SOIL-WATER INTERACTION

Precipitation
CO2 + H2O  H+ + HCO3-

Topsoil

Subsoil

Limestone CaCO3(s) + H+  Ca2++HCO3-

MgCO3(s) + H+  Mg2++HCO3-

Result: Mobilization of different ions in the groundwater from the

minerals constituting the topsoil and subsoil
EXAMPLE:
Rainwater falls on a soil surface and is under open atmosphere in
contact with soil containing abundant amount of limestone (calcium
carbonate). What will be the pH in this case? Ksp of calcium
carbonate is 10-8.42.
There is abundant quantity of calcium carbonate and it is sparingly soluble
in water. So, the aqueous system is always in equilibrium with solid calcium
carbonate. It is also in equilibrium with the air.
CO2
So, the relevant reactions are: The situation is :

CO2 ( g )  CO2 (aq.) KH =10 -1.5 M/atm. CO2 (aq.)

CO2 (aq.)  H   HCO3 Ka1 =10 -6.3
  2 H++HCO3- H++CO32-
HCO  H  CO
3 3 Ka2 =10 -10.3
Also, Ca2++CO32-
CaCO3  Ca 2  CO32 KSP =10 -8.42
CaCO3
The electro-neutrality condition is now different from before. We have a
divalent calcium ion.
2[Ca 2 ]  [ H  ]  [OH  ]  [ HCO3 ]  2[CO32 ]
From CO2 equilibrium,
10.3
2 K [ HCO 
3 ]
10 *107.8 pCO2 1018.1 pCO2
[CO3 ]  a2

  2

[H ] [H ] [ H  ]2
From solubility of calcium carbonate,
K sp K sp [ H  ]2 108.42[ H  ]2 109.68[ H  ]2
[Ca 2 ]  2
  
[CO ]
3 1018.1 pCO2 10 18.1
pCO2 pCO2
Hence,

10 9.68
[H ]  2
1014
107.8 pCO2 1018.1 pCO2
2*  [H  ]  
 
 2*
pCO2 [H ] [H ] [ H  ]2
 pCO2= pressure exerted by 370 ppm (by volume) gas= 370 * 10-6
atm
109.68[ H  ]2  10 14
10 7.8
* 370 *10 6
10 18.1
* 370 *10 6
2* 6
 [ H ] 
 
 2*
370 *10 [H ] [H ] [ H  ]2

14 11.23 21.23

10 10 10
1013.41[ H  ]2  [ H  ]   
[ H ] [ H ] [ H  ]2
 

For a test case, lets consider that [H+]=10-7

100.59  107  107  104.23  107.23

This means that only first term and second term in the equation is
significant for obtaining an approximate solution.
11.23
10 [ H  ]3  1024.64
1013.41[ H  ]2 
[H  ]
[ H  ]  108.21 pH= 8.21
 9.68  2 [ H  ]  108.21
2 10 [H ]
[Ca ] 
pCO2 p CO2  360 *106 atm
9.68 8.21 2
2 10 [10 ] 4
[Ca ]  6
 5.05 *10 M [Ca 2 ]  20mg / L
360 *10
This eventually means that the rainwater which has a pH of 5.6, when
comes in contact with a limestone deposit on the surface, the whole
chemistry changes because of the dissolution of limestone into the water.
The water turns alkaline with pH of 8.2 and with calcium being dissolved at
a concentration of about 20 mg/L.
Soil contains multitude of different minerals. The rainwater when comes
in contact with soil , dissolves many metal cations , also anions, into the
water and the pH also rises so that the natural waters, surface as well as
underground, normally have a pH in the envelope of 6.5 to 8.5. Also, the
surface- and groundwater contains minerals many of which are
physiologically significant.
 ALKALINITY
Alkalinity is a measure of the acid buffering capacity of water. In other
words, it measures the water’s capability to consume hydrogen ion
without making any change in the pH of the system.

What happens then to H+ ions added to the system?

The H+ ions would react with the components in water mainly, HCO3-,
CO32- and OH- according to the following reactions and would get
consumed and will be unavailable for lowering the pH.
H   CO32  HCO3 H   HCO3  CO2 (aq.) H   OH   H 2O

This means that presence of these ions provide some buffer capacity for the
system, so that the pH does not change even if acid is added to the system.

The summation of all these H+ buffering ions is called acid buffering ability or
alkalinity .
Alkalinity (meq / L)  [ HCO3 ]  2[CO32 ]  [OH  ]  [ H  ]
EXAMPLE

A sample of water at pH 10 has 32 mg/L of CO32-. Find the alkalinity of

the water in the following units: M as well as mg/L as CaCO3.
SOLUTION Estimate all the acid buffering ions.

pH =10 [ H  ]  1010 pOH = 4 [OH  ]  104

3
32 *10 g/L
32 mg/L of CO3 
2-
 0.53 *103 M  103.27 M
60 g / mole
HCO3  H   CO32 Ka2 =10 -10.3
[ H  ][CO32 ] 10.3
Ka2   10
[ HCO3 ]
 2 10 3.27
[ H ][CO ] 10 *10
[ HCO3 ]  3
  10  2.97

Ka2 1010.3
Alkalinity (meq / L)  [ HCO3 ]  2[CO32 ]  [OH  ]  [ H  ]
 102.97  2 *103.27  104  1010
 Alkalinity (meq / L)  [ HCO3 ]  2[CO32 ]  [OH  ]  [ H  ]
 102.97  2 *103.27  104  1010  2.246 *10-3

Alkalinity ( M )  [ HCO3 ]  [CO32 ]  [OH  ]  [ H  ]

 102.97  103.27  104  1010 M  1.71*10-3 M

1 eq/L CaCO3 = 50 g/L of CaCO3

Alkalinity = 2.246*10-3*50 g/L =112.3 mg/L as CaCO3