ATMOSPHERE - WATER

INTERACTIONS

THEHYDROLOGICALCYCLE
Representationof:

flows
water
energyfromsun
suspended/dissolvedmaterialsnatural,anthropogenic

inputs/outputsto/fromsubsystems
catchment/watershedagrichemicals
atmosphereairpollutants
waterstores(atmosphericwater,surfacewater,ground
waterandocean)

COMPONENTSOFTHEHYDROLOGICALCYCLE
Evaporation:istheprocessinwhichaliquid(water)
changesintowatervapor.
Transpiration:istheprocessinwhichwaterthatis
takeninthroughplantsrootsevaporatesfromthe
plantsleaves,stemsandflowers.
Condensation:istheprocessinwhichwatervapor
changesintoliquid.
Precipitation:istheprocessinwhichliquidwater
formsfromcondensationinsidecloudsandfallsas
rain,sleet,snowandhail.
GroundWater:iswaterinthesoil.Plantrootscan
growdowntoreachgroundwater.
Runoff:Iswaterthatrunsoffthegroundintolakes,
rivers,streams,sea.

EVAPORATION & TRANSPIRATION

Fig.4.1

GLOBAL WATER BALANCE (VOLUMETRIC)

Units are in volume per year relative to precipitation on
land (119,000 km3/yr) which is 100 units
Precipitation
100

Atmospheric moisture flow

39

Precipitation
385

Evaporation
424

Evaporation
61
Surface Outflow
38

Land (148.7 M km2)

(29% of earth area)

Subsurface Outflow
1

Ocean (361.3 M km2)

(71% of earth area)

GLOBAL WATER BALANCE (mm/in OF RAIN)

Precipitation
800 mm (31 in)

Atmospheric moisture flow

316 mm (12 in)

Precipitation
Evaporation
1270 mm (50 in) 1400 mm (55 in)

Evaporation
480 mm (19 in)
Outflow
320 mm (12 in)

Land (148.7 M km2)

(29% of earth area)

(Values relative to land

area)

Ocean (361.3 M km2)

(71% of earth area)

WATERDENSITY
Waterasasolid(ice)
islessdensethanitis
asaliquid
Maximumdensityisat
4C
Veryimportantfor
fishincoldclimates

AIROCEANINTERACTION
Differencesinsolarenergy(heating)across
theEarthcombinedwiththeEarthsspin
createwinds
Windscarrythemoistureawayfromocean
Likewise,certainatmosphericphenomenaare
manifested(originate)intheoceansviz.
cyclones,storms,hurricanesetc.

AIROCEANINTERACTION
Earthsatmosphereiscomposedmainlyof
Nitrogen,Oxygen,andWaterVaporexact
compositioninnextslide

Airisnevercompletelydry,howeverwatervapor
(H2O)maybeashighas4%
Amountofmoistureisexpressedby:
Absolutehumidity:isthetotalmassofwatervapor
presentinagivenvolumeofair.
Relativehumidity:istheratioofpartialpressureof
watervaportothesaturatedvaporpressureofwaterat
agiventemperaturegenerallyonascaleof100.

COMPOSITIONOFAIR(DRYBASIS)

CO2levels:
6500yearsbefore=180ppm
August1,2015=399.54ppm

AIROCEANINTERACTION
Temperatureandhumiditydeterminethe
densityofairmasses,whichinturndetermines
whethertheseairmasseswillriseorsink
Aircontainingwatervaporislessdensethan
dryairatthesametemperature
Also,whenheated,airexpandsandbecomes
lessdense
Thismeansthatcoldairisdenserthanwarm
airandcold,dryairismuchdenserthan
warm,moistair

AIROCEANINTERACTION
Moistairislessdensethancoldairbecause
theweightofwatervapor(H2O)islessthan
thatofNitrogen(N2)andOxygen(O2)
Whenwatervaporincreasesinair,theamount
ofO2andN2decreasesperunitvolume
MolecularweightofO2=16+16=32
MolecularweightofN2=14+14=28
MolecularweightofH2O=1+1+16=18

