ATMOSPHERE - WATER - SOIL INTERACTIONS

CONTENTS:

1. 2. 3. 4.

Reactions and partitioning at gas-water interface; Henrys Law Environmental implications A few example problems Soil Water Interaction & Alkalinity

Hydrologic Cycle

Water a minor component of the atmosphere. Also, only 0.001% of the total water in the world is in cloud or in atmosphere). Hydrogeochemical cycles couple 1. Atmosphere, 2. Water 3. Land

Atmosphere is an important conveyor belt for many pollutants. Example: China is a major source of pollution in Japan, Canada is affected by emission from the Northeast USA

Mercury Transport

Up the Food Chain

Atmosphere (Oxygen)-Surface Water Interactions: Mechanism behind the Sustenance of Aquatic Life O2 O2 is central to the sustenance of life of aerobic life-forms.

Similarly, aquatic ecosystem depends on the oxygen dissolved in the water Oxygen enters the surface water and oceans in two different pathways: a) Diffusion from atmosphere to water b) Through photosynthesis by algae in presence of sunlight. At any time in steady state condition, there is an equilibrium partitioning of oxygen between the water and the atmosphere.

RAINWATER DROPLET IN THE AIR

CO2 NH3 NO2

As the droplet passes through the atmosphere to fall on the earth surface, various gases, liquid and solids that are either part of the atmosphere or are suspended in air, tend to get inside the water droplet.

Dust

SO2

Aerosols

Organic acids

Many of the species establish a quick equilibrium, thus imbibing impurities even before the rain water reaches the earth surface.

Gas-Water Partitioning: Henrys Law

Gas molecules strike the water surface, some becomes dissolved. Some of the dissolved molecules also strike the surface, and escape in the gas phase. At dynamic equilibrium, the rate of dissolution into water equals the rate of escape into gas phase. The equilibrium situation is described by Henrys law

pA

[A]aq
Sealed vessel: liquid and gas phase.

The Statement: The amount of volatile species (gas) dissolved in a solution is directly proportional to the partial pressure of the gas above the solution.
For any species A, [ A] p aq A

[ A]aq K H p A

KH

[ A]aq pA

M unit : atm.

KH is called the Henrys law constant

Partial Pressure and Molar Concentration Ideal Gas R = 0.0820578 L.atm/(K.mol) pV nRT Law: n P Molar concentration: C V RT Partial pressure of each gas in a gas mixture, such as the atmosphere, is the portion of the total pressure that a particular gas would exert Daltons Law

Ptot = pA + pB + pC + = (nA + nB + nC + )RT/V = (ntot)RT/V

The atmosphere: (by volume) N2 78% O2 21% Ar 0.9345% CO2 0.0314% Other gases Rest

Partial pressure of O2 = pO2 = 0.21*Ptot=0.21*1 atm =0.21 atm

Partial pressure of CO2 = pCO2 = 0.000314*1 atm =10-3.5 atm

Example 1.

Find out the aqueous solubility of oxygen in a fully aerated water at 25 deg C in a treatment plant. KH of O2 at 25 deg C = 1.26X10-3 M/atm Partial pressure of oxygen in the atmosphere = 0.21 atm. Aqueous concentration of oxygen = KH*pO2 = 1.26 X10-3 M/atm. * 0.21 atm. =0.0002646 M = 8.467 mg/L
[1M O2= 32 g/L]

Is KH or Henrys law constant is really a constant?

The value of Henrys Law constant changes inversely with temperature.

Implication: In the summer, the rivers and lakes shall have less dissolved oxygen as compared to the dissolved oxygen concentration in winter

Carbon dioxide -Water Interaction: Natural Acidity

Unlike dissolution of oxygen, gases like carbon dioxide, sulfur oxides or nitrogen oxides after dissolution form further hydrated species which add acidity to the water. Carbon dioxide is a natural constituent of atmosphere. The acidity imposed by carbon dioxide is referred as natural acidity. When carbon dioxide dissolves in water it forms aqueous carbon dioxide which is popularly known as carbonic acid (H2CO3). Depending upon the solution pH, the species further dissociates into hydrogen ion and bicarbonate ion. Bicarbonate ion can get further dissociated into hydrogen ion and carbonate ions.

CO2

CO2 (aq.) H++HCO3H++CO32-

Carbon dioxide : Natural Acidity (contd)

CO2 ( g ) CO2 (aq.)
According to Henrys Law:

KH =10 -1.5 M/atm.

[CO2 ]aq K H pCO2 101.5 pCO2

Ka1 =10 -6.3

CO2 (aq.) H HCO3

[ H ][HCO3 ] K a1 106.3 [CO2 ]( aq.)

