ES 722

GEOHYDROL
OGY

Recommended books
Fundamentals of groundwater F.W. Schwartz and H. Zhang

Groundwater Science C.R. Fitts

Geochemistry, groundwater and pollution C.A.J. Apello and D. Postman

Physical and Chemical hydrogeology P.A. Domenico and F.W. Schwartz

Environmental Hydrology A.D. Ward and S.W. Trimble

Groundwater R.A. Freeze and J.A. Cherry

Groundwater Hydrology D.K. Todd

Etc

Recommended Journals

Journal of hydrology

Water research

Hydrological science journal

Etc

Water and energy cycles

The most abundant substance on earth surface.
1.4 billion km3 in all three phases: liquid, ice and water.
Inventory of water on earths surface
Reservoir

Volume(106km
3
)

% of total

Oceans

1370

97.25

Ice caps & glaciers

29

2.05

Deep groundwater(7504000m)

5.3

0.38

Shallow
groundwater(<750m)

4.2

0.30

Lakes

0.125

0.01

Soil moisture

0.065

0.005

Atmosphere

0.013

0.001

Rivers

0.0017

0.0001

Biosphere

0.0006

0.00004

Structure of Water
Covalent bonds between H and O
105o angle H-O-H
Water molecule is polar
Hydrogen bonds join molecules

105o

tetrahedral structure
Polar molecules bind to charged species
to hydrate ions in solution

Groundwater Hydrology
Science of occurrence, distribution and movement of water bodies on the
surface of the earth.
Geohydrology has an identical connotation.
Groundwater hydrology

engineering applications

Hydrogeology

geology

Why study groundwater?

Key source of drinking water

Groundwater makes up only 0.06% of the earths available water, however,

it represents 98% of the freshwater readily available to humans

Distribution of water stored on earth

(in U.S.A)
Pool of water/
reservoir

Stored
volume(km3)

Detention
period(year)

Glaciers

67

40

Freshwater lakes

19,000

100

Salt lakes

58

10

Streams

50

0.03

Shallow (800m)

63,000

200

Deep (>800m)

63,000

10,000

Soil moisture

630

0.2

Atmosphere

190

0.03

Groundwater

Groundwater
Mean water occupying all the voids within a geologic stratum
Groundwater and the hydrologic cycle

Groundwater occurrence

Soil water zone

Vadose or unsaturated zone
Phreatic or saturated zone

Water table: imaginary surface separating saturated and

unsaturated zone
Groundwater: water occurring in the zone of saturation,
below water table

Water balance equation

Input-output = change of storage
Water moving in the hydrological cycle is neither gained nor lost

Water balance for land

P-E-T-Ro=S
P=Precipitation on land
E= evaporation from land
T=transpiration from land
Ro= Total outflow from land to oceans
S= change of water storage on land
and under land
Unit= volume/time(L3/T)

Example: On a global scale, it is known that P=4200bgd, E+T=2900bgd and

Ro=1300bgd. Calculate the water storage on the land area.

BASIC PRINCIPLES OF GROUNDWATER FLOW

POROSITY
Ratio of void volume to the total
volume of material
nT = Vv = VT Vs
VT

VT

nT= Porosity
Vv=Vol. of voids,
Vs= Vol. of solid
VT= Total vol.
Porosity is expressed in percentage(%)

POROSITY
2Types

PRIMARY
*Original interstices
*Eg. Pores in soil or

SECONDARY
*After rock was formed
*Eg. Joints, faults,

fractures
sedimentary rocks,

in Ig. Sedi & Meta. rocks

vesicles, lava tubes and

& solution openings in

cooling fractures in basalts.

carbonates

Primary and Secondary porosity

Porosity in terms of bulk density

nT = 1 - b
s
s = Bulk density, s = Grain density(solids)
Porosity depends on: * Degree of compaction
* Shape of grains
* Particle size distribution
What is Strongly/ poorly sorted??

WELL SORTED
Coarse (sand-gravel)

POORLY SORTED
Coarse - Fine

WELL SORTED
Fine (silt-clay)

Permeability and Hydraulic Conductivity

High

Low

Sorting of material affects groundwater movement. Poorly sorted (well graded)

material is less porous than well-sorted material.
S. Hughes,

Range in value of porosity

Material

Porosity
Sediments

Gravel

24-38

Sand

26-53

Silt

34-61

Clay

34-60

Sedimentary rocks
Sst.

5-30

Siltstone

21-41

Lst./dolomite

0-41

Shale

0-10

Crystalline rocks
Fractured crystalline

0-10

Basalt

3-35

Weathered granite

34-57

Effective porosity
Ratio of the volume of the interconnected interstices to the total
volume of the soil/rock
Effective porosity can differ significantly from the total porosity
Porosity%

Effective Porosity
%

Anhydrite

0.5-5

0.05-0.5

Limestone

0-40

0.1-5

Granite

0.1

0.0005

DARCYS LAW

K= Constant of proportionality, hydraulic conductivity;

=Darcy velocity(q) or specific discharge

Velocity of flow Hydraulic gradient

= Hydraulic gradient

LIMITATION OF DARCYS LAW

Darcys equation is valid for laminar flow
turbulent flow- more tortuous path
Actual flow velocity/pore velocity is greater than the Darcy velocity
RELATION B/W PORE VELOCITY AND DARCYS VELOCITY
Pore velocity/ Linear velocity is the volumetric flow rate per unit interconnected
pore spaces.
V= pore velocity; ne =effective porosity; q= darcy velocity
Pore velocity--True velocity, Darcy velocity/ specific discharge--Apparent velocity
Av voids

A = total area

Reynolds no.

