DR Deshpande

Tutorial lecture at training programme on Himalayan Glaciology. JNU Convention Centre, 3 September, 2014.
Oxygen and Hydrogen

Isotope Systematics for
Hydrological Applications
R.D. Deshpande
Physical Research Laboratory (PRL)
(A Unit of Dept. of Space, Govt. of India)
Navrangpura, Ahmedabad 380009 INDIA
Lecture note for the tutorial lecture at training programme on Himalayan Glaciology.
JNU Convention Centre, 3 September, 2014
For correspondence: [email protected]
Page 0 of 28
Oxygen and Hydrogen Isotope Systematics for Hydrological Applications

R.D. Deshpande*
Physical Research Laboratory, Navrangpura, Ahmedabad, Gujarat India 380 009
Abstract
The study of oxygen and hydrogen isotopic composition of water is a powerful
tool to trace the origin and movement of water (and vapour) throughout the
hydrological cycle. As H2O molecules travel through hydrological cycle, various
isotopic molecular species, having different isotopic combinations of oxygen (18O and
16
O) and hydrogen (1H and 2H or D) in them are differentially partitioned between
vapour, liquid and solid phases, imparting distinguishable isotopic signature to all the
three phases. This partitioning of isotopes of the same element between two different
phases is referred to as isotope fractionation, which is governed primarily by
temperature (in case of thermodynamic equilibrium between two phases in contact)
and relative humidity (in case of diffusive evaporation). The oxygen and hydrogen
isotopic composition is usually expressed in terms of its d values in per mil (‰ = per
thousand), which is nothing but per mil deviation of isotope ratios (18O/16O and 1H/2 H
or D) of sample from an international standard reference material.
It is primarily because of the isotope fractionation that various water sources
(sea water, atmospheric moisture, rainwater, river water, surface water, groundwater,
snow and glaciers), at different geographical locations, have characteristic long terms
average isotopic composition (d18O and dD) with typical seasonal variations governed
by local hydro-meteorological and geo-hydrological processes and geographic factors.
The isotope fractionation changes the isotopic composition of a given water source in
a predictable manner depending on the extent to which the fractionating process (e.g.
evaporation, condensation, rainout, sublimation, vapour deposition) has proceeded.
Therefore, during a phase change process, it is possible to quantitatively estimate the
flux of H2O molecules across the boundary between the two phases. The isotopic
composition of a given H2O reservoir (e.g. atmospheric moisture, groundwater, river
water, sea water) can also change due to mixing of another H2O flux, of different
isotopic composition. In such cases of mixing, no isotopic fractionation is involved,
but H2O flux associated with this mixing process can be estimated quantitatively by
isotopic mass balance. Thus, oxygen and hydrogen isotopic composition can be
advantageously used as a tool to (i) characterize various H2O reservoirs within
hydrological cycle; (ii) understand subtle hydro meteorological and hydrogeological
processes (phase change or mixing); and (iii) quantitatively estimate the fluxes across
various reservoir boundaries.
This lecture note discusses some of the fundamental concepts of oxygen and
hydrogen isotope systematics and general thumb rules based on which oxygen and
hydrogen isotope tracer technique is employed in hydrological studies.
*
For Correspondence: [email protected]
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1. Introduction
Among various isotopes used as tracers in hydrology, stable isotopes of
oxygen (16O and 18O) and hydrogen (1H and 2H, also known as deuterium; D) are the
most important since these isotopes form integral parts of a water molecule. As H2 O
molecules travel through hydrological cycle, various isotopic molecules, having
different isotopic combinations of oxygen (18O and 16O) and hydrogen (1H and 2H or
D) in them are differentially partitioned (fractionated) between vapour, liquid and
solid phases, imparting distinguishable isotopic signature to all the three phases.
Therefore, oxygen and hydrogen isotopic composition of H2O molecules forms a
powerful tool to trace the origin and movement of water (and vapour) throughout
hydrological cycle. Isotope tracing can provide useful insights, in particular, about
those subtle hydro-meteorological and hydro-geological processes which cannot be
studied with common hydrometric approach of measuring volumes or fluxes (rainfall,
groundwater level, river water level, reservoir level, river discharge).
Detailed understanding of such subtle processes is very important in the
present times where hydrological cycle is simultaneously influenced by three forcing
factors. These forcing factors are: (i) engineered interventions (construction of dams
and inter-basin transfer, rain water harvesting and artificial groundwater recharge);
(ii) global climate change due to emission of greenhouse gases and atmospheric
aerosols; and (iii) natural climatic variability. The combined hydrological
consequences of these three forcing factors are not yet understood very clearly even
as extensive monitoring, documentation and research efforts are going on, collectively,
under the aegis of the Intergovernmental Penal on Climate Change (IPCC).
Beyond purely academic perspectives, it is also important to fill the existing
knowledge gap to more efficiently manage the already stressed water resource
scenario of the country and meet the increasing water demand for agricultural,
industrial, domestic and livestock requirements (Gupta and Deshpande, 2004; Rakesh
Kumar et al., 2005). In such a situation, improved understanding about water related
natural processes and their monitoring using isotope approach can be useful to
strengthen the water resource development and management strategy and possibly
help foresee the undesirable hydrological consequences of global changes based on
which appropriate mitigation strategy can be advocated.
Importance of water isotope applications in hydrological investigations have
been discussed at length in vast literature based on studies in different parts of the
world (Araguas-Araguas et al., 1998; Clark and Fritz, 1997; Dincer et al., 1974; Gat
and Matsui, 1991; Gonfiantini, 1986; Kendall and McDonnell, 1998; Rozanski et al.,
1993; Salati et al., 1979). Several Indian case studies have also been reported over the
last few decades (Achyuthan et al., 2013; Bhattacharya et al., 2003; Bhattacharya et
al., 1985; Chandrasekharan et al., 1992; Dalai et al., 2002; Das et al., 1988; Datta et
al., 1994; Datta et al., 1996a; Datta et al., 1996b; Datta et al., 1991; Deshpande et al.,
2003; Deshpande et al., 2011; Deshpande and Gupta, 2012; Deshpande et al., 2013a;
Deshpande et al., 2010; Deshpande et al., 2013b; Deshpande et al., 2013c; Gupta and
Deshpande, 2003; Gupta and Deshpande, 2005a; Gupta and Deshpande, 2005b; Gupta
et al., 2005; Krishnamurthy and Bhattacharya, 1991; Kumar et al., 1982; Kumar et al.,
2010; Maurya et al., 2011; Navada et al., 1993; Navada and Rao, 1991; Nijampurkar
et al., 2002; Pande et al., 2000; Purushothaman et al., 2012; Rai et al., 2009; Ramesh
and Sarin, 1992; Rao et al., 2012; Saha et al., 2013; Sarin et al., 1992; Sengupta and
Sarkar, 2006; Shivanna et al., 2004; Shivanna et al., 2008; Singh et al., 2010;
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Srivastava et al., 2010; Srivastava et al., 2007; Srivastava et al., 2012; Sukhija et al.,
1998; Warrier et al., 2010; Yadav, 1997). In spite of numerous publications from
Indian researchers the application of isotope tracer techniques in hydrology, has
remained within the domain of a few leading research institutions in the country, even
today.
Considering its proven potential, as evident from above references,
application of oxygen and hydrogen isotopes in hydrological studies should be treated
as a useful and necessary tool rather than just sophistication. Realizing the need and
potential application of oxygen and hydrogen isotopic monitoring of water sources, a
multi-institutional collaborative National Programme on isotope fingerprinting of
waters of India (IWIN) is currently underway in which some of the important central
agencies, are also participating and getting familiarised with isotope applications
((Deshpande et al., 2011; Deshpande and Gupta, 2008; Deshpande and Gupta, 2009;
Deshpande and Gupta, 2012).
With a view to disseminate the working knowledge about oxygen and
hydrogen isotope systematics, and highlight and facilitate its practical applications in
hydrology, fundamental concepts and general thumb rules are discussed in the
following.
2. Isotopes of Oxygen and Hydrogen
The basic fact-sheet of the isotopes of oxygen and hydrogen is given in Table
1. The oxygen has three natural stable isotopes (16O, 17O, 18O). The most abundant
oxygen isotope (16O) is a principal isotope i.e. formed during stellar evolution,
directly by stars that were made exclusively of hydrogen. Most 16O is thus,
synthesized at the end of the helium fusion process in stars. Other isotopes of oxygen
are secondary isotopes, meaning that their nucleosynthesis requires seed nuclei. The
oxygen has fourteen radioactive isotopes but all of them decay in less than 123
seconds with 15O having the longest half-life of 122.24 s; and 12O having the shortest
half-life 580×10 -24 s. The hydrogen has two natural stable isotopes (1H - Protium and
2
H - Deuterium) and one natural radioactive isotope (3H - Tritium). There are
synthetic radioactive isotopes of hydrogen 4H to 7H with half-lives in the range of 10-
22
s.
Since oxygen and hydrogen together form a water molecule, isotopes of
oxygen and hydrogen are collectively referred to as water isotopes in some literature.
3. Isotopic Molecular Species of Water (isotopologues)
A water molecule is formed by combination of two hydrogen atoms (any two
of the two stable isotopes; 1H and D) and one oxygen atom (any one of the three
stable isotopes 16O, 17O, and 18O). Thus, 9 possible combinations of these 2 isotopes
of hydrogen and 3 isotopes of oxygen are possible, which gives rise to following 9
isotopic molecular species, also referred to as water isotopologues. These 9 possible
isotopic molecules of water are: (1) 1H216O; (2) 1H217O; (3) 1H218O; (4) 1HD16O; (5)
HD17O; (6) HD18O; (7) DD16O; (8) DD17O; (9) DD18O. The four most abundant
isotopic molecules of water are given in Table 2 along with their relative abundance
and molecular masses.
Any water or vapour reservoir is basically composed of the above nine
isotopologues, with minor variation in relative abundance of these isotopologues,
caused by their differential partitioning in two phases during phase change processes
within hydrological cycle. Consequently, different hydrological resources (vapour,
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rain, groundwater, river water, snow, and glacier) have only slightly different isotope
abundance ratios (18O/16O, 17O/16O or D/H). For example, surface water of Arabian
Sea may have 18O/16O ratio of 0.002006 and that of Himalayan snow may have this
ratio of 0.001960. The differences in abundance ratios in various reservoirs are so
small that expressing the isotopic composition of various reservoirs in terms of
abundance ratios is not practical. Therefore, instead of expressing the isotopic
compositions in terms of absolute abundance ratios, it is expressed in terms deviation
of abundance ratio from an international standard reference material. The
conventional way of expressing isotopic composition is discussed in the following.
Table 1. The fact sheet of isotopes of oxygen and hydrogen (Compiled from (CRC,
1980) and other literature).
Name (Symbol) Oxygen (O) Hydrogen (H)
Atomic number 8 1
Standard Atomic Mass 15.9994(3) g/mol 1.00794(7) g/mol
Chemical Series Non-metals, chalcogens non-metals
Group, period, block 16, 2, p 1, 1, s
Electronic
1s2 2s2 2p4 1s1
configuration
16
Stable isotopes and O: 99.762% 1
17 H: 99.985%
their Natural O: 0.038% 2
18 H (or D): 0.015%
abundance O: 0.200%
16
O: 15.9949146 u 1
17 H (Protium): 1.00782503 u
Isotopic mass O 16.9991315 u 2
18 H (Deuterium): 2.01410177 u
O 17.999160 u
18
O /16O = 0.002004171 2
H / 1H = 0.0001500225
Abundance ratio
= 2004.17× 10–6 = 150 × 10–6
Oxygen has fourteen radioactive
Hydrogen has one radioactive
isotopes from 12O to 15O and
isotope 3H (tritium) With half-life
Radioactive isotopes from 19O to 28O All radioactive
of 12.32(2) years, which b -
isotopes have half-life less than 3
decays to 3He.
minutes
Table 2. The four most abundant isotopologues of water and their molecular masses.
Isotopologue H216O H218O H217O HD16O D216O