[ HCO3 ]

K a1[CO2 ]( aq.) [H ]

106.3 * K H pCO2 [H ]

107.8 pCO2 [H ]

HCO 3 H CO32

Ka2 =10 -10.3

Ka2

[ H ][CO32 ] 10.3 10 [ HCO3 ]

10 K [ HCO 2 a2 3 ] [CO3 ] [H ] 10.3

*107.8 pCO2
2

[H ]

1018.1 pCO2 [ H ]2

Carbon dioxide : Natural Acidity (contd)

Imposing Electro neutrality condition

[ H ] [ HCO3 ] 2[CO32 ] [OH ]

[H ]

107.8 pCO2 [H ]

2*

1018.1 pCO2 [ H ]2

1014 [H ]

In atmosphere, there is 370 ppm of carbon dioxide on mole basis. p 370*106 atm.
CO2

11.2 21.5 14 10 10 10 [H ] 2* 2 [H ] [H ] [H ]

Comparing 1st and 3rd term on the right hand side, 3rd term is at least 600 times smaller than 1st term. So, it can be neglected

11.2 21.5 10 10 [H ] 2* 2 [H ] [H ]

For trial, if the pH is 6 or [H+]=10-6, then left hand side and first term in the right hand side are dimensionally similar, whereas the last term is about 2000 times smaller than the other two terms. Hence, the last term can be neglected. 11.2

10 [H ] [H ]

[ H ] 10

11.2

[ H ] 10 5.6

pH log[ H ] 5.6

In general, for rainwater containing only CO2 approximately,

[ H ]2 106.3 *101.5 * pCO2

Find out the pH if the atmospheric CO2 concentration is doubled.

pCO2= 2*370*10-6 atm. =10-3.13

[ H ] 106.3 *101.5 *103.13
pH log[ H ] 5.47
This means that rise in atmospheric CO2 concentration does not change the acidity of rain water by a significant amount
For a can of carbonated drink,

pCO2= 5 atm.
[ H ] 106.3 *101.5 * 5
pH log[ H ] 3.56

pH?

 If CO2 is the only species, that affects the rainwaters acidity, its natural pH is 5.6
When additional acidic species are present at appreciable levels due to manmade activities, pH of rainwater becomes lower than 5.7 ACID RAIN Major contributors to acid rain : H2SO3, H2SO4 and HNO3

Find out the pH of acid rain when the atmosphere has 5 ppb of SO2 along with 370 ppm of CO2 as discussed earlier. KH for SO2 is 100.096 M/atm , Ka1=10-1.77 ; Ka2=10-7.21

SO2 ( g ) SO2 (aq.)

According to Henrys Law:

KH =10 0.096 M/atm.

[SO2 ]aq K H pSO2 100.096 pSO2

Ka1 =10 -1.77

SO2 (aq.) H HSO3

[ H ][HSO3 ] K a1 101.77 [ SO2 ]( aq.)

[ HSO3 ]

K a1[ SO2 ]( aq.) [H ]

101.77 * K H pSO2 [H ]

101.674 pSO2 [H ] 109.97 [H ]

pSO2 = 5*10-9 atm.

[ HSO3 ]

101.674 pSO2 [H ]

HSO3 H SO32

K a 2 10 7.21

Ka 2

[ H ][SO32 ] 7.21 10 [ HSO3 ]

7.21 9.97 17.18 K [ HSO ] 10 * 10 10 [ SO32 ] a 2 3 2 [H ] [H ] [ H ]2

Imposing electro-neutrality condition,

[ H ] [ HCO3 ] [ HSO3 ] 2[CO32 ] 2[ SO32 ] [OH ]

11.2 9.97 21.5 17.18 14 10 10 10 10 10 [H ] 2* 2 2* 2 [H ] [H ] [H ] [H ] [H ]

With an initial guess of pH =5, third, fourth and fifth terms on the RHS are found to be negligible compared to the other terms in the equation.

Therefore, considering only significant terms, the previous equation can be approximated as,
11.2 9.97 10 10 [H ] [H ] [H ]

[ H ]2 10 11.2 10 9.97 10 9.96 [ H ] 10 4.98 pH log[ H ] 4.98

We observe that the presence of trace amount SO2 can significantly alter the pH of the rainwater, the acid causing potential being more than carbon dioxide. NOx have the same effect as SOx for imparting acidity to rainwater.