Dimensionless ratio of inertial to viscous forces

Distinguish between laminar and turbulent flow

NR = vD

NR= Reynolds no., v= velocity, D=dia. of pipe (effective grain size d 10), =
viscosity of fluid

Darcy law is valid for NR<1 (upto10)

In sedi. rocks subjected to compaction, measurement shows that porosity

decreases with depth of burial.

nz= no e-az
nz=porosity at depth z, no= porosity at surface, a= constant

Hydraulic head
Energy available to flow
Higher the water level, greater the energy for flow
o Piezometer: field
o Manometer: lab

Hydraulic head relates to elevation, pressure and velocity

Groundwater, flow velocity is slow, neglecting energy contained in
velocity

With reference to fig.(previous), assume that the elevation of the ground surface
is 1000m above sea level, depth of water is 25m, total length of the piezometer is
50m, water density= 1000kg/m3. What are (a). Total hydraulic head at the measurement point
(b). Pressure head
(c). Pressure
(g=9.81m/s2; 1 Pascal= 1kg/m/s2)

Hydraulic gradient and groundwater flow direction

Hydraulic gradient= Change in hydraulic head in given direction
-ve sign indicates flow of water in the direction of decreasing head

Lines of equal hydraulic gradient= Equipotential lines

Hydraulic Gradient defines the direction of flow from region of high hydraulic head
to low hydraulic head.

At a minimum it takes 3 hydraulic head measurements to determine the hydraulic

gradient and the direction of groundwater flow.
B(h=140m)
B(h=140m)
316m

316m
300m

300m

D
95m
959

A
(h=140m)

100m

C
(h=140m)

A
(h=140m)

83
100m m

iCD = hC-hD
CD
Find out hydraulic gradient and flow direction?

B
(h=150m)

Hydraulic conductivity and permeability

Constant of proportionality relating the specific discharge to the hydraulic
gradient
Parameter describing the ease with which flow takes place
Large values for permeable units sands, gravels
Small values for poorly permeable units clay, shale
Unit of velocity= (L/T), m/day
Q. Groundwater flows through a buried valley aquifer with a cross-sectional area
of 1.0106m2 and a length of 2104m. Hydraulic heads at the
groundwater entry and exit points in the aquifer are 1000m and
960m resp. At the downstream end of the aquifer, groundwater
discharges into a stream at a rate of 1.0105m3/day.
1.

What is the hydraulic conductivity of the aquifer?

2.

If effective porosity of the material is 0.3, what is linear groundwater velocity?

Representative values of hydraulic conductivity

Material

Hydraulic conductivity

Gravel

310-4-310-2

Fine sand

210-7-210-4

Clay

110-11-4.710-9

Lst.

110-9-610-6

Shale

110-13-210-9

Basalt

210-11-4.210-7

Ig. And Meta. rocks

310-14-210-10

INTRINSIC PERMEABILITY
Hydraulic conductivity depends on both properties of the porous medium and
the fluid(density, viscosity)
DARCY EQUALTION IN THE FORM OF PROPERTIES OF MEDIUM
AND FLUID
Intrinsic permeability of a rock or soil is a measure of its ability to transmit
fluid as the fluid moves through it.
Permeability is independent of the fluid
UNIT

1m 2 = 1.0131012 darcy; 1 darcy= 9.8710-9 cm 2

Relation between hydraulic conductivity and permeability

Where, w=998.2kg/m3, = 1.00210-3 kg/cm.sec

k=(1.02310-7m.sec)K
Q. What is intrinsic permeability of a water saturated medium that has a hydraulic
conductivity of 15.24 m/day?

Hydraulic conductivity of geologic material

Depends on variety of physical factors:
Porosity
Particle size and distribution
Shape of particles
Empirical estimation of K:
K= Cd210

(Hazen)

C= constant, 100 to 150(cm/s-1)

for loose sand
d10= effective grain size cm
(10%particles finer, 90% coarser)

Fig. Hydraulic conductivity of various proportion of two

uniform sands

Laboratory measurement of K

Constant head permeameter

K = QL
AH
a= Cross-sectional area of standpipe

Falling head permeameter

 From Darcy law it follows, groundwater movement depends on:

Hydraulic conductivity of an aquifer
Hydraulic gradient
Groundwater velocities, vary normally between 2m/year to 2m/day
Q. K=75m/day, i= 10m/1000m. What is Darcy velocity?
TUTORIAL
Q1. In an experiment, groundwater flows through a sediment column
(43.5 cm in length and 5cm in diameter) at a rate of 4.4 ml/min. The
porosity of the sediment is 0.4. Calculate the Darcy velocity and
linear groundwater velocity. If the hydraulic conductivity is 0.11
cm/s, calculate the hydraulic gradient.

Q2. In a constant head test, the Darcy flux is 5 cm3/s for a column of 5cm in
diameter and 50 cm in length. The constant head is 60 cm.
Calculate the hydraulic conductivity.
Q3. In a falling head test, the initial head at t=0 is 60 cm. At t=30min, the head is
57 cm. The diameters of the stand pipe and the specimen are 1cm and 20 cm
respectively. The length of the specimen is 20 cm. Calculate the hydraulic
conductivity and intrinsic permeability of the specimen.
Q4. What is the intrinsic permeability of a water saturated medium that has a
hydraulic conductivity of 15.24m/day?
Q5. If d10= 0.004mm, what is the K and k? c= 6.5410-4

Darcy law for anisotropic material

Directional dependency
Permeability is same in all directions- isotopic
Davis(1962)- In bedded sediments, permeability is greater in the direction of stratification and
smaller perpendicular to stratification
Darcy law in anisotropic materials:
q= -Kh --------------------------------------------(1)

qzz

qyy
qyx
qzx

In Cartesian coordinates
qx
qxy
z
qxx

q= qxi + qyj + qzk ------------------------------------(2)