Relative natural
99.78% 0.20% 0.03% 0.0149% 0.022 ppm
abundance
Molecular mass 18 20 19 19 20
4. Expressing Isotopic Composition

Isotopic compositions are normally expressed in d–notation, as deviations of
heavy to light isotopic ratios relative to an international standard of known
composition, in units of parts per thousand or per mil (denoted as ‰). The isotopic
composition in terms of d values can be calculated using following equation.
éR ù
d ( in ‰ ) = ê Sample -1ú ´1000 (1)
ë R Stan dard û
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In the above equation, Rsample and Rstandard denote the ratio of heavy to light
isotope (e.g. 18O/16O or D/H) in the sample and standard respectively. The oxygen and
hydrogen isotopic compositions are normally referred to as dD and d18O. Both, dD
and d18O values, are usually reported relative to an international standard reference
material such as SMOW (Standard Mean Ocean Water; (Craig, 1961b) or the
equivalent VSMOW (Vienna-SMOW; (Gonfiantini, 1978)).
The SMOW defined by Craig (1961b) never existed physically. It was
hypothetical water calibrated relative to the isotopic content of NBS-1, a sample from
the Potomac River catalogued by former NBS. The 18O/16O ratio in SMOW was 1.008
times that in NBS-1 and the 2H/1H ratio in SMOW was 1.050 times that in NBS-1.
Subsequently, the IAEA prepared the standard water from distilled sea water that was
modified to have an isotopic composition close to SMOW. This reference was
identified as VSMOW (Vienna Standard Mean Oceanic Water). The values of
measured abundance ratios (2H/1H and 18O/16O) in SMOW and VSMOW are given in
Table 3.
Table 3. Measured abundance ratios in international standard reference material
Isotopes Standard Abundance Ratio

2
H/1H SMOW 0.000158 [158(±2) × 10-6]
18
O/16O SMOW 0.0019934 [1993.4(±2.5) × 10 -6
2
H/1H VSMOW 0.00015575 [155.75(±0.45) × 10-6]
18
O/16O VSMOW 0.0020052 or [2005.2(±0.05) × 10 -6]
To understand how d values are calculated from ratios, one can do the
following simple exercise. If the 18O/16O and 2H/1H ratios in a sample are given to be
0.0020104 and 0.00015735 respectively, its oxygen and hydrogen isotopic
compositions (d18O = 2.59‰ and dD = 10.27‰) with respect to VSMOW can be
easily calculated using Equation (1) and the isotopic ratios for VSMOW, as given in
Table 3.
In addition to the commonly used SMOW and VSMOW, there are two more
international standard reference materials, namely, SLAP (Standard Light Antarctic
Precipitation) and GISP (Greenland Ice Sheet Precipitation). The oxygen and
hydrogen isotopic compositions of SLAP and GISP are given in Table 4.
Table 4. The oxygen and hydrogen isotopic compositions of SLAP and GISP
Standard Light Antarctic Precipitation Greenland Ice Sheet Precipitation
(SLAP) (GISP)
d OSLAP = –55.50‰ VSMOW
18
d OGISP = –24.76‰ VSMOW
18
dDSLAP = –428.0‰ VSMOW dDGISP = –189.5‰ VSMOW