ATMOSPHERICCIRCULATION
Air masses will move from regions of high
pressure(denseair)toregionsoflowpressure
(lessdenseair)
A low pressure zone results from moist
and/orwarmair
A high pressure zone results from dry
and/orcoldair
The flow of air from regions of high to low
pressurecreatethewinds

ATMOSPHERICCIRCULATION
Because warm and/or moist air is less dense, it
rises
Likewise, cool and/or dry air is more dense and
soitsinks
Asairrises,itexpandsandcools;watervaporin
rising, expanding air will condense into clouds
becausethecoolerairisnolongerabletoholdas
muchwatervapor
Precipitationresults

CAUSESOFPRECIPITATION

COMPARISON OF THE SIZE OF THE CONDENSATION NUCLEI TO

THE SIZE OF TYPICAL CONDENSATION DROPLETS

PRECIPITATION(RAIN)
Single strongest variable driving hydrologic
processes
Formed by water vapor in the atmosphere
As air cools its ability to hold water
decreases and some turns to liquid or ice
(snow)

WEATHER VS. CLIMATE PATTERNS

Weather (day to day) vs. climate (yearsdecades and patterns - Monsoon)
Climate and geography result in biome
classification

BIOMES AND RAINFALL

Snowfedforest

 Group

BIOMES

of ecosystems with the same climate and

dominant communities

Tropicalrainforest
Tropicaldryforest
Tropicalsavanna

Temperategrassland
Desert
Temperatewoodland
andshrubland

Temperateforest

Tundra

Northwestern
coniferousforest

Mountainsand
icecaps

Borealforest
(Taiga)

WATERANDPOLLUTANTUPTAKEIN
PLANTS
Fig.4.4

PLANT TRANSPIRATION (POLLUTANTS PICKUP)

Most water absorption occurs in upper half of root zone
Pollutants are picked up from agriculture operations/
polluted water usage on land

A TYPICAL CASE OF POLLUTANT TRANSPORT (MERCURY)

Up the Food Chain

Atmosphere-Surface Water Interactions:

Mechanism behind the Sustenance of Aquatic
O Life
2

O2 is central to the sustenance

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

RAINWATER DROPLET IN THE AIR

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.

CO
2

NH

N
O2

SO

Dus
t

Aeroso
ls

Organ
ic
acids

Many of the species establish a quick equilibrium, thus

imbibing impurities even before the rain water reaches the
earth surface.

Gas-Liquid Partitioning:
Henrys Law

pA

William Henry in
1803
constant
temperature,

At a
the
amount of a given gas that dissolves
in a given type and volume of liquid
is directly proportional to the partial
pressure of that gas in equilibrium
with that liquid.

[A]a
Gas - Liquid
System

An equivalent way of stating the law is that the

solubility of a gas in a liquid is directly
proportional to the partial pressure of the gas
above
the liquid.
For any species
A,[ A] p
[ A]aq K H p A
aq
A
KH

[ A]aq
pA

KH is called the Henrys Law

constant

M
unit :
atm.

Partial Pressure and Molar Concentration

Ideal Gas
pV nRT R = 0.0820578 L. atm/(K.mol)
Law:
n
P
Molar
C
V RT
concentration:
Daltons Law: The pressure exerted by a mixture of gases
in a fixed volume is equal to the sum of the pressures
that would be exerted by each gas alone in the same
Pvolume.
=p +p +
tot

= (nA + nB +
)RT/V
= (ntot)RT/V

The atmosphere
(by volume)
N2
78%
O2
21%
Ar
0.9345%
CO2
0.038%
Other gases Rest
Partial pressure of O2 = pO2 = 0.21*Ptot=0.21*1
atm =0.21 atm
Partial pressure of CO2 = pCO2 = 0.00038*1 atm
=3.8*10-4 atm

Example

Find out the aqueous solubility of oxygen in a fully

aerated water at 25 oC in a watewater treatment plant.
KH of O2 at 25 oC = 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
[1M O2= 32
= 8.467 mg/L
g/L]