-h= hi + hj + hk
x
K= kxx

-----------------------------(3)

qy
z

kyy kzz

kyx

kyy kyz

kzx

kzy

-----------------------------(4)

kzz

Where i, j, k are unit vectors along x, y and z directions

qyy
qy
x

When equations (1) and (4) are combined, the Darcy velocity vector may be
broken down into components in x- y- z- directions
qx= -Kxx h- Kxy h Kxz h----------------(5)
x
y
z
qy= -Kyx h- Kyy h Kyz h----------------(6)
x
y
z
qz= -Kzx h- Kzy h Kzz h----------------(7)
x
y
z
Where, Kxy= Kyx, Kxz=Kzx, Kyz= Kzy--------(8)
If the principal directions of anisotropy coincide with x-, y-, z- directions, the nondiagonal components of hydraulic conductivity tensor in eq. (4) becomes zero.
Kxy=Kyx=Kxz=Kzx=Kyz=Kzy=0----------------(9)
And the Darcy velocities in the x-, y- and z- directions are
simplified as,
qx = -Kxx h-------------------(10)
x
qy = -Kyy h-------------------(11)
y
qz = -Kzz h-------------------(12)
z

Hydraulic conductivity in horizontal and vertical direction

Darcy equation:
Homogenous ad isotropic, value of K was same in all directions.
Rarely, particularly for undisturbed unconsolidated alluvial material
Anisotropy is the rule, where directional properties of hydraulic conductivity
exists
Different layers, different K values
qz
q1

Z1

K1

q2

Z2

K2

Kx= Hydraulic conductivity in horizontal direction

Kz= Hydraulic conductivity in vertical direction
Kx/Kz= 2-10 for alluvium, for clays values up to 100 or more.

Q. Consider a 300m sequence of interbedded sst. & shale that has 75% sst. The
sst has a horizontal & vertical hydraulic conductivity of 10 -5m/s , shale has a
horizontal and vertical hydraulic conductivity of 1.9210 -12m/s. Calculate the
equivalent horizontal and vertical hydraulic conductivity.

Occurrence of groundwater
Aquifers and confining beds
Aquifer is a geologic unit that stores and transmits water.
Aquifer can be co-existence with geologic formation, a group of formation, or a
part of a formation.
Confining beds- Units of low permeability that bounds aquifer.
Aquifer: Groundwater reservoir or water bearing formation
Unconfined aquifers: Water is in contact with atmospheric pressure
drill and well hit the water table.
Confined

aquifers:

Confinement

of

the

water

between

impermeable layers.
Potentiometric surface: is defined by the heads measured in wells in a confined
aquifer.
Artisian aquifer: Water flows to surface under pressure, without

1. Aquiclude: A saturated but relatively impermeable material that does not

yield appreciable quantity of water. E.g. Clays
2. Aquifuge: A relatively impermeable formation neither containing nor
transmitting water. E.g. solid granite
3. Aquitard: A saturated but poorly permeable stratum that impedes
groundwater movement and does not yield water freely to wells, but that
may transmit appreciable water to or from

Groundwater system

Specific surface: Water retention capacity

Diameter
of particle
, mm

Type

No. of
particles/
cm3

Total
surface
area, cm2

10

Gravel

3.14

Sand

1103

31.4

0.02

Silt

1.25108

1,570

0.002

clay

1.251011

15,700

Vertical distribution of groundwater

Vadose zone: Zone above water table, pore pressure < atmospheric pressure
Water table: pore pressure = atmospheric pressure
Phreatic zone: Water pressure > atmospheric pressure

Vertical cross-section showing groundwater terminology

Aquifers

High hydraulic conductivity

Confining layers /Aquitards

low hydraulic conductivity

Which is an aquifer?
E.g. Marine clay with K=10-9cm/s ; glacial till with K= 10-4cm/s
Glacial till K= 10-4cm/s; sand and gravel layer K = 10-2cm/s

Capillary rise
hc =

2 Cos
r

= surface tension
= specific weight of water
r= tube radius(pore space)
= angle of contact between the
meniscus & the wall of the tube
For pure water in clean glass, =0 &
at 20C, = 0.0749g/cm & =1g/cm3,
so that capillary rise approximates

Capillary rise is inversely proportional to pore size

Material

Grain size, mm

Capillary rise,
mm

Fine gravel

5-2

2.5

Coarse sand

1-0.5

13.5

Fine sand

0.2-0.1

42.8

Silt

0.1-0.05

105.5

Measurement of water content

1. Direct method- Heat, change in weight
2. Indirect method- Electrical & thermal conductivity

Transmissivity
The ease with which water moves through an aquifer.
It is the rate at which water of prevailing kinematic viscosity is
transmitted through a unit width of the aquifer under a unit hydraulic
gradient.

T= bK
b= thickness of aquifer; K= hydraulic conductivity
Q. Express Darcy law in terms of width of aquifer and transmissivity?
Q. The hydraulic conductivity of a confined aquifer with a thickness of
10m is 300m/s. Calculate the T?

Storativity
Ability to store water, drainage of water from pores.
It is the volume of water that an aquifer releases from or takes into storage per unit
surface area of the aquifer per unit change in head.
S= volume of water

= m3/ m3

(unit area)(unit head change)

Confined aquifers 10-3 to 10-5

Specific storage
Ss= volume of water
= 1/m
(unit area)(unit aquifer thickness)(unit head change)
RELATION BETWEEN STORATIVITY & SPECIFIC STORAGE

S= Ssb

Specific Retention(Sr)

Vr= Vol. occupied by retained water

VT= Bulk volume of soil/water

Specific yield(Sy)

Vd= vol. of water drained

RELATION WITH POROSITY

= Sr + Sy

Sr increases with decrease of grain size and pore size of a soil/ rock
Material

Porosity

Sy

Sr

Soil

55

40

15

Clay

50

48

Sand

25

22

Gravel

20

19

Limestone

20

18

Granite

0.1

0.09

0.01

Basalt

11

Q. After the soil is drained by gravity, the weight of the soil sample is
85g. After the sample is oven-dried, the sample weighs 80g. The bulk
density of the wet soil is 1.65g/cm3, & the density of water is 1g/cm3.
Calculate the Sy, Sr and of the sample. Assume water that was drained
by gravity is 20g.