5. Isotope Fractionation
During any phase change process, the heavier (e.g. H218O and HD16O) and
lighter (H216O) isotopologues of water are differentially partitioned between the two
interacting phases due to the differences in physical properties of various
isotopologues. Consequently, the heavy and light isotopes are also differentially
Page 5 of 28
partitioned between two phases. This differential partitioning of isotopes between the
two phases is known as the isotope fractionation. Fractionation can, thus, be
visualized as ratio (Phase 1/Phase 2) of isotope abundance ratio (heavy/light) between
the two phases. Sometimes the term isotope discrimination is also used to convey the
isotope fractionation, although fractionation is more commonly used.
The isotope fractionation takes place due to the fact that although chemical
properties of various isotopologues of water are identical, their physical properties
(bond strength, rotational, vibrational and translational frequencies, density, vapour
pressure, collision frequency) are different due to their mass differences. Though
difference in physical properties of various isotopologues is very small, it is large
enough to cause the measurable difference in the abundance ratio of these isotopes in
the two phases, using sensitive mass spectrometers.
The mass differences between isotopologues of water directly influence their
mobility, diffusive velocity, collision frequency and binding energy. Two important
controlling factors for fractionation, namely, temperature and diffusive velocities are
discussed in the following.
5.1 Effect of temperature
At a given temperature, all isotopologues have similar kinetic energy (kT =
½mv2; where k = Boltzmann constant, T = absolute temperature, m= molecular mass,
v = average molecular velocity). Since heavier isotopologues have higher mass, their
velocity is smaller and consequently their mobility is less at molecular level. Thus,
heavier isotopologues have lower velocity compared to lighter isotopologues. Due to
their lower velocity, collision frequency of heavier isotopologues is smaller. Due to
smaller collision frequency, rate of chemical reaction is smaller for heavier
isotopologues whereas lighter isotopologues react faster. In case of equilibrium
conditions, this mass dependent velocity differences affect the equilibrium
fractionation in an indirect way, via its effect on bond strength and not directly as in
case of diffusivity related fractionation (see section 5.2).
Due to their mass difference, the heavier isotopologues have greater binding
energy compared to lighter isotopologues. The difference in the strength of bonds
formed by the light versus heavier isotopes of a given element is the basis for isotope
fractionation. This difference in binding energy can be understood with a simple
potential energy distribution model of the relationship between potential energy of a
molecular bond and inter-atomic distance for heavy and light isotopes of a molecule.
The two oppositely charged particles in a molecule experience competing forces. One
of these is the repulsive force which rapidly increases with decreasing distance (~
1/r13). Another is the attractive force which increases less rapidly with decreasing
distance (~ 1/r2 in ionic crystals; ~ 1/r7 between uncharged particles). Balanced by
these two competing forces, the two particles will be located at an ideal inter-atomic
distance from each other depending on the net attractive force between the two.
Therefore, it will require additional energy either to push the atoms together or
separate them. The energy required to break apart the molecules is referred to as
dissociation energy (also known as binding energy or bond strength) and differs for
isotopically different molecules. The heavier isotope will have stronger bond and
require more energy to dissociate compared to lighter isotope.
Even at absolute zero temperature (-273.15°C) particles will have certain
minimum energy called zero-point energy which decides three modes of motion of a
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molecule –rotation (of the molecule around certain molecular axes), translation
(displacement of the molecule as a whole) and vibration (vibrations of the atoms in
the molecule with respect to each other). The zero-point energy for lighter isotopes
will be more than heavier isotopes. The heavier particle has smaller zero-point energy
and is located deeper in the potential energy well than the lighter particle.
Consequently, the heavier particle requires more energy to escape from the potential
energy well, or in other words has greater binding energy. Thus, heavier isotopes get
preferentially enriched in the phase in which their binding energy is higher.
With increase in temperature, relatively smaller energy is required for
breaking the bond, and hence bonds can break more easily at higher temperature than
at lower temperature; thought bonds of lighter molecules continue to break more
easily compared to heavier irrespective of temperature. Thus, with increasing
temperature, fractionation continues but magnitude of fractionation decreases. In
other words, at higher temperature the substance is less fractionated compared to a
lower temperature.
From the perspectives of statistical mechanics, strong temperature
dependence of fractionation can also be understood in terms of partition function (Q)
which describes the statistical properties of a system in thermodynamic equilibrium.
The partition function is a function of temperature of the system, mass of the
molecule, symmetry of the molecule and the summation of energy states from zero-
point energy to the energy of dissociated molecule. The dissociation energy of a
molecule is related to its partition functions which are based on three molecular
movements (rotational, translational and vibrational) or energy frequencies. The
partition function can be defined for each of these three molecular movements, and is
given by:
Q = s-1m3/2 å e-E/kT (2)

In Equation(2), s is a symmetry value; m is mass; E is the energy state
(Joul.mole-1), k is the Boltzmann constant (JK-1) and T (K) is the temperature in
Kelvin.
The partition functions are defined for each isotopic molecular species in a
given isotope exchange reaction at a given temperature. Since translational and
rotational frequencies for isotopic species are nearly identical, it is only the
differences in vibrational frequencies which cause effective partition of isotopes in
two phases. The total partition function ratio for light and heavy isotopes is given by:
æ Q* ö æ Q* ö æ Q* ö æ Q* ö
ç ÷ = ç ÷ ´ ç ÷ ´ ç ÷ (3)
ç Q ÷ ç Q ÷ ç Q ÷ ç Q ÷
è ø total è øtrans è ørota è ø vibra
In Equation(3), * indicates heavy isotope.
The equilibrium fractionation, defined as ratio of isotope abundance ratio of
one phase to another, is then nothing but the ratio of partition functions for heavy to
light molecular species in one phase to another, as given by:
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æ Q* ö
ç xQ ÷
(isotope abundance ratio )x çè x ÷ø
= (4)
( isotope abundance ratio )y æ Q*y ö
ç ÷
ç Qy ÷
è ø
5.2 Effect of diffusive velocities
In addition to the differences in bond-strength which cause isotope
fractionation under equilibrium conditions, differences in diffusive velocities of
molecules is another physical parameter which causes isotope fractionation
particularly in case on systems not in equilibrium. Isotope fractionation due to
difference in diffusive velocities corresponds to the ratio of diffusive velocities which
in turn relate to the reduced mass of the isotopic molecule. A system in which a gas or
solute diffuses through another medium, the mass of the medium also needs to be
taken into account by incorporating reduced mass instead of just molecular mass of
the species which is diffusing. The reduced mass is the effective inertial mass of the
molecule in a two component system (e.g. diffusion of water vapour through air). The
reduced mass m is given by:
1 1 1
= + (5)
m m M
In Equation(5), m refers to molecular mass of various isotopic species, M
refers to the molecular mass of the medium through which diffusion occurs and m is
the reduced mass.
The fractionation due to differences in diffusive velocities can then be
calculated using following equation:
kT
v* 2pm* m
Diffusive Fractionation = = (6)
v kT m*
2 pm
In Equation(6), v is the molecular velocity of isotopic molecule, m refers to the
reduced mass, k is Boltzmann constant, T is absolute temperature and * refers to
heavy isotopic molecular species.
5.3 Equilibrium and Kinetic Fractionation
The isotope fractionation can occur due to: (i) physicochemical reactions
under equilibrium condition; (2) physicochemical reactions under non-equilibrium
condition; and (3) molecular diffusion. In the first case, reactant and product interact
for sufficiently long duration so that isotopic equilibrium is established. In the second
case, sudden change in temperature or addition or removal of product or reactant
prevents the isotopic equilibrium in a given physicochemical reaction. In the third
case, product under isotopic equilibrium is slowly diffusing out of the product
reservoir but the product reservoir may remain in isotopic equilibrium with large
reservoir of reactant. Although these three types of fractionating processes are known
to occur, for all practical purposes, fractionations are conveniently grouped in to two
major classes namely, equilibrium and kinetic. Isotopic fractionation can occur
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during: (i) equilibrium isotopic exchange reactions and (ii) non-equilibrium (kinetic)
processes.
5.3.1 Equilibrium Fractionation
Equilibrium exchange reactions involve thermodynamic equilibrium between
the two phases during a phase change process during which redistribution of the
isotopes between the two phases (products and reactants) takes place. When forward
and backward rates of phase change reaction are equal the thermodynamic
equilibrium is said to have been attained. The equilibrium fractionation is primarily
governed by the binding energy of the isotopologues in two phases. Since the binding
energies depend on temperature, the equilibrium fractionation depends on temperature.
The heavier isotopologues, gets concentrated in the phase in which they have greater
binding energy. As a 'rule of thumb', among different phases (vapour, liquid, solid) in
which H2O can exist, the denser the phase, the more it tends to be enriched in the
heavier isotopes (D and 18O).
The natural example of an equilibrium fractionation is vapour to liquid phase
change in cloud, where liquid phase remains in contact with surrounding vapour and
is believed to have attained the isotopic equilibrium with vapour phase, before it rains
out from the cloud.
5.3.2 Non-equilibrium or kinetic fractionation
In systems out of equilibrium, forward and backward reaction rates are not
identical, and isotope reactions become unidirectional and irreversible. This can
happen due to sudden change in temperature or sudden addition or removal of product
or reactant. Under these circumstances, relative amount of the reactant or product
suddenly changes and hence the two cannot attain thermodynamic equilibrium with
each other. Isotope fractionation due to such reactions is called non-equilibrium or
kinetic fractionation. Although this is a non-equilibrium fractionation, it still strongly
depends on temperature, like equilibrium fractionation.
Natural example of this type of fractionation is sudden uplift of warm vapour
loaded air mass and resultant cloud burst; immediate removal of vapour emanating
from water bodies (lakes, flowing rivers, surface water spread for irrigation) due to
strong winds etc.
5.3.3 Diffusive fractionation
Fractionation due to differences in diffusive velocities is a variant of the non-
equilibrium or kinetic fractionation. In this case, different isotopic molecules diffuse
out of the bulk reservoir, with different diffusive velocities. Actually, the reservoir
from which the molecules diffuse out should become progressively enriched in
molecules with lower diffusive velocities (see section 5.2). However, if the system,
from which molecules are diffusing out, is being continuously replenished while in
equilibrium with parent reservoir, it is possible to establish a steady-state diffusion
regime such that steady state is maintained in isotopic composition of the bulk
reservoir from which molecules are diffusing out. In other words, even though
outgoing flux has different isotopic ratio than the bulk reservoir, isotopic composition
of the bulk reservoir remains the same. Unlike the kinetic fractionation caused by
sudden temperature change or sudden addition / removal of mass, which has strong
temperature dependence, the diffusive fractionation is strongly governed by diffusive
velocities and has only slight temperature dependence, which is for all practical
Page 9 of 28
purposes can be ignored in actual calculations of fractionation factors. The diffusive