Henrys law constant is

temperature
The value of Henrysdependent
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

CARBONDIOXIDEWATERINTERACTION:
NATURALACIDITY
Carbon Dioxide (CO2) makes up approximately 0.0399
% of the Earths atmospheric gases now.
Carbon dioxide concentrations in the atmosphere is
regulated by:
Removal of CO2 from the atmosphere as green plants fix the
CO2 into complex carbohydrates- photosynthesis process
Exchanges of CO2 between the atmosphere and the oceans
Dissolution of CO2 in rain water
Chemical reactions between the rain water and limestone CaCO3(s) + H2CO3(aq) = Ca(HCO3)2(aq)

CARBONDIOXIDEWATERINTERACTION:NATURALACIDITY
Unlike dissolution of oxygen, gases like
CO
carbon dioxide, sulfur oxides or nitrogen
2
oxides after dissolution form further
hydrated species which add acidity to the
Carbon
water. dioxide is a natural
CO2
constituent of atmosphere. The
acidity imposed by carbon
(aq.)
dioxide is referred as natural
+
H
When carbon dioxide dissolves
acidity.
+HCO3in water it forms aqueous
H+
carbon dioxide which is
+CO32popularly 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.

Carbon dioxide : Natural Acidity

-1.5
(DeterminationCO
of(pH)
K
=10
g
)

CO
(
aq
.)
H
2
2
M/atm.

According to Henrys Law:

[CO2 ]aq K H pCO2 10 1.5 pCO2

CO2 (aq.) H HCO3

Ka1 =10

-6.3

[ H ][ HCO3 ]
K a1
10 6.3
[CO2 ]( aq.)
[ HCO3 ]

K a1[CO2 ]( aq.)

[H ]

10 6.3 * K H pCO2
[H ]

HCO3 H CO32

Ka2

Ka2 =10

10 7.8 pCO2
[H ]
-10.3

[ H ][CO32 ]
10.3

10
[ HCO3 ]

10
K
[
HCO
2
a2
3 ]
[CO3 ]

[H ]

10.3

*10 7.8 pCO2

2

[H ]

10 18.1 pCO2
[ H ]2

Carbon dioxide : Natural Acidity (Determination

ofCharge
pH)
Balance: The sum of the equivalent
concentration of cations is equal to the sum of
equivalent concentration of anions.

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

Because for divalent ions,

equivalent conc. = 2 X
molar
conc.
7.8
18.1

[H ]

10

pCO2

[H ]

2*

10

pCO2

[ H ]2

10 14

[H ]

In atmosphere, there is 370 ppm of carbon dioxide on

mole basis.
pCO2 370 *10 6 atm.
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

Carbon dioxide : Natural Acidity

11.2
21.of
5
(Determination
pH)
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 10 6.3 *10 1.5 * pCO2

[ H ] 10 6.3 *10 1.5 * pCO 2

EXAPMLE
Find out the pH if the atmospheric CO 2
-6
concentration
is doubled.
pCO2= 2*370*10
atm. =103.13

[ H ] 10 6.3 *10 1.5 *10 3.13

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 (hypothetical,

Actual=
[ H ] ?)10 6.3 *10 1.5 * 5
pH log[ H ] 3.56

120 kPa at 4oC and 250

kPa at 20 oC

 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
man-made activities, pH of
rainwater becomes lower than 5.7
ACID RAIN
Major contributors to acid rain :
H2SO3, H2SO4 and HNO3

EXAMAPLE
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 ; 0.096
Ka2=10-7.21

KH =10

SO2 ( g ) SO2 (aq.)

M/atm.

According to Henrys Law:

[ SO2 ]aq K H pSO2 10 0.096 pSO2

Ka1 =10

-1.77

[ H ][ HSO3 ]
K a1
10 1.77
[ SO2 ]( aq.)
[ HSO3 ]

K a1[ SO2 ]( aq.)

[H ]

pSO2 = 5*10-9
atm.