Geologic formations as Aquifers

Types of
porosity

Sedimentary
Consol.

Intergranular

Uncons
ol.

Carbonat
es

Gravelsand
Clay
sand

Ig. and
meta.

Volcanic
Consol.

Weathe Weathere
red
d zone of
zone of
basalt
granite,
gneiss

InterBreccia,
granular Conglo
and
merate,
fracture
Sst.,
d
Shale

Zoogenic
lst.,
Calcareo
us grit

Volcanic
tuff,
Cinder
pumice

Fracture
d

Lst.
Dolomite

Granite,
Basalt,
Gneiss, Andesite,
Gabbro, Rhyolite
quartzit
e

Uncons
o.
Volcani
c
ejecta,
Ash

Hydro geochemical reactions & groundwater compositions

G.J. Chakrapani, IITR
Objective: To understand various rock-water reaction mechanism &
resultant water compositions.
To cover:
chemical background
equilibrium thermodynamics
activity- concentration relationship
dissolution-precipitation reactions
oxidation-reduction reactions
micro-organisms in groundwater

dissolved mass in groundwater

water quality standards
groundwater sampling
data presentation

References:
Fundamentals of groundwater- F.W. Schwartz & Zhang
The geochemistry of natural waters- J.I. Drever
Geochemistry, groundwater & pollution- C.A.J. Apello & D.Postman
Physical and chemical hydrogeology- P.A. Domencio & F.W. Schwartz

Ions, molecules or solid particles in water undergoes reactions.

Water chemistry: Hazardous to human or ecological health, decides water
use.
E.g. Mineral Fluorite (CaF2) and by doing solubility calculations we can
predict concentration ranges of Ca2+ and F- in groundwater.
Dissolved constituents:
Cations: +ve charge, Ca2+, Na+
Anions: -ve charge, HCO3, ClNonionic: uncharged, Most organic compounds(trichoroethene, TCE)
Halite dissolution: NaCl= Na++ ClCalcite dissolution: CaCO3+H+= Ca2++ HCO3TCE dissolution: TCE= TCEaq

Concentration scales
Molar concentration(M): No. of moles/litre of solution
1.42g Na2SO4=?M
Molal concentration(m): No. of moles/kg of solvent
Equivalent charge(eq/L): No. of equivalent charge of ion/litre of solution
Mass per unit mass: ppm, ppb, mg/kg, mg/g
Mass per unit volume: mg/L
Molarity= mg/L10-3
formula weight
meq/L= mg/L
formula weightcharge
Q. The concentration of SO42- in water is 8.5 mg/L. Express the concentration as
molarity and meq/L.

Equilibrium Kinetics
aA + bB + = cC + dD +
Keq = (C)c(D)d...

(A)a(B)b
Law of mass action
K=Equilibrium constant
When a reaction is at equilibrium in a closed system, there is no chemical
energy available to alter the relative distribution of mass between the
reactants and the products in a reaction.
Dilute solution- concentration units can be used

Activity- concentration Relationship

If a solution of the two species A& B has the properties that the energy of
reaction between two A molecules is identical to the energy of interaction between
an A molecule & a B molecule, or between two B molecules, the solution will be
ideal.
In real solution of groundwater these conditions are not met.
Electrostatic interactions between charged ions
Once a solution is no longer dilute, to use thermodynamically effective
concentration or activities instead of actual concentrations.

ai Ci
ai= log iCi
(log i= activity coefficient)
log i= -AZi2(I)0.5A
A= constant(function of temp.); Zi= ionic charge
I= ionic strength (I= miZi2)
Computer codes- SOLMNEQ, EQ3/6, PHREEQE

Free Energy
Change in Enthalpy :
H2 + O2 H2O + 68.3 Kcal
H = Hprod. - HReac. = -68.3 Kcal
2H2 + O2 2H2O

H = -136.6 Kcal
Exothermic reaction :

H = - ve

Exothermic reaction :
H = +ve
N2 +O2 = 2 NO
H = +43.2Kcal.
NaCl = Na+ ClH = +0.9Kcal.
If the equation reverses, the sign changes.
Heat of Formation of a reaction: can be added/subtracted.
H2S + 3O2 2H 2O +SO2
H2 +S H2S H = -4.8Kcal.
H2 + O 2 H 2 O

H = -68.3Kcal.

Change in equilibrium constant with temperature:

Vant Hoff equation:
dlnK / dT

H / RT2

R = Gas constant , PV = nRT

(1.99cal/ mol)
d In K = In K = H/ R

dT/ RT = - H/T2 + C

Where C in a c constant of integration

log

K =

- H

2.303RT

2.303 x 1.99 x 298 (250C) = 1,364 cal or 1.364 KCal

How to use this equation ?

CO + H2O = CO2 + H2 at 4170C, K = 10
H = - 10.2 KCal
From Table
Putting these values, integration constant C can be found out,
log 10 =
+10.2
+C
2.303x0.00199x690

(Kcal/mol)

0.00458
C = - 2.24
How to use this equation ?
CO + H2O = CO2 + H2 at 4170C, K = 10
H = - 10.2 KCal
From Table
Putting these values, integration constant C can be found out,
log 10 =
+10.2
+C
2.303x0.00199x690

0.00458
C = - 2.24

(Kcal/mol)

Now to find K at another temperature, say 25 C, the equation can be used with
the value of C
logK = 1.2/ (0.00458 x 298) - 2.24 = 5.26
K = 105.26 = 1.82 x 10 5 (at 25 C)
K = 10 at 4170C
Kequil. Decreased with increase in temperature
300

10

2.0

logSiO2 (ppm)

ppm SiO2

100

Solubility of silica
as a
function of temperature

1.0
0.003 1/T 0K
25 c

0.002
200c

Enthalpy changes as a measure of reactivity

KNO3 K+ + NO3-

H = +8.4 Kcal.