fractionation is also referred to as transport fractionation in some literature.
Natural scenarios where diffusive fractionation occurs are evaporation from
open water body and diffusion of vapour from surface of water to air above.
In isotope hydrology, the most accepted model for non-equilibrium
evaporation from a water body involves diffusion of water vapor across a hypothetical
microns thin boundary layer over the liquid water interface. The boundary layer has
virtually 100% water saturation. This layer is in isotopic equilibrium with the
underlying water column. Between the boundary layer and the mixed atmosphere
above is a transition zone through which water vapor is transported in both directions
by molecular diffusion. It is within the transition zone that non-equilibrium
fractionation arises due to the fact that diffusive velocity of 1H216O in air is greater
than that of 2H1H16O or H218O.
The vapour over ocean is isotopically depleted with respect to ocean water and
the total fractionation is the sum of: (i) the equilibrium fractionation between ocean
water and thin boundary layer; and (2) the diffusive fractionation between boundary
layer and mixed atmospheric air above.
6. Terminologies symbols related to Isotope Fractionation
There is considerable variety in the terminologies, symbols and approaches
that can be used to express the same phenomenon - fractionation. Therefore, it is
important to be familiar with different approaches of expressing fractionation.
The isotope fractionation is mathematically expressed by the ratio of
abundance ratios of the heavy/light isotope for reactant and product (a = Rreactant /
Rproduct or Rproduct / Rreactant) and is referred to as the fractionation factor (a). For
example, in case of water-vapour system in equilibrium, the fractionation factor is
given by;
é 18 O ù
ê 16 O ú
18
a (water - vapour) = ë 18 û Water (7)
é Où
ê 16 O ú
ë û Vapor
The definitions of both the terms a and d involve the abundance ratios for
heavy to light isotopes. Therefore, a and d are related by following equation.
dx
1+
1000 + dx
a x - y = 1000 = (8)
dy 1000 + d y
1+
1000
The isotope fraction effects are usually very small in magnitude and therefore
fractionation factor a (= Rreactant/Rproduct or Rproduct/Rreactant) always has values very
close to unity. However, depending on (i) whether product becomes isotopically
depleted or enriched compared to reactant, during the fractionation process; and (ii)
the way in which the fractionation factor is expressed (i.e. Rreactant / Rproduct or
Rproduct/Rreactant), the fractionation factor (a) can be slightly greater or smaller than 1.
For example, the 18O/16O ratio in water is always greater than that in vapour in
Page 10 of 28
equilibrium with it, and hence value of 18a expressed as Rwater / Rvapor will be greater
than 1 (e.g. 1.00937 at 25°C; (Majoube, 1971)). However, if expressed as Rvapor /
Rwater, value of 18a will is 0.990717. Similarly, the 18O/16O ratio in water is always
smaller than that in ice in equilibrium with it, and hence the value of 18a expressed as
Rwater / Rice will be less than 1 (e.g. 0.996905 at 0°C; (Majoube, 1971; O'Neil, 1968)).
However, if expressed as Rice / Rwater, value of 18a will is 1.00310. Craig and Gordon
(1965) had introduced a convention of using different symbols to clarify how the
fractionation factor has been expressed [a* >1 and a+ <1 such that a*=1/a+] (Gat,
1996). However, this convention was not adopted by successive researchers. Instead,
various researchers adopted their own styles and specified it in their papers.
Since values of a are very close to 1 and differ only at 4th decimal place,
another numerical term e [= (a-1) × 1000] is defined to comprehend the fractionation
in a manner corresponding to the definition of d. The term e is referred to as
“fractionation” rather than “fractionation factor”. Sometimes e is also referred to as
the “enrichment factor” or just “enrichment”. The +ve values of e convey enrichment
of heavier isotopes and –ve values of e convey depletion. It must, however, be noted
that in some literature a-1 is not multiplied by 1000.
The terms a and e are related to the abundance ratios for heavy to light
isotopes and can be expressed by following equation.
æR ö
e x - y = (a - 1).103 = ç x - 1 ÷ .103 (9)
ç Ry ÷
è ø
To convey the fractionation which occurs under non-equilibrium conditions,
often some prefix or subscript is used such as De, ekin, a kin etc.
Based on the definition of d, another term isotope separation (D) is also
used to convey the difference in isotopic composition of any two substances, such
that:
D x - y = dx - d y (10)
In view of this multitude of expressions, one needs to be careful while using

the equations presented in different papers, for their calculations.
7. Calculating the Values of Fractionation Factors
7.1 Equilibrium fractionation factor
In principal, the equilibrium fractionation factor can be theoretically calculated
from partition functions using Equations(2), (3) and (4), provided sum over the all
energy states (which involves probabilistic statistical mechanics) can be accurately
ascertained. Several researchers have experimentally determined the values of
equilibrium fractionation factors for different phases of water (solid, liquid and
vapour), at different temperatures, by controlled experiments (Arnason, 1969; Craig
and Gordon, 1965; Kakiuchi and Matsuo, 1979; Majoube, 1971; O'Neil, 1968;
Suzuoki and Kumura, 1973). These values may differ slightly from one another due to
differences in experimental setups.
Based on the regression of most of the experimental values reported in
literature, following equations for determining the equilibrium fractionation factor (a)
between the liquid and vapour phase, at a given temperature (K) is proposed by Horita
Page 11 of 28
and Wesolowski (1994) for oxygen (Equation (11)) and hydrogen (Equation (12))
isotopes.
æ 103 ö æ 106 ö æ 109 ö
103 ln a (l-v) ( 18 O) = 6.7123 ç ÷ -1.6664 ç 2 ÷ - 7.685 + 0.35041ç 3 ÷ (11)
è T ø èT ø èT ø
Equation(11) is valid from 0°C to the critical temperature of water (374.1 °C)
within ±0.11(1s).
æ T3 ö æ T2 ö æ T ö æ 109 ö
103 ln a(l- v) (D) =1158.8 ç 9 ÷ -1620.1ç 6 ÷ + 794.84 ç 3 ÷ - 161.04 + 2.9992 ç 3 ÷ (12)
è 10 ø è 10 ø è 10 ø èT ø
Equation(12) is valid from 0°C to the critical temperature of water (374.1 °C)
within ±1.2( 1s) (n = 157).
The fractionation terms in Equations (11) and (12) is expressed as 10 3lna
because of the fact that trend line between a and absolute temperature has a
polynomial form which produces a linear graph when lna is plotted against the
inverse of temperature. However, lna is nearly zero, so multiplying by 1000 (i.e.
103lna) offers a quantity which corresponds to d in per mil units. The values of
103lna, fractionation factor a, and enrichment e calculated using Equations (11) and
(12) for a range of temperatures are given in Table 5.
From the forgoing one can notice that various terms (fractionation factor a,
enrichment e, isotopic composition d, isotope separation D and 10 3lna) express the
isotope fractionation and can be interchangeably used in calculations, after proper
conversion. However, fractionation factor a (or 103lna) is the only fundamental
parameter which is derived theoretically or experimentally. All other terms involve
mathematical approximations and can slightly differ numerically. These differences
can be ignored when fraction effect is small. However, when fractionation is large
these numerical differences are pronounced and can yield erroneous results. In such
case it may be necessary to use 103lna instead of e in the calculations.
Table 5. Values of 103ln a, fractionation factor a, and enrichment e calculated using