10 1.77 * K H pSO2

[H ]

[ HSO3 ]

10 1.674 pSO2
[H ]

10 1.674 pSO2
[H ]

10 9.97

[H ]

HSO3 H SO32
Ka2

K a 2 10 7.21

[ 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

Mathura Refinery 58 km by road and 46 km (air)

from Agra
Acid rain damaged the shine of Taj
Sulphur recovery systems installed at Refinery
now
The cupolas in Taj trapezium relocated

RECOVERY OF GASES FROM BIPHASIC

FLUIDS
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 biphasic
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

DISSOLVED GASES USAGE - POWER

GENERATION

CASE STUDY: LAKE NYOS

DISASTER

On August 21, 1986, more than 1700 people and

numerous wild lives were lost 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 size and 250 m
deep. Under the bed, the volcano is
leaking carbon dioxide into the

High partial pressure of

CO2, High conc. of
bicarbonate and low pH

About
250 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 air, unless there

is a strong dispersion force such as high wind, it
tend to be at the bottom of the atmosphere, causing

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

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
CO
equilibrium
with
the
air.
So, the relevant

The situation
2
reactions are:
is :
CO2 ( g ) CO2 (aq.)
KH =10 -1.5
CO2
M/atm.
(aq.)
CO2 (aq.) H HCO3 Ka1 =10
H+
-6.3

2
HCO3 H CO3
Ka2 =10
+HCO3Als
2
2
o,
CaCO

Ca

CO
3
3

-10.3

KSP =10
-8.42

Ca2+
+CO32CaCO3

H+
+CO32-

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
K
[
HCO
2
a2
3 ]
[CO3 ]

[H ]

10.3

From solubility of calcium

carbonate,

[Ca 2 ]

K sp

2
3

[CO ]

K sp [ H ]2

10 18.1 pCO2

*10 7.8 pCO2

2

[H ]

10 18.1 pCO2
[ H ]2

10 8.42 [ H ]2 109.68 [ H ]2

18.1
10
pCO2
pCO2

Hence,

2*

10

9.68

[H ]

pCO2

[H ]

14

10

[H ]

10 7.8 pCO2

[H ]

2*

10 18.1 pCO2
[ H ]2

pCO2= pressure exerted by 370 ppm (by volume)

gas= 370 * 10-6 atm
14
7.8
6
18.1
6
109.68 [ 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
1013.41[ H ]2 [ H ]

[ H ] [ H ] [ H ]2

For a test case, lets consider that

[H+]=10-7
0.59
7
7
4.23

10

10 10 10

10 7.23

This means that only first term and second term in the
equation is significant for obtaining an approximate
solution.
10 11.23
3
24.64

1013.41[ H ]2

[H ]

[ H ] 10

[ H ] 10 8.21

pH=
8.21

[Ca ]

10

9.68

[ H ] 10 8.21

[H ]

pCO2

p CO2 360 *10 6 atm

9.68
8.21 2
10
[
10
]
2
4
[Ca ]

5
.
05
*
10
M
6
360 *10

[Ca 2 ] 20mg / L

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

for lowering
the pH.
Hunavailable
CO 2 HCO
H HCO
CO (aq.) H OH H O
3

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 CaCO
3.
SOLUTION
Estimate
all the acid buffering ions.
pH
=10

[ H ] 10 10

[OH ] 10 4

pOH =
4

3
32
*
10
g/L
232 mg/L of CO3
0.53 *10 3 M 10 3.27 M
60 g / mole

HCO3 H CO32

Ka2

Ka2 =10

-10.3

[ H ][CO32 ]
10.3

10
[ HCO3 ]

2
10
3.27
[
H
][
CO
]
10
*
10
2.97
3
[ HCO3 ]

10
Ka2
10 10.3
Alkalinity ( M / L) [ HCO3 ] 2[CO32 ] [OH ] [ H ]

102.97 2 * 103.27 104 1010

 ] 2[CO 2 ] [OH ] [ H ]
Alkalinity ( Meq / L) [ HCO3

3
10 2.97 2 *10 3.27 10 4 1010

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 Meq/L CaCO3 = 50 g/L of CaCO3

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

CaCO3