Enthalpy - not an infillible measure of the tendency of a reaction to take place

A + B A, B

H = 0

Tendency to react = H - D
The measure of degree of disorder is a quantity called Entropy
( = quotient of energy divided by absolute temperature)
D = TS

S = q/T

F = H -T S
H2 + O 2 = H 2 O

F = -56.7Kcal.

H2 O = H 2 + O 2

F = +56.7Kcal

2H2O = 2H2 + O2

F = +113.4Kcal

Free energy of formation

SO2 + CO2 = SO3 + CO
-71.7
-94.3
-88.4
-32.8
F = ?
Free energy as a criterion of equilibrium:
F < 0 , Spontaneous reaction
F > 0, Energy to be supplied
F = 0, Equilibrium

Relation : F K equili.

F = -RTlnK +RTln [Y]y[Z]z/ [B]b[D]d....

F0 = -RT lnKa

= -2.303 x 1.99 x 298 x log Ka

=0, at unit activity
= -1.364 log K
(F 0 in Kcal)
CaSO4 = (Ca2+) (SO42-) Kequil = 3.4 x 10-5
F = ? Predict the reaction !
Oxidation of galena to anglesite
PbS + 2O2 = PbSO4
F = -171.8 Kcal.
-22.1
0
-193.9
K=?

Q.

Given a groundwater with the molar concentration as follows. Calculate

the saturation state with respect to Calcite and dolomite. The activity
coefficients for Ca2+ , Mg2+, CO32- are 0.57, 0.59, 0.56 respectively. The
equilibrium constants defining the solubility of calcite and dolomite are
4.9 10-9 and 2.7 10-17 respectively.
Ca2+ = 3.74 10-4
Mg2+=4.11 10-6
CO32- =5.5 10-5

Ion Activity Product

IAP= [C]c[D]d
[A]a[B]b
IAP>K; precipitation; IAP=K; equilibrium; IAP<K; dissolution
CaSO4=Ca2+ + SO42When IAP/K<1, the groundwater is under saturated with respect to
the given mineral
When IAP/K=1, equilibrium with mineral
When IAP/K<1, under saturation

Oxidation- Reduction Reaction

Oxidation- Reduction Reaction or redox reaction are enormously important in
controlling the geochemistry of natural water.
Involves transfer of e- and are medicated by microorganisms as
catalysts.
Oxidation: Fe2+ Fe3+ + eReduction: Fe2+ Fe3+ + eOx1+ Red2 = Red1 + Ox2
Where Ox and Red refer to oxidants and reductants respectively.

Mass law expression for the half-reaction

Ox+ ne- = Red
K= [Red]/[Ox] [e-] n
1/n

In the same way pH defines [H+], pe defines electron activity [e-]

When a half-reaction is written in terms of a single e- or n=1, the logK term is

written as pe0.

Example: A groundwater has (Fe2+)=10-3.3M and (Fe3+)=10-5.9 M. Calculate the pe at

250 C assuming that the activities of Fe species are equal to their concentrations.
What would be the measured Eh of the solution?
From standard tables:
Fe3+ + e- Fe2+ with pe0= 13.0

Ion Exchange
Important process in groundwater chemistry, especially where clays prominent
(e.g. many soils)
Mineral surfaces often bind cations and anions.
Because these ions are held loosely, there is an opportunity for them to
exchange with ions in solution.
Ca2+ + Na-clay = 2Na+ +Ca-clay
Mg2+ + Na-clay = 2Na+ +Mg-clay
+

+ +

+ - - +
+ +-

--

--

Solution

- -

Retardation of pollutant cations in groundwater

VA+= velocity of cation A+

V= velocity of groundwater
= bulk density of sediment
= porosity of sediment
Kd= distribution coefficient

Groundwater composition
Major constituents (>5 mg/L)
HCO3-, Ca2+, Cl-, Mg2+, SiO2, Na+, SO4 2Minor constituents (0.01-10.0 mg/L)
B, CO3-, F, Fe, NO3, K, Sr
Trace constituents (<0.01 mg/L)
As, Al, Ba, Be, Co, Cd, Cu, Ga, Au, Mo, Mn, Ni, Ag, Zn, Th, U,
PO43Organic compounds (shallow)
Humic acid, fulvic acid, amino acids, hydrocarbons, tannins and
lignins
Organic compounds (deep)
Acetate, Propionate

Evaluating Electrical Neutrality

Cations

Mg/L

Meq/L

Ca2+

1.0

0.05

Mg2+

1.0

0.08

Na+

550

23.9

K+

3.5

0.09

Fe

8.7

0.31

Total

24.4

Anions

Mg/L

Meq/L

HCO3-

1315

21.6

SO42-

59

1.22

Cl-

45

1.27

F-

0.25

0.01

Total

24.1

Cation/Anion ratio = 1.01

NICB - Net Inorganic Charge Balance

NICB = Tz+ - Tz-/Tz+ 100

Hardness of water
Presence of divalent metallic cations (Ca2+& Mg2+)
Reacts with soaps to form precipitates
With HCO3-, forms scales
HT= 2.5 Ca + 4.1 Mg
Where HT, Ca & Mg are measured in mg/L
Hardness

Water class

0-75

Soft

75-150

Moderately hard

150-300

Hard

>300

Very hard

Microorganisms in groundwater
Occur ubiquitously
Bacteria, protozoa, fungi
Quantifying??
Water (sterile), soil samples, water slurry, incubate, count bacterial colonies
CFU/ml Colony forming unit per milliliter
MPN Most portable number

Water Quality Standards

Chemical analysis are commonly used to determine whether water needs
various standards for use by human or for support of the of aquatic
ecosystem.
Water quality standards changes quite often & vary from country to
country.
USA-NPDWR, India- WHO, BIS, NIH
MCL(Maximum contaminant level) Highest level of a contaminant that
is allowed in drinking water. MCLs are enforceable standards that must be
met by public drinking water system.
MCLG(Maximum contaminant level Goal) Level of contaminant in
drinking water below which there is no known or expected health risk.

Representing chemical data

(a). Bar diagram

(b). Pie diagram

(c). Piper diagram

(d). Stiff diagram

Graphical representation of chemical data

Mg/
L

SiO2

35

55

31

SiO2

13

29

14

SiO2

4.3

19

SiO2

8.4

SiO2

10

19

11

18

17

21

20

44

123

74

35

5.1

27

126

5.6

11

70

9.5

33

1.0

5.7

43

12

9.6

60

61

24

28

4.5

16

13

3.5

3.5

0.4

4.1

2.2

7.0

1.3

3.8

0.7

2.1

SiO2

72

177

74

327

539

277

241

80

138

440

SiO2

6.9

15

0.1

22

283

19

88

13

9.6

319

SiO2

3.8

6.9

8.8

4.4

3.5

24

2.5

8.0

14

Isotope and age dating

Widely used n groundwater hydrology

Stable and radiogenic varieties
Stable isotopes ---- used for flow systems, tracing and climate reconstruction
Radiogenic isotope ---- to date
Isotopes are atoms of the same element that differ in terms of their mass
1H (stable) 2H 3H (Radiogenic)
3H
3He
During decay isotopic concentration changes due to processes like evaporation,
condensation and water-rock interaction
In groundwater studies: H, O, C & S are useful(low atomic no.)

Hydrogen:

H (99.98% abundance) ,

H (0.015) ,

H (10-14 to 10-16)

RADIOACTIVE
Oxygen:

16

O (99.76%), 17O (0.037), 18O (0.10) RADIOACTIVE

Carbon: 12C (98.89%), 13C (1.11), 14 C ((10-10) RADIOACTIVE

Sulphur:

32

S (95.02%), 33S (0.75), 34S(4.21), 36S (0.02)

Groundwater studies involves: 2H or D, 18O , 13C and

34

One isotope dominates the rest in terms of abundance, thus changes due to
fractionation are too small to measure accurately.
Positive or negative deviations of isotope ratios away from standard
(=per mil)

34S sample= (34S/32S)sample - (34S/32S)standard 1000

(34S/32S)standard
34S value of -20% means that the sample is depleted in 34S by 20%
relative(or 2%) to the standard
Instrument: Mass spectrometers
2

H and

18

O standard SMOW(Standard Mean Ocean Water)

Stable isotopes: Not involved in any natural radioactive scheme.

Radiogenic: formed by radioactive decay, but do not themselves decay.
Radioactive: undergo radioactive decay
Radioactive isotopes are used to measure age
Stable isotopes: (i). To understand source of water
(ii). Processes that have affected water, since it was formed
Chemical properties of an element- determined by atomic no.
Differences in atomic mass
Differences in mass cause isotopic fractionation in nature.

Fractionation
Fractionation is any process that causes the isotopic ratios in particular phases or regions to
differ from one another.
The ratio of 18O/16O in rains is different from the ratio in the oceans, which is
different from the ratio in carbonate shells forming in the oceans.
18

O, 16O in nature=1:500, not convenient to use absolute isotopic ratios

18O sample= (18O/16O)sample - (18O/16O)standard 1000

(18O/16O)standard
Fractionation may be caused by:
Chemical processes such as reaction between a solid and a solution
Physical process such as evaporation and diffusion
Biological processes
Exchange of 18O between water and carbon monoxide
H218O + C16O = H216O + C18O
Kequi. = aC18O aH216O
aC16O aH 18O
2
= (18O/16O)CO
(18O/16O) H2O
Kequi. Is called the Fractionation factor()

Isotopic fractionation processes in the water cycle

Heavier isotopes(18O, 2H(D) tends to be more abundant in the condensed phase

Water vapor in equilibrium with ocean water D= -80%0 and 18O= -10%0
= (18O/16O)water
(18O/16O)vapor
In terms of delta notations(do it yourself)
= 1000 + 18Owater
1000 + 18Ovapor

The fractionation factors for liquid-vapor transformation are 1.0098 for

O and 1.084 for D at 25C

18

Q. Calculate the isotopic composition of a vapor in equilibrium with

sea water at 0C. The fractionation factors for 18O and D are 1.0117
and 1.111 respectively. 18Owater=0

METEORIC WATER LINE

D= 8 18O + 10%0

D= 8 18O + 10%0

Meteoric water
line

Radioactive age dating of groundwater

Direct approach involves interpreting the concentration distribution of

radioactive elements that allow a continuous age determination.
Tritium, Carbon-14 and Chlorine

Age of groundwater

t1/2= half life for decay

Ao= activity assuming no decay occurs
Aobs.= observed or measured activity of the sample
H
14
C
3

36

Cl

t1/2= 12.35 yr

<40 yr old

Contaminated

t1/2= 5730 yr

Up to 40,000
yr

Related to organic processes

t1/2=
3.0110-5 yr

Needs tandem accelerator

mass spectrometer

Tritium- 3H
Tritium unit(TU)
1 TU corresponds to one atom of 3H in 108 atoms of 1H
Useful as natural tracer of groundwater
In nature, precipitation concentration is <20 TU

Nuclear testing(1952-1963) concentration were greater than 1000 TU, present day
levels are higher than the natural background
3

He + -

Q. Groundwater was found to contain 14.8 TU of tritium and 31.6TU of tritiogenic

helium. If t1/2 of 3H is 12.3 years, what is the age of groundwater?

Carbon-14
Measurement of 14C are reported as Percent modern 14C(PMC)
Ratio of Sample activity to that of the international standard, Expressed as %
14C
14N + e14C decreases with time

Half-life
Time = 0

C-14

5,730 years
1 half-life
N-14

C-14

11,460 years
2 half-lives
N-14

C-14

(14C)t = (14C)0 e-kt)

(14C)t = amount present at time, t
(14C)o = amount present at time, t=0
K= decay constant
(14C)o = is determined by tree rings for the most recent 7000 years, not accurate
>7000 years
Groundwater flow velocity?

Chlorine-36
Dating up to 2million years old of water
Ratio of 36Cl/ Cl with a typical value for meteoric water lying in the range from
100 to 500 -1510
Like 3H, level of 36Cl have been elevated
Provides clear indication of relatively young age of the groundwater

Indirect approaches to date groundwater

Isotopically Light Glacial Recharge

Tens of thousand of years old

Isotopically lighter water-Older (originating during glacial climate)

Chlorofluorocarbons

Not isotopes
CCl3F or CFC-11 and CCl2F or CFC-12
Dates young water

Ghyben- Herzberg Relationship

Saline water is the most common pollutant in fresh groundwater

Saline water displaces or mixes with fresh water in an aquifer
Locating the interface

Ghyben- Herzberg found that salt awater occurred underground, not at sea
level but at a depth below sea level of about 40 times the height of the
freshwater above sea level.

Ghyben-Herzberg Relation:

s g z

f g (h f z )

f = freshwater density = 1.0g/cm3

s = saltwater density = 1.025g/cm3

hf + z = height of freshwater column

z = height of saltwater column

hf = hydraulic head above sea level

f
z
hf
s f

z 40h f

Groundwater level and environmental influences

Secular variations
Extending over periods of several
years or more.
Alternating rainfall in years will
produce long term fluctuations of
groundwater level
Not rainfall recharge is the
governing factor

 Seasonal variations
Highest levels occurs in late spring & lowest in winters

Short term variations

Pumping for industrial and municipal purposes

Surface investigation of groundwater

Surface investigations: incomplete hydrologic picture

Less costly
Important first step

Geologic Methods

Collection, analysis and hydrologic interpretation of existing topographic

maps, aerial photographs, geologic maps, logs, etc.

Field reconnaissance: stream flow, springs, well yields, groundwater

recharge, discharge levels, quality.

Depositional and erosional events, rock formation, dip of formation for

drilling depths

Land forms: Glacial outwash, eskers, terraces, sand dunes, faults

Remote sensing
Difference in geology, soils, soil moisture, vegetation and land
use
Aerial photographs: fracture patterns
Hydro botany:
Phreatophytes: shallow alluvial fans
Halophytes: high tolerance for soluble salts
Xerophytes: desert plants, minimal water

Surface Geophysical Techniques

Electric Resistivity Method: Measure electrical conductivity
Rocks and ions conduct electricity ions in solution, charge in particles & metals
Measure the electric potential difference between the electrodes in an electric field, as
induced by two current electrodes

Apparent resistivity

V= voltage difference
I= electric current induced into the ground
K= geometric factor that depends on the patterns of electrode spacing

Profiling and Sounding: Modes of field operations

a = RA
L
R= Resistance, A= cross sectional, L= length
No fixed limits of resistivity for various rocks
Ig. And meta. Rocks

102 to 108 ohm-m

Sed. And unconsol.

102 to 108 ohm-m

Wenner arrangement

a = 2aV/I
a= distance between adjacent electrodes

Schlumberger arrangement

b
L
a = {(L/2)2 (b/2)2} V
b
L>>b, L>=5b

Electromagnetic methods

Induce a current in the ground with an alternating current transmitting coil

Magnetic field around the coil: properties of medium, moisture content

Seismic refraction method

Seismic reflection: 1000s m below

the surface
Seismic refraction: 100s m deep

Gravity and magnetic methods:

Water witching:
Distance, meter

Ground penetrating radar (GPR)

Reflection of radio waves from discontinuities under the earths surface.
In principle, reflection seismic method, except that electromagnetic
reflections, rather than acoustic returns are recorded at the surface
Depth of investigation: few meters to 100 meters, mostly < 300m

Sub-surface investigation of groundwater

Aquifer: location, thickness, composition, permeability, yield
Groundwater: location, movement and quality
Conducted entirely by personnel on the surface who operate equipments extending
underground
Surface drilling(Test drilling)
Geophysical logging

Test drilling
Small diameter holes
Pumping well(large diameter)
Unconsolidated formations- Cable tool and hydraulic rotary method- quicker and
cheaper method
Shallow depths: Auger

Geologic log
Sampling and examination of well cuttings
DRILLING TIME LOG
Useful supplement to test drilling
Drilling time can be correlated to formation
types and depth
WATER LEVEL MEASUREMENT
Depth of groundwater
Lowering a steel pipe
>50m, electric water-level sounder
Air-line method

Geophysical logging
Involves lowering sensing devices in a bore hole and recording a physical
parameter that may be interpreted in terms of formation characteristics:
groundwater quantity, quality and movement or physical structure of the
borehole
Required information

Possible logging technique

Lithology & stratigraphic correlation

of aquifers & associated rocks

Resistivity, Sonic , Capillar logs

Total porosity or bulk density

Sonic, Neutron log, Gamma-gamma

logs

Clay or shale content

Natural gamma logs

Permeability, porosity

Resistivity logs

Moisture content

Neutron logs

Source of movement of water in a

well

Temperature logs

Resistivity logging

Current and potential electrodes can be lowered to measure electric

resistivity of the surrounding media and to obtain a trace of their variation
with depth.
The result is a resistivity log.
The multi-electrode method is most commonly employed

Use of multiple electrodes because:

1. It minimize effects of the drilling
fluid and well diameter and also
makes possible a direct comparison
of several recorded resistivity curves.
2.
Four electrodes, two for emitting
current and two for potential
measurements, constitute this system.
3.
Resistivity curves indicate the
lithology of rock strata penetrated by
the well and enable fresh and salt
waters to be distinguished in the
surrounding material
. Shale, clay & saltwater sand - low
resistivity
. Freshwater sand- moderate to high
values
. Cemented Sst. & non-porous Lst.high value

Spontaneous Potential Logging

Measures natural electrical potentials, mv values from zero to several
hundred millivolts

Radiation logging
Measures fundamental particles emitted from unstable radioactive isotopes

Natural- gamma logging

The radiation originates from unstable isotopes of K, U and Th
In general, the natural-gamma activity of clays formations is significantly
higher than that of quartz sands and carbonate rocks.

Gamma-Gamma Logging:
Gamma radiation originates from a source
probe and recorded after it is back
scattered

and

attenuated

within

the

borehole and surrounding formation

Source: Co-60 or Cs-137

Neutron logging:
Accomplished by a neutron source and
detector arranged in a single probe, which
produces a record related to the hydrogen
content of the borehole environment

Temperature logging:

Artificial recharge of groundwater

Artificial recharge can be defined as augmenting the natural movement of
surface water into underground formations by same method of
construction, by spreading of water, or by artificially changing natural
conditions.
Various methods:
Water spreading
Recharging through pits and wells
Pumping to induce recharge from surface water bodies
Choice depends on:
Topography
Geologic and soil conditions
Quantity of water to be recharged
Ultimate water use
Land value
Water quality
Water use

Why artificial recharge?

Benefits are related to:
Elevation of the water table,
water storage, horizontal discharge,
water budget, flow patterns, stops land subsidence

Economical value of the benefits depends on:

Context, risk degree, project goals
Cultural values, practice, recent trends
Water conservation mechanism/overdrafts
Artificial recharge began in Europe in early 19th century, California-300 projects

Recharge methods
Water spreading
Spreading efficiency, recharged rate expressed
as the velocity of downward movement

Spreading methods:

Basin method Basin formed by the construction of dikes or levees or by

excavation, silt free water

Periodic maintenance of basin to improve infiltration rate

Stream channel

Ditch and furrows

Flooding method Least cost

Irrigation method

Recharge well method

A well that admit water from the surface to freshwater aquifers
Its flow is reverse of pumping well
Needed where deep confined aquifers must be recharged or where economy of
space, such as in Urban area is an important consideration.
Filtered material/dissolved air/ reduced permeability by air binding
Bacteria/ chemistry is different/ deflocculates

Incidental recharge
Incidental or unplanned recharge occurs where water enters the ground as a result
of human activity whose primary objective is unrelated to artificial recharge of
groundwater.
*Water from irrigation
*waste disposal facilities
*cesspools
*canals, reservoirs
*septic tanks
*landfills
*water mains
*municipal and industrial wastes
*sewers

Groundwater management

Max. development of groundwater resources

Basin scale
Management objectives must be selected in order to develop and operate the basin
Geologic, hydrologic, economic, legal, political and financial aspects
Integrated approach that coordinates the use of both surface water and groundwater
resources
Action decision by appropriate public agencies

CONCEPTS OF BASIN MANAGEMENT

The decision goal is to obtain the max. quantity of water to meet predetermined quality
requirements at least cost
Extraction of water in a groundwater basin at one location influences the quantity of
water available at other locations within the basin
Groundwater extraction, similar to other minerals such as oil, gas or gold. Water
renewal natural resource(?)
Continued development without management plan could eventually deplete the
groundwater resources
Regulate inflow and outflow

Hydrologic Equilibrium
A balance must exist between the quantity of water supplied to the basin and amount
leaving the basin

[Surface inflow+ subsurface inflow+ precipitation+ imported water+

decrease in surface storage+ decrease in groundwater storage] =
[ surface outflow+ subsurface outflow+ consumptive use+ exported
water+ increase in surface storage+ increase in groundwater storage ]

Advantages and disadvantages of subsurface and

surface reservoirs
Subsurface reservoir

Surface reservoir

Advantages

Disadvantages

Many large capacity sites

available

Few sites available

Slight to no evaporation loss

High evaporation loss

Requires little land area

Requires large land area

No danger of structural failure

Danger of catastrophic failure

Uniform water temp.

Fluctuating water temp.

High biological purity

Easily contaminated

No conveyance system

Water must be conveyed

Disadvantages

Advantages

Water must be pumped

Gravity flow

Highly mineralized

Low mineral content

Power head not available

Power head available

Groundwater basin management

Preliminary examination
Reconnaissance
Feasibility
Define project
Sequence of activities preceding start of groundwater management investigation
Identification
of problem

Formulate
alternative
management
objectives

Define
elements of
management
plan

Select scope
of
investigation

Develop goal
for
investigation

Obtain
authorization
and finance

Develop work
program

Create
planning
organization

Commence
investigation

Sequence of activities during a feasibility investigation for

groundwater management
Projecting
water failure
water
demand

Report on the
investigation

Surface &
subsurface
exploration

Assessment
of water
resources

Capability of
extraction &
recharge
facilities

Alternate
plans for
water
resource
assessment

Legal &
organizationa
l
consideration
s

Aquifer
boundary
conditions

Water balance within a groundwater basin:

RN+ Qi- T- Qo- QP= S

RN= Recharge to groundwater
Qi= Surface water inflow to groundwater storage
T= Transpiration
Qo= Outflow from groundwater storage to surface water
QP= Total pumping rate in the basin
S= Change in storage

Safe Yield
Rate of groundwater extraction from a basin for consumptive use over an
indefinite period of time that can be maintained without producing
negative effects
Long-term balance between groundwater use & replacement

Relationship between annual land subsidence & net groundwater extraction rate
in Shanghai city

Conjunctive use
Conjunctive use involves the coordinated use of surface and
groundwater to meet same specified water demand in a given area
Objective:
To maximize net benefits
To minimize costs
To minimize degradation of environment
NET BENEFITS = REVENUES - COST