Equations (11) and(12).
Temp. æ 103 lna 2 ö

10 3lna18 18
a 18
e 10 3lna2 a2 e2 ç 3 18 ÷
ç 10 lna ÷
°C
è ø
0 11.75 1.0118 11.82 105.96 1.1118 111.78 9.0
5 11.19 1.0113 11.25 99.00 1.1041 104.06 8.8
10 10.67 1.0107 10.73 92.54 1.0970 96.96 8.7
15 10.18 1.0102 10.24 86.55 1.0904 90.40 8.5
20 9.73 1.0098 9.78 80.97 1.0843 84.34 8.3
25 9.30 1.0093 9.35 75.79 1.0787 78.74 8.1
30 8.90 1.0089 8.94 70.96 1.0735 73.54 8.0
40 8.17 1.0082 8.20 62.24 1.0642 64.21 7.6
50 7.51 1.0075 7.54 54.61 1.0561 56.13 7.3
60 6.93 1.0069 6.95 47.90 1.0491 49.07 6.9
70 6.40 1.0064 6.42 41.98 1.0429 42.88 6.6
Page 12 of 28
80 5.92 1.0059 5.93 36.74 1.0374 37.42 6.2

90 5.48 1.0055 5.49 32.07 1.0326 32.59 5.9
100 5.08 1.0051 5.09 27.90 1.0283 28.29 5.5
7.2 Kinetic fractionation factor
Calculating the values of kinetic fractionation factor, either theoretically or
experimentally, is not as straight forward as calculating equilibrium fractionation
factor. This is because the two possible scenarios, (see section 5.3.2 for temperature
change or addition / removal mass; and section 5.3.3 for diffusion) are difficult to
experimentally evaluate and requires to be modelled separately. The most useful and
exhaustive model for estimating isotope fractionation during evaporation is that
proposed by Craig and Gordon (1965), which is based on Langmuier linear resistance
model for evaporation and has stood the test of the time (Craig and Gordon, 1965;
Gat, 1996). In addition, isotope effects during diffusive evaporation for surface water
bodies have been experimentally and theoretically examined by other workers (Clark
and Fritz, 1997).
It is important to understand why humidity is so critical in determining the
kinetic fractionation factor. Using molecular masses of various isotopic molecular
species of water (m: H218O = 20; HD16O =19; H216O =18) and that of air (M: 28.8 for
79% N2 and 21% O2) in Equations(5) and (6), one can calculate kinetic fractionation
factors for oxygen and hydrogen, due to diffusion of vapour from microns thick
boundary layer at the air-water interface into well mixed atmospheric air above. This
calculation yields kinetic fractionation factor 18ak = 1.0323 and 2ak = 1.0166. These
fractionation factors translate into De18 = 32.3‰ and De2 = 16.6‰. Such extreme
fractionation is never observed in nature because these theoretical calculations are
based on dry air, with humidity = 0. In nature, however, relative humidity is rarely
close to 0 therefore, relative humidity needs to be incorporated in the calculation of
fractionation factor. The isotopic enrichment (De) of evaporating water due to kinetic
fractionation at relative humidity (h; fractional) can be approximated by the two
empirical relationships that ignore all other controlling factors except the humidity
(Gonfiantini, 1986).
De18O(bl-v) = 14.2× (1 – h ) ‰ (13)
De2 H(bl-v) = 12.5× (1 – h ) ‰ (14)
These equations provide only approximate value of enrichment because other

factors such as surface temperature, wind speed, salinity of water etc are ignored.
It is seen from the above equations that relative magnitude of kinetic
fractionation for oxygen isotopes is greater than that for hydrogen isotopes, whereas
in case of equilibrium condition fractionation for oxygen is lower than that for
hydrogen.
The total fractionation between water column and open air is the sum of the
enrichment factor for equilibrium water vapour exchange (el®v) and the kinetic factor
(Debl-v). For 18O, this would be:
d18Ol - d18O v = e18

(l - bl) + De(bl - v)
18
(15)
Page 13 of 28
The RHS in Equation (15) indicates the total fractionation (equilibrium +

kinetic) during evaporation. Because the boundary layer is at 100% saturation,
e18Ol®bl corresponds to equilibrium fractionation between water and vapour. Under
conditions of 100% humidity (h = 1), the vapour is in isotopic equilibrium with
seawater (De18Obl-v = 0). When humidity is low the vapour is strongly depleted in 18O
compared to D, resulting in excess deuterium over 18O.
The kinetic fractionation can also occur during vapour deposition (vapour to
solid condensation) under supersaturated condition, due to differences in diffusive
velocities through air layer supersaturated with vapour. The kinetic fractionation
factor in such cases can be estimated using following equation (Jouzel and Merlivat,
1984):
Si
a kin = (16)
é D ù
êë aequ ´ D' ´ ( Si - 1) úû + 1
In Equation(16), D and D’ refers to diffusive velocities of light and heavy

isotope, Si refers to saturation index (actual vapour pressure/ saturation vapour
pressure) which in such cases is <1.
8. Rayleigh Distillation
The rain (or snow) is prodiced when an air mass containing vapour cools. The
cooling occurs by (i) adiabatic (without loss of heat) expansion as the warm air rises
to lower pressure; or (ii) radiative loss of heat. When the temperature of the air parcel
drops below the dew point (temperature at which relative humidity is 100%) vapour
condenses in to liquid (rain) or snow (solid), in order to maintain the thermodynamic
equilibrium at that temperature. The vapour and condensate remain in an intimate
contact at a given temperature in the cloud. If the temperature drops further,
condensation of vapour proceeds further and if temperature increases, the evaporation
of liquid or snow occurs. The first condesantes are tiny particles which float and
remain in close contact with vapor under equilibrium. When tiny particles coalesce
and sufficiently massive particle is formed, it begins to fall under gravity. This is how
we receive rain on ground.
During equilibrium condensation at prevalent in-cloud temperature, isotopic
molecular species (see section 3) differentially partition between vapor and liquid (or
solid) phase such that more condensed phase is always enriched in heavier isotopes
and vapor is depleted in heavier isotopes. Thus, with progressive rainout along the
wind trajectory from marine vapor source region into continental interiors, the
remaining vapor becomes progressively more and more depleted in heavier isotopes.
At every stage of rainout, the condensate is always enriched in heavier isotopes
compared to vapor. Since vapor is progressively depleted at successive stage of
rainout, the resultant rain at succesive stage is also isotopically depleted.
One can model isotope evolution during rainout according to Rayleigh
distillation equation:
R = R 0f (a-1) (17)
The Rayleigh equation gives isotopic ratio (R) of a vapour reservoir
progressively diminishing in its mass due to outflux by condensation, at an instance
when residual fraction (f) of the original reservoir with isotope ratio (R0) has
Page 14 of 28
diminished from initial value f = 1 to a value f < 1, with a being the equilibrium
fractionation factor at temperature at which condensation takes place. The Rayleigh
equation can also be expressed in the form of d-notation, in which R and a are
translated into d and e respectively.
d = d 0 + e ln f (18)
In Equation (18), d refers to instantaneous isotopic composition of

progressively diminishing vapor reservoir at an instance when residual fraction (f) of
the original reservoir with isotopic composition d0 has diminished from initial value f
= 1 to a value f < 1, with e being equilibrium enrichment at temperature at which
condensation takes place.
The Equation (18) is useful for theoratical estimation of isotopic variation at
succesive stages of condensation or evaporation under equilibrium condition.
However, in natural situations, the application of Rayleigh equation is more complex
due to the fact that non-equilibrium fractionation effects are involved (mainly during
evaporation) and the mass and the isotopic composition of residual vapor reservoir
may be altered due to addition of secondary vapor flux by evapotranspiration.
The effect of the admixture of evapotranspiration flux on the isotopic
composition of the downwind atmospheric vapour and subsequent precipitation
depends on the details of the evapotranspiration process. Transpiration returns
precipitated water essentially un-fractionated back to the atmosphere, despite the
complex fractionation in leaf water (Forstel, 1982; Zimmermann et al., 1967). Thus
transpiration, by returning vapour mass with isotopic composition RV (= Rl/a) in the
downwind direction, in a way restores both the vapour mass and the heavy isotope
depletion caused by the rainout in such a way that the next rainout event is not as
depleted as it would have been without the transpiration flux. Under such
circumstances, the change in the isotopic composition along the air mass trajectory is
only due to the fraction ‘fnet’, representing the net loss of water from the air mass,
rather than being a measure of the integrated total rainout. This causes apparent
reduction in the downwind isotopic gradient. The evaporated water, on the other hand,
is usually depleted in heavy species relative to that of transpired vapour, thus restoring
the vapour mass to the downwind cloud but reducing its isotopic composition. This
may cause apparent increase in the downwind isotopic gradient.
9. Global Meteoric Water Line (GMWL)
Craig (1961a) for the first time showed that in spite of the great complexity in
different components of the hydrological cycle, d18O and dD in fresh surface waters
(representing precipitation) correlate on a global scale. The regression line between
d18O and dD is referred to as meteoric water line. Craig's global meteoric water line
(GMWL) defines the relationship between d18O and dD in global meteoric water (i.e.
derived from precipitation) as:
dD = 8 ´ d18O + 10 ( ‰ SMOW ) (19)