60 years.
pH

CASE STUDY: LAKE NYOS DISASTER

On August 21, 1986, more than 1700 people and numerous wild life were killed by a silent and mysterious killer, CO2 gas

LAKE NYOS, CAMEROON

It is a lake in the volcano crater, 1.2 miles X 0.75 miles in area, but 682 feet deep. Under the bed, the volcano is leaking carbon dioxide into the water. This changes the water into carbonic acid.

High partial pressure of CO2, High conc. of bicarbonate and low pH

About 230 m deep, Pressure is about 25 atm

Volcanic gases containing CO2 from the underlying magma seeps into the bottom of lake

Due to such a high partial pressure of carbon dioxide, the pH was substantially low, HCO3- concentration was pretty high.

Carbon dioxide gas is heavier than atmosphere, unless there is a strong dispersion forces such as high wind, it tend to sit at the bottom of the atmosphere, causing asphyxiation http://www.geogonline.org.uk/g1_nyos.htm

REMEDIATION EFFORTS

The method is simple, consisting of a vertical pipe between the lake bottom and the surface. A small pump raises the water in the pipe up to a level where it starts releasing the gas from the diphasic fluid. At this point there is a pressure gradient which causes the water to rise to the surface and erupt like a fountain. Therefore, once it has primed the gas lift, the pump is not needed, and the process becomes self-powered. Isothermal expansion of gas bubbles drives the flow of the gas-liquid mixture as long as dissolved gas is available for ex-solution and expansion.
http://mhalb.pagespersoorange.fr/nyos/2006/index2006.htm http://www.geo.arizona.edu/geo5xx/geos577/ projects/kayzar/html/lake_nyos_disaster.html

http://www.okeanosgroup.com/blog/aquatic-architecture-2/how-to-transform-a-poisonousexplosive-lake-into-electricity/

Other Applications/ Phenomena Linked with Gas Water Interaction

SOIL-WATER INTERACTION Precipitation CO2 + H2O H+ + HCO3-

Topsoil
Subsoil

Limestone

CaCO3(s) + H+ Ca2++HCO3MgCO3(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.)

HCO H CO
Also,
3 2 3

KH =10 -1.5 M/atm. Ka1 =10 -6.3

CO2 (aq.) H++HCO3Ca2++CO32H++CO32-

CO2 (aq.) H HCO3

Ka2 =10 -10.3

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 ] [ HCO 3 ] 2[CO32 ]

From CO2 equilibrium,
10 K [ HCO 2 a2 3 ] [CO3 ] [H ] 10.3

*107.8 pCO2
2

[H ]

1018.1 pCO2 [ H ]2

From solubility of calcium carbonate,

[Ca 2 ]
Hence,

K sp [CO ]
2 3

K sp [ H ]2 1018.1 pCO2

108.42 [ H ]2 109.68 [ H ]2 18.1 10 pCO2 pCO2

2*

10

9.68

[H ]

pCO2

[H ]

10 [H ]

14

107.8 pCO2 [H ]

2*

1018.1 pCO2 [ H ]2

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

14 11.23 21.23 10 10 10 10 13.41[ H ]2 [ H ] [ H ] [ H ] [ H ]2

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

100.59 107 107 104.23 107.23

This means that only first term and second term in the equation is significant for obtaining an approximate solution.
11.23 10 10 13.41[ H ]2 [H ]

[ H ]3 10 24.64
[ H ] 10 8.21
pH= 8.21

[Ca ]

10

9.68

[H ]

[ H ] 10 8.21

pCO2

pCO2 360*106 atm

[Ca 2 ] 20 mg / L

9.68 8.21 2 10 [ 10 ] 2 4 [Ca ] 5 . 05 * 10 M 6 360 *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 waters 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 HCO 3

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( M ) [ 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 232 mg/L of CO3 0.53 *10 3 M 10 3.27 M 60 g / mole

HCO 3 H CO32

Ka2 =10 -10.3

Ka2

[ H ][CO32 ] 10.3 10 [ HCO3 ]

2 10 3.27 [ H ][ CO ] 10 * 10 2.97 3 [ HCO3 ] 10 Ka2 1010.3 Alkalinity (M ) [ HCO3 ] 2[CO32 ] [OH ] [ H ]

102.97 2 *103.27 104 1010

 Alkalinity (M ) [ HCO3 ] 2[CO32 ] [OH ] [ H ]

102.97 2 *103.27 104 1010 M 2.246*10-3 M

Alkalinity (meq / L) [ HCO3 ] [CO32 ] [OH ] [ H ] 102.97 103.27 104 1010 eq/L 1.71*10-3 eq / L
1 eq/L CaCO3 = 50 g/L of CaCO3

Alkalinity = 1.71*10-3*50 g/L =85.5 mg/L as CaCO3