International Journal of Advanced Academic Research | Sciences, Technology and Engineering | ISSN: 2488-9849

Vol. 5, Issue 10 (October 2019)

ISOTOPE GEOCHEMISTRY AND ITS APPLICATION IN

HYDROLOGICAL STUDIES: A REVIEW

*1Onyeocha, N.C., 1Okeke, O.C. and 2Adeyi, G.O.

1
Department of Geology, Federal University of Technology, Owerri, Imo State, Nigeria.
2
Department of Nautical Science, Maritime Academy of Nigeria, Oron, Nigeria.
*Corresponding author‟s email: charlybravo.oc@gmail.com

Abstract
Isotopes may be defined as alternative forms of an element produced by variations in the
number of neutrons in nucleus (Richard, 2006). Isotopes in hydrology give a direct insight into
the movement and distribution processes within the hydrological system. Water in its natural
state contains environmental isotopes and conclusions may be drawn from their abundance
variations. Isotopes which are naturally produced and incorporated into the hydrological cycle,
are often referred to as "Environmental Isotopes" (Yurtsever and Araguas, 1993). Examples are
Oxygen isotopes (16O, 17O and 18O), Hydrogen isotopes (1H, 2H and 3H), Sulphur isotopes (32S,
33
S and 34S) etc. Included in this group are also isotopes released due to man-made activities,
but distributed in the environment at regional or global scale due to natural processes. The
isotopes commonly employed in hydrological studies are the heavy stable isotopes of the water
molecule, deuterium and oxygen-18 and the radioactive isotopes, tritium and carbon-14. The
stable isotopes are excellent indicators of the circulation of water, while the radioactive
isotopes are of special value in detecting the residence time, assuming no contamination of the
water has occurred. The applications of these characteristics in connection with surface and
groundwater resources are discussed briefly with few case histories.
Keywords: Isotopes, Water resources, Hydrological, Geochemistry, Applications.

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1. Introduction
Isotope geochemistry is an aspect of geology that is based upon the study of natural variations
in the relative abundances of isotopes of various elements. Variations in isotopic abundance are
measured by isotope ratio mass spectrometry, and can reveal information about the ages and
origins of rock, air or water bodies, or processes of mixing between them (Nada and Dusan,
2006). Isotope hydrology is the study of the Isotope signatures of water (Nwachukwu et al.,
2014).

Isotopes are atoms of the same element that have different numbers of neutrons(Richard,
2006). Differences in the number of neutrons among the various isotopes of an element mean
that the various isotopes have different masses. The superscript number to the left of the
element designation is called the mass number and is the sum of the number of protons and
neutrons in the isotope.

For example, among the hydrogen isotopes, deuterium (denoted as D or 2H) has one neutron
and one proton. This mass number of 2 is approximately equal to twice the mass of protium
(1H), whereas tritium (3H) has two neutrons and its mass is approximately three times the mass
of protium. Isotopes of the same element have the same number of protons. For example, all
isotopes of oxygen have 8 protons; however, an oxygen atom with a mass of 18 (denoted 18O)
has 2 more neutrons than oxygen with a mass of 16 (16O).

Isotopes which are naturally produced and incorporated into the hydrological cycle, are often
referred to as "Environmental Isotopes" (Yurtsever and Araguas, 1993). Examples are Oxygen
isotopes (16O, 17O and 18O), Hydrogen isotopes (1H, 2H and 3H), Sulphur isotopes (32S, 33S and
34
S) etc. Included in this group are also isotopes released due to man-made activities, but
distributed in the environment at regional or global scale due to natural processes.

Variations in the stable isotopes of water, such as 18O and 2H, are widely used as
environmental tracers in studying hydrological processes (Buttle, 1998, Clark, 1997, Calligaris
et al., 2018). Short and long-term isotope signals in precipitation are thus transmitted through
the whole (Clark, 1997.) Isotopes of particular interest for hydrological studies include the
stable isotopes of water (18O catchment, 2H), which are incorporated within the water molecule
(H218O, 1H2H16O), and exhibit systematic spatial and temporal variations as a result of isotope
fractionations that accompany water-cycle phase changes and diffusion (Clark, 1997).
The developments in isotope geochemistry have lead to significant advances in the ability to
undertake source determinations at contaminated sites; unravel commingled plumes of
contaminants; and monitor natural attenuation at contaminated sites.

Isotope techniques are effective tools for fulfilling critical hydrological information needs,
such as:

i. The origin of groundwater;

ii. The determination of its age, velocity, and direction of flow;
iii. The interrelations between surface waters and groundwaters;
iv. The possible interconnections between different aquifers; and

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v. Aquifer characteristics such as porosity, transmissivity, and dispersivity.

The cost of such investigations according to Pradeep et al., (2002) is often relatively small in
comparison with the cost of classical hydrological techniques, and in addition isotopes provide
information that sometimes could not be obtained by other techniques.
“Applications of isotopes in hydrology are based on the general concept of “tracing,” in which
either intentionally introduced isotopes or naturally occurring (environmental) isotopes are
employed. Isotopes employed in hydrological studies could either be stable or unstable
(radioactive) isotopes.

Environmental isotopes (either radioactive or stable) have the distinct advantage over injected
(artificial) tracers that they facilitate the study of various hydrogeological processes on a much
larger temporal and spatial scale through their natural distribution in a hydrological system.
Thus, environmental isotope methodologies are unique in regional studies of water resources to
obtain time and space-integrated characteristics of groundwater systems. The use of artificial
tracers generally is effective for site-specific, local applications” (Pradeep et al., 2002).
This review paper provides an overview in the use of naturally occurring stable isotopes
including radiogenic isotopes which are important hydrological tracers for hydrological
studies. It is a matter of fact that the isotopic systematics of specific ratios or single isotopic
abundances are well known, whereas other isotopes are considered not too exhaustively
discussed as no many data are still available. Eventually, new isotopic pairs have recently been
applied to the context of environmental geochemistry and can be considered as new frontiers in
this important discipline.

2. Occurrence and Characteristics of Environmental Isotopes

The environmental isotopes represent one of the most useful tools in geochemistry to
investigate groundwater quality, geochemical evolution, recharge processes, rock–water
interaction, and the origin of salinity and contaminant processes (Barbara et al. 2014).

“Environmental isotopes, both stable and radioactive, occur in the atmosphere and the
hydrosphere in varying concentrations. So far, the most frequently used environmental isotopes
include those of the water molecule, hydrogen (2H or D, and 3H) and oxygen (18O), as well as
carbon (13C and 14C) occurring in water as constituents of dissolved inorganic and organic
carbon compounds. 2H, 13C and 18O are stable isotopes of their respective elements whereas 3H
and 14C are radioactive isotopes. The stable isotopes are usually measured using an isotope
ratio mass spectrometer, in terms of the isotope ratios of the less abundant to more abundant
isotope, for example, 2H/1H and 18O/16O (1H and 16O being the number of atoms of the most
abundant isotopes of the respective elements). The radioactive isotopes are measured either by
the counting of their radioactive decays (low-level counting, for example, by liquid
scintillation counter) or the number of atoms (using accelerator mass spectrometry) in a given
sample”(Pradeep et al., 2002).

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2.1 Stable Isotopes

Stable isotopes are naturally occurring isotopes of light elements which do not undergo any
decay to produce daughter isotopes (Nwachukwu et al., 2014) for example Nitrogen (14N, 15N),
Oxygen (16O, 18O), Sulphur (32S, 34S), etc. Stable isotopes of many different elements are used
in hydrology; however, the most commonly used are those of oxygen and hydrogen. Variations
in stable isotope ratios of natural compounds are governed by chemical reactions and phase
changes because of the energy difference between chemical bonds involving different isotopes
of an element. Such energy differences are caused by the relative mass difference between
isotopes (Pradeep et al., 2002). The stable isotopes of light elements show greater variations
because they have larger relative mass differences. For example, the magnitude of variations in
2
H/1H is greater than in 18O/16O because the mass difference between 2H and 1H is 2:1 while
the same for 18O and 16O is 1.1:1. Stable isotope ratios in hydrology are conventionally
reported as per mil (‰) deviation from those of a standard using the δ (delta) notation:
𝑅𝑠𝑎𝑚𝑝𝑙𝑒 − 𝑅𝑠𝑡𝑎𝑛𝑑𝑎𝑟𝑑
𝜕‰ = 𝑥 1000 … … … … … … … … … … … … . 1
𝑅𝑠𝑡𝑎𝑛𝑑𝑎𝑟𝑑
where R is isotope concentration ratio (2H/1H, 13C/12C, 15N/14N, 18O/16O, 34S/32S) of a sample or
a standard.

Table 1: Environmental Stable Istopes and their Applications.

(After Archana et al., 2014)

Isotope Ratio % Natural Reference (ppm) Commonly Application in

abundance measured phases hydrology
2 2
H H/1H 0.015 VSMOW (155) H2O,CH4 Origin of water
13 13 12
C C/ C 1.11 VPDB CO2, Carbonates Carbonates source,
Groundwater Dating
15 15
N N/14N 0.366 Air N2 (3677) N2, NH4NO3 Source of pollution
18 18 16
O O/ O 0.204 VSMOW (2005) Origin of water
34 34 32
S S/ S 4.21 CDT Origin of salinity,
Redox condition of
aquifer
37 37
Cl Cl/35Cl 24.23 SMOC (0.324) Saline waters Source of pollution
87 87
Sr Sr/86Sr 07.00 USGS Tridacna Solution Provenance of water
11 11 10
B B/ B 80.1 NISTRM 951 – Solution Source of pollution
(Sodium borate)

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Table 2: Stable Isotope in Hydrological Studies and their Applications.

(After Yurtsever and Araguas, 1993)

Isotope Potential Application

Oxygen – 18 (18O) - Genesis of water
and - Source of replenishment to groundwater and process
Deuterium (2H) tracing
- Component tracing – mixing proportion of different
components of flows; hydraulic interconnections
- Paleohydrological indicators
- Geothermal activity
Carbon – 13 (13C) - Origin of carbon compounds
- Correction for 14C age dating
Sulphur – 34 (34S) - Natural tracer for sulfates in water
- Identification of source pollution
Nitrogen – 15 (15N) - Origin of nitrates
- Identification of sources of pollution

2.2 Radioactive (Unstable) Isotopes.

Radioactive (Unstable) Isotopes are nuclides that have unstable nuclei that decays, emitting
alpha, beta, and sometimes gamma rays (Nwachukwu et al., 2014). Examples are decay of
radioactive 18F to stable 18O, 14C to stable 14N, etc. Among the environmental radioisotopes,
tritium and carbon-14 have found the widest application in groundwater studies. Radioactive
isotopes (also called radioisotopes) occurring in groundwater originate from natural and/or
artificial nuclear processes Cosmogenic radioisotopes are