It must be noted that Craig’s GMWL is based on fresh surface water and not
the actual precipitation.
Improving the precision of the Craig’s GMWL, Rozanski et al.(1993)
compiled the isotope data of precipitation from 219 stations of the IAEA/WMO
Page 15 of 28
operated Global Network for Isotopes in Precipitation (GNIP). This refined

relationship between 18O and D in global precipitation (Figure 1) is given by:
dD = 8.17 ( ±0.07 ) ´d18O + 11.27 ( ±0.65 ) ( ‰ VSMOW ) (20)
The d18O-dD regression equation of Rozanski et al.(1993) is based on actual

precipitation whereas that of Craig (1961a) was based on fresh surface waters.
Figure 1. The linear regression line between d18O and dD of global precipitation
samples. Data are weighted average annual values for precipitation monitored at 219
stations of IAEA/WMO global network. Redrawn from Rozanski et al (1993).
The GMWL indicates that the isotopic composition of meteoric waters behave
in a fairly predictable fashion. The GMWL is average of many local or regional
meteoric water lines, which may differ somewhat in slope and intercept from each
other due to varying climatic and geographic parameters. A Local Meteoric Water
Line (LMWL) can differ from global line in both slope and deuterium intercept.
Nonetheless, GMWL provides a reference for interpreting the hydrological processes
and provenance of different water masses.
There are specific reasons why the slope of the GMWL is around 8 and
deuterium intercept is around 10. Further, the d18O-dD regression lines for local
precipitation (LMWL) and for any other H2O reservoir can differ from GMWL in
slope and intercept. This deviation of slope and intercept from that of GMWL
provides important insights about the hydro-meteorological processes operating in a
given geographical region or at a given time.
In order to understand why the slope of GMWL is around 8 and what does it
signify, the following exercise may be necessary.
Analogous to Equation(18), following two equations can be set up for oxygen
and hydrogen isotopes.
(
d18 O = d18 O0 + 18 e´ ln f ) (21)
Page 16 of 28
(
dD =dD0 + 2 e´ ln f ) (22)
By eliminating the term ln f, following equation can be derived:

æ 2e ö é æ 2 e öù
dD = d 18 O ´ ç ÷ + êdD0 - d 18 O 0 ´ ç ÷ú (23)
ç 18 e ÷ ê ç 18 e ÷ ú
è ø ë è øû
Equation (23) is a straight line (y = mx+c) in the coordinates of d18O and dD,
which is nothing but the GMWL. It can be noticed by comparing Equations(19) or
(20) with (23) that the slope of the regression lines correspond to ratio æç e 18 ö÷ i.e.
2
è eø
the ratio in which 18O and D are partitioned between vapour and liquid phases during
æ 103 lna 2 ö
condensation. From Table 5 it is seen that at 25°C temperature the ratio ç ÷
ç 103 lna18 ÷
è ø
has a value of 8.1, nearest to the slope of GMWL. This, however, is just a close
æ 103 lna 2 ö
approximation. In fact, the ratio ç ÷ varies only narrowly between 8 at 30 °C
ç 103 lna18 ÷
è ø
and 9 at 0°C (see Table 5. Therefore, the slope 8 of GMWL only signifies the ratio of
fractionation for hydrogen and oxygen under equilibrium condition which is around 8.
It is important to understand that the slope 8 of GMWL does not signify condensation
temperature of ~25°C, but it conveys that the condensation is largely under
equilibrium.
The intercept of GMWL on the other hand signifies the non-equilibrium
fractionation during formation of vapour. If only equilibrium fractionation was
prevalent in nature, the intercept of the d18O-dD regression should have a value of 0.
This is because, under equilibrium condition (such as during condensation of vapour
æ 2e ö
in cloud), dD 0 = d 18 O0 ´ ç ÷ and therefore, GMWL should have intercept value of
ç 18 e ÷
è ø
é æ 2e ö ù
0 and should have passed through origin êdD0 - d18 O0 ´ ç ÷ = 0 ú . However, the
êë ç 18 e ÷ ú
è ø û
GMWL has an intercept of ~10, which signifies that original vapour parcel is formed
æ 103 lna 2 ö
under the condition in which ç ÷ is considerably different from 8, which
ç 103 lna18 ÷
è ø
means that kinetic fractionation is effective during evaporation from the oceans. The
evolution of d18O and dD values of meteoric waters begins with evaporation from the
oceans, where the rate of evaporation controls the water - vapour exchange and hence
the degree of isotopic equilibrium. Increased rates of evaporation impart a kinetic or
non-equilibrium isotope effect to the vapour. Kinetic effects are influenced by surface
temperature, wind speed (shear at water surface), salinity and, most importantly
humidity. At lower values of humidity, evaporation becomes an increasingly non-
equilibrium process.
Page 17 of 28
9.1 The deuterium excess (d-excess)

The observed intercept of the GMWL was advantageously used by Dansgaard,
(1964) to define a parameter (d-excess), which can be calculated for individual pair of
d18O and dD using following equation.
d-excess = dD - 8 ´ d18O ( ‰ ) (24)
The basic premise behind defining such a parameter is that whenever kinetic
fractionation is involved, the net ratio of fractionation for deuterium to oxygen is
different from 8. This is because, unlike equilibrium fractionation, the magnitude of
kinetic fractionation for oxygen is more than that for hydrogen
é De2 H ù
(bl-v)
ê » 0.88ú (see Equations (13) and (14)). Since 18O is more fractionated
ê De18O(bl-v) ú
ë û
2
compared to H due to kinetic fractionation during evaporation, the liquid phase is
relatively more enriched in 18O compared to 2H. Consequently, the resultant vapour is
relatively more enriched in 2H compared to 18O, due to kinetic effects. These isotope
imprints of kinetic evaporation can be easily detected in the d-excess. The average d-
excess of meteoric waters is ~10‰. As a thumb rule, the d-excess of water decreases
if it undergoes kinetic evaporation and consequently the d-excess of resultant vapour
correspondingly increases.
It is must be understood that deuterium excess (d-excess) and the deuterium
intercept of d18O-dD regression lines are two different parameters and should not be
confused while interpreting the data set. While deuterium intercept is the property of a
dataset under investigation the d-excess can be calculated for individual pair of d18O-
dD. Therefore, based on d-excess, individual sample can be separately interpreted
whereas intercept is not useful for individual sample. In fact, a set of samples defining
a regression line intercept can have very different d-excess values.
The d-excess as defined above represents the excess dD than 8 times d18O for
any water or vapour sample. Since magnitude of equilibrium fractionation for D is
about 8 times that for 18O, any value of dD in vapour, in excess of 8 times d18O
signifies the effect of kinetic fractionation due to evaporation. As mentioned earlier,
the intercept (~10‰) of GMWL also signifies the kinetic fractionation during
evaporation but the difference between intercept and d-excess is that the intercept of a
meteoric or any other water line is valid for an entire dataset whereas, the d-excess
parameter can be calculated for a single water sample whose dD and d18O values are
known.
As the evaporation proceeds, because of relatively higher enrichment of 18O in
the residual water, the d-excess of the evaporating water body decreases and that of
the resulting vapour increases. Therefore, if the original water was meteoric in origin,
the residual water not only gets enriched in heavier isotopes but also shows
progressively lower d-excess values as the evaporation proceeds i.e. its position on the
d18O – dD plot will be below the Local Meteoric Water Line. The resulting vapour on
the other hand shows the opposite effect. Further, since condensation is an
equilibrium process (with slope ~8), it does not significantly alter the d-excess until
significant rainout occurs from the same vapour parcel. Thus, d-excess provides an
additional handle on identifying vapours of different histories and their mixing. Due
to the effect of evaporation, most meteoric and subsurface processes shift the d18O–
Page 18 of 28
dD signatures of water to a position below the LMWL. It is rare to find precipitation

or groundwater’s that plot above the LMWL, i.e., showing higher d-excess. However,
in low-humidity regions, re-evaporation of precipitation from local surface waters
and/or soil water/ water table creates vapour masses with isotopic content that plots
above the LMWL. If such vapours are re-condensed in any significant quantity before
mixing with the larger tropospheric reservoir, the resulting rainwater will also plot
above LMWL, along a condensation line with slope ~8. It is however, important to
recall that recycling of water back to the atmosphere in the form of vapour from soil
moisture by plant transpiration is a non-fractionating process that does not affect the
d-excess.
A small fraction of rain percolates down through the soil layer eventually to
become groundwater. For many ground waters, their isotopic composition has been
shown to equal the mean weighted annual composition of precipitation (Bhattacharya
et al., 1985; Douglas, 1997; Hamid et al., 1989; Krishnamurthy and Bhattacharya,
1991) (Rank et al., 1992). However, significant deviations from precipitation are also
found in several cases. Such deviations from local precipitation are more pronounced
in arid zones due to extensive evaporation from the unsaturated zone or even
evaporative losses from water table (Allison et al., 1984; Dincer et al., 1974).
Considering that only a small percentage of precipitation actually reaches the water
table in most situations, the meteoric signal in ground water can get significantly
modified. Isotope variations in precipitations get attenuated and seasonal biases in
recharge are imparted to the newly formed ground water. This bifurcation of the
hydrological cycle between precipitation and surface water on one hand and
groundwater on the other hand, ends where groundwater discharges and re-joins
surface runoff in streams and rivers. Thus, oxygen and hydrogen isotopes can play a
significant role in quantifying relative contribution of groundwater to stream flow and
in understanding the hydraulic processes operating in a catchment area.
10. Isotope Effects
As discussed in the forgoing, the magnitude of isotope fractionation, expressed
by the fractionation factor is primarily governed by the temperature and relative
humidity in the environment where phase change process is occurring. The extent to
which the isotopic composition of the reactant and the product reservoir changes
depends on the extent to which a phase change process has occurred, or in other
words, the extent to which mass loss has occurred from the diminishing reservoir (due
to rainout from cloud or evaporation from any water body ranging from a falling
raindrop to surface reservoir). These two basic controlling factors (magnitude of
isotope fractionation and progress of phase change reaction) determine the eventual
isotopic composition of product or reactant reservoir. In nature, the influence of these
two factors is manifested in terms of characteristics isotopic signatures in water.
These characteristic isotopic signatures are more popularly known in terms of various
isotope effects as listed below.
10.1 Temperature Effect (d-T Relationship)
A very common isotope effect observed in nature is that the isotopic
composition of precipitation (and consequently other associated hydrological
components) becomes progressively lighter (i.e. d18O and dD values decrease) with
decreasing temperature. In the Indian context, the d18O and dD values of precipitation
at cooler stations (e.g. Rishikesh, Badrinath, Ladakh etc) would be lower than at
warmer stations (e.g. Mumbai, Ahmedabad, Jaipur, etc). In the global context, the
Page 19 of 28
isotopic composition at locations nearer to Arctic and Antarctic regions (e.g. Canada,
Alaska, Greenland, Sweden, Finland, and Island) would be lower than at warm
tropical stations (e.g. Mumbai, Colombo, Bangkok).
Dansgaard (1964) established a linear relationship between surface air
temperatures and d values for mean annual precipitation on a global basis as follows:
d18O = 0.695 Tannual – 13.6‰ SMOW and dD = 5.6 Tannual – 100‰ SMOW
Based on the monthly average temperatures the global relationship is:
d18O = (0.338 ± 0.028) Tmonthly – 11.99 ‰ SMOW
On average, a 1‰ decrease in average annual d18 O corresponds to a decrease
of about 1.1 to 1.7 ºC in the average annual temperature. Corresponding variations
occur also for dD and this covariance is the principal reason for the linear relationship
between the two, better known as the GMWL.
It must, however, be noticed that the global linear relationship between d18O
and T is only an approximation and on a regional basis it is far from linear. Departure
from the global relationship occurs at the regional to local scale due to physiographic
variations. Strong differences between d18O-T relationships for marine, continental
and interior stations are observed (Rozanski, 1993). The departure from global
relationship may also occur when data is available only for a small time scale. The
correlation between d18O and T may be even poorer when daily or event based data
are analyzed. This is because weather patterns, storm tracks and air mass mixing can
be very unsteady in space and time making it impossible to derive any clear d18O – T
relationship. The stochastic nature of weather does not permit use of d18O as a proxy
for temperature at anything less than seasonal to multi-annual scale.
10.2 Latitude Effect
It is commonly observed in nature that isotopic composition of precipitation
(and consequently other associated hydrological components) becomes progressively
lighter (i.e. d18O and dD values decrease) with increasing Latitude. This effect is
known as the latitude effect. In a way, the latitude effect can be considered as another
manifestation of the temperature effect as discussed previously. The temperature
decreases progressively with increasing latitude and hence the isotopic composition
becomes progressively lighter as discussed above. In addition to temperature
dependence, Polar Regions are located at the end of Rayleigh rainout process and so
the d18O-T gradient becomes increasingly steeper with increasing latitude.
Consequently, d18O-latitude gradient also becomes increasingly steeper with
increasing latitude. For example, for continental stations of North America and
Europe a latitude gradient of -0.6‰ per °latitude is reported whereas a considerably
steeper gradient (-2‰ per °latitude) is observed for the colder Antarctic stations. It is
to be noted that latitude gradient is much gentle in the lower latitudes where over 60%
of atmospheric water vapor originates.
10.3 Continental Effect
It is observed that the isotopic composition of precipitation (and consequently
other associated hydrological components) becomes progressively lighter (i.e. d18O
and dD values decrease) with increasing in-land distance from coast. As the vapour
mass moves away from its source region towards inland stations across a continent, its
isotopic composition evolves more rapidly due to topographic effects and the
Page 20 of 28
temperature extremes that characterize continental climates. Continental stations

experience strong seasonal variations in T, because of their distance from coast which
reduces the moderating marine influence. Coastal precipitations are isotopically
enriched, while the colder inner continental regions receive isotopically depleted
precipitation with strong seasonal differences.
10.4 Altitude Effect (Alpine effect or Elevation effect)
It is observed that at higher altitude where average temperatures are lower,
precipitation is generally isotopically depleted. This effect of isotopic depletion of
increasing altitude is commonly known as the altitude effect. When a vapour parcel
leaves the oceanic area and encounters the continental region, vapour mass rises over
the landscape even with the minor relief and cools adiabatically (just by expansion,
without losing temperature) causing orographic precipitation. If the orographic barrier
is high, there can be copious rain and steeper isotopic gradient. The isotopic depletion
in 18O is reported to range from -0.15 to -0.5 ‰ per 100 m rise in altitude. That in the
deuterium is reported to range from -1 to -4‰ per 100m. Altitude effect can be
importantly used to identify and distinguish between the ground waters recharged at
high altitudes from those recharged at low altitude. This effect can be advantageously
used to identify the recharge area for the springs in the mountainous regions so that
the dying springs can be rejuvenated.
10.5 Seasonal effect
It is observed that greater seasonal extremes in temperatures generate strong
seasonal variation in isotopes of precipitation, commonly known as the seasonal
effect. The strong seasonal variation in isotopic composition of precipitation can be
advantageously used to trace the groundwater circulation through tracing the
movement of such a precipitation with seasonal isotopic character. Seasonal effects
can also be advantageously used to understand the watershed response to
precipitation, to figure out the time during the year when most recharge occurs, and to
understand the recharge characteristics of shallow groundwater.
10.6 Amount Effect
It is observed in general that heavy rain events are isotopically depleted
whereas light rain events are isotopically enriched. This inverse relationship between
the amount of rain and its isotopic composition is commonly known as the amount
effect. Friedman et al. (1962) first showed that evaporation during rainfall would shift
the water away from the meteoric water line along an evaporation slope less than 8.
Later on Dansgaard (1964) described such evaporation as amount effect on the
isotopic composition of precipitation, although in-cloud phenomena and mixing also
appears to play a role. The simplest way to understand the amount effect is that lighter
rain events can undergo considerable evaporation during its fall from cloud base to
ground level, resulting in isotopic enrichment. In contrast, heavier rain events may not
undergo so much evaporation during its fall and may not be enriched due to
evaporation (i.e. it will be depleted) because once the air column become water-
saturated, such evaporation from falling raindrops may diminish. Consequently, the
heavy rain events will be isotopic depleted compared to lighter rain event. Obviously,
the amount effect is best observed in arid regions.
It must be noted, however, that weather patterns, storm tracks and air mass
mixing can be very unsteady in space and time and hence individual rain events may
Page 21 of 28
or may not exhibit the relationship with amount of daily rainfall. Instead, it is
desirable that the amount effect is discussed for monthly average rainfall.
11. Interpretative Significance of slope, intercept and d-excess
In order to understand the interpretative significance of various isotopic
parameters it is necessary to visualize how various theoretical concepts and equations
discussed in the forgoing can be practically used and how it would manifest in the
data under a given hypothetical condition.
For example, let us begin with tropical ocean surface water with isotopic
composition of d18O = 0‰ and dD = 0‰. This is indeed a very close approximation
to real situation. Suppose evaporation is taking place at 25 °C temperature and under
the relative humidity of 85%. Using Equations (11) and (12) one can calculate 18e and
2
e values (9.37‰ and 79.3‰ respectively) for 25 °C. Using Equations (13) and (14)
one can also calculate D18e and D2e values (2.13‰ and 1.88‰ respectively) for
relative humidity of 85%. The effective total fractionation (e + De) can be calculated
as the sum of the two types of fractionations, as given in the RHS of Equation (15).
Thus the approximate isotopic composition of ocean vapour can be estimated as d18O
= -11.5‰ and dD = -81.21‰. Using the Rayleigh distillation equation in d notations,
as given in Equation (18), one can compute the evolution of the isotopic composition
of vapour as it rains out progressively. Correspondingly, one can also estimate the
instantaneous isotopic composition of rain in equilibrium with vapour at each stage.
The evolution of isotopic composition of vapour and rain, as a function of fraction of
original vapour remaining at successive stage of rainout, is shown in Figure 2.
Important point to be noticed here is that with successive rainout, both the vapour and
the rain diminishes in its heavier isotope content as reflected in progressively
decreasing d18O and dD values. It is also seen that the d-excess also decreases with
progressive rainout.
This example is just for visualization of isotopic variations. In reality,
situations are more complex than simple addition of equilibrium and kinetic
fractionation. Formation of atmospheric vapour is a more complex process involving
mixing between evaporated water vapour and residual atmospheric water vapour
following condensation and rain over sea (Craig and Gordon, 1965). According to the
Craig and Gordon (1965) model mass is conserved such that net evaporation equals
net precipitation and the mean isotopic composition of outgoing oceanic vapour
equals the global mean for precipitation.
As an example, the effect of relative humidity on isotopic evolution of water
during evaporation is shown in Figure 3. The isotopic evolution of a hypothetical
water sample (d18O = –4‰ and dD = –22‰; which is also the mean global
precipitation value according to Craig and Gordon (1965) Model) on the GMWL, as
it evaporates under two different Rh regimes (100% and 10%), but at the same
temperature (30ºC), can be computed using Equations (11), (12), (13), (14), (15) and
(18). As shown in Figure 3, the water evolves along a line with very low slope and
intercept values in case of 10% Rh. However, in case of 100% Rh, water evolves
along a line which has slope value slightly greater than GMWL. This simple exercise
conveys why lower slope value of any data set is ascribed to evaporation.
These simple fractionation processes are at the core of some of the
interpretative aspects.
Page 22 of 28
The slope and intercept of d18O-dD regression lines for a set of samples and d-
excess of individual water sample can provide some useful hydrological insights. If
the slope of d18O-dD regression line for a set of samples is less than that of GMWL it
is an indication that the water under consideration has undergone certain degree of
evaporation. Lower the slope greater the evaporation. The intersection point of
LMWL and GMWL is indicative of the average isotopic composition of precipitation
at that location. Intersection point of LMWL and d18O-dD regression line for
groundwater is indicative of the average isotopic composition of the surface water
from which the groundwater is recharged.
The intercept of the d18O-dD regression line can provide useful hydrological
insights, only if the slope of the regression line is ~8. If the slope is much different
from ~8 the intercept cannot be assigned any interpretative significance. If the slope
of LMWL is ~8 and intercept is >10‰ it is an indication that precipitation is derived
from vapour which is produced by kinetic evaporation under considerably lower
relative humidity. For example, the Eastern Mediterranean Water Line (EMWL)
defined by Gat and Carmi (1970) has slope = 8, but intercept = 22.
The d-excess is the most useful parameters in deriving hydrological insights
from water isotope data. Lower than average d-excess of a rainwater sample could be
due to evaporation from falling raindrops or it could as well signify considerable
rainout from original marine vapour parcel. Higher (than average) d-excess in a
particular rainwater sample signifies either formation of marine vapour parcel under
lower (than average) relative humidity (for e.g. from Mediterranean Sea) or
contribution of recycled vapour from continental areas for that particular event. It may
be possible to rule out one the two possible interpretations in case of both high or low
d-excess values if the d-excess value of a sample is interpreted in combination with
d18O or dD values. For example, if lower d-excess values are associated with
significantly higher d18O values, it indicates the evaporation from falling rain drops
because, as discussed earlier, evaporation causes decrease in d-excess and increase in
d18O or dD values. On the other end, considerable rainout from a given vapour parcel
results in progressive decrease in both d-excess and d18O.
12. Epilogue
This tutorial lecture note was prepared by me initially for the participants of
the DST-SERC sponsored one week training workshop on isotope hydrology
organised at NIH, Roorkee in December, 2011, as part of the IWIN National
Programme. Since then, this lecture note has been in circulation among students and
new entrants in the field of isotope hydrology research. I have tried to revise and
update this note periodically, maintaining its simplistic style of presenting the isotope
concepts so that a researcher not much familiar with isotope systematics can also
grasp the basic philosophy and prepare oneself for the advanced learning from text
books.
I am singularly responsible for the typographic errors or factual mistakes, if
any. I apologies for the same and request you to please bring it to my knowledge, for
the benefit of other students.
Page 23 of 28
Figure 2. Isotopic evolution of vapour and rain as a function of fraction of original

marine vapour remaining at successive stages of rainout.
Figure 3. Isotopic evolution of water (d18O = –4‰ and dD = –22‰ under different
relative humidity conditions but at the same temperature.
Page 24 of 28
Acknowledgement
Most of the little bit that I could learn about “isotope hydrology”, is due to my
close scientific interactions and long-term association with three distinguished
scientists of India, namely, Dr. S.K. Gupta, Prof. R. Ramesh and Prof. S.K.
Bhattacharya, who were my teachers and senior colleagues at PRL, Ahmedabad. I
sincerely thank and dedicate this lecture note to them. However, I am singularly
responsible for any error in this lecture note.
My close friend and colleague Dr. M.G. Yadava of Radio Carbon Laboratory
of PRL, tirelessly helped me in overcoming a geologist’s limitations in physics and
mathematics. I have no words to thank him.
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Tutorial lecture at training programme on Himalayan Glaciology. JNU Convention Centre, 3 September, 2014.

Oxygen and Hydrogen

For correspondence: [email protected]

Oxygen and Hydrogen Isotope Systematics for Hydrological Applications

Isotopologue H216O H218O H217O HD16O D216O

4. Expressing Isotopic Composition

Table 3. Measured abundance ratios in international standard reference material

Isotopes Standard Abundance Ratio

dDSLAP = –428.0‰ VSMOW dDGISP = –189.5‰ VSMOW

Q = s-1m3/2 å e-E/kT (2)

purposes can be ignored in actual calculations of fractionation factors. The diffusive

In view of this multitude of expressions, one needs to be careful while using

Table 5. Values of 103ln a, fractionation factor a, and enrichment e calculated using

Temp. æ 103 lna 2 ö

80 5.92 1.0059 5.93 36.74 1.0374 37.42 6.2

De18O(bl-v) = 14.2× (1 – h ) ‰ (13)

De2 H(bl-v) = 12.5× (1 – h ) ‰ (14)

These equations provide only approximate value of enrichment because other

d18Ol - d18O v = e18

The RHS in Equation (15) indicates the total fractionation (equilibrium +

In Equation(16), D and D’ refers to diffusive velocities of light and heavy

In Equation (18), d refers to instantaneous isotopic composition of

dD = 8 ´ d18O + 10 ( ‰ SMOW ) (19)

operated Global Network for Isotopes in Precipitation (GNIP). This refined

dD = 8.17 ( ±0.07 ) ´d18O + 11.27 ( ±0.65 ) ( ‰ VSMOW ) (20)

The d18O-dD regression equation of Rozanski et al.(1993) is based on actual

By eliminating the term ln f, following equation can be derived:

9.1 The deuterium excess (d-excess)

d-excess = dD - 8 ´ d18O ( ‰ ) (24)

dD signatures of water to a position below the LMWL. It is rare to find precipitation

temperature extremes that characterize continental climates. Continental stations

Figure 2. Isotopic evolution of vapour and rain as a function of fraction of original

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