 4 0 2 0 N a + H
KCO 3 + C3O 2 0 4 0 6 0 8 0 C l
(K

C a lc iu m ( Ca ) C h lo r id e ( C l)
% m e q / l
)

C A T
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 Ke h e w ( 2 0 0 1 )

l)
An example of a

(C
e
Piper diagram with

d
ri
lo
TDS circles.

8
0

C
0
C
8

a
)+

lc
4
3

iu
6
5
0 0 0

0 0 0

0 0 0

0 0 0

0 0 0

0
O

m
6
(S

(C
te
1 ,

2 ,

3 ,

4 ,

5 ,

a
0

0
a

)+
lf
T o t a l D is s o lv e d S o lid s 4 8

)
u

3
( P a r t s P e r M ilo n )
S

O
2

a
Plot the radius of TDS
0

g
0

C
2
2

n
4 using suitable scale

(H
e
s
(5000 ppm)

te
iu
7

am
n
(M
o
M g S O TDS – represents

rb
4
2

g
0
overall salt content of
0

a
)

)
2
g

ic
the water
(M

B
2

8
0

0
S

7
4

)+
0

0
0
m
8

2
0
o

3
iu

O
iu
s

S
4

6
3
0

0
6
e

(C

5
m
0

u
0
6

4
0
n

lf
(N

te

4
g

a
a

te
a

5
6

4
n
0
M
0

8
)+

(S
0

0
o
6
0
4

0
P

rb

6
8

O
o

4
3
8

2
ta
0

0
C

)
0

0
7
2

8
s

1 41 2
s
iu

6 6
m

C a 8 0 6 0 4 0 2 0 N a +H
KC O 3 + C3O2 0 4 0 6 0 8 0 C l
(K

C a lc iu m ( C a ) C h lo r id e ( C l)
)

C A T I O N S % m e q / l A N I O N S
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 Can you guess the type of
karst rivers systems aquifer of this groundwater ?

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 Thank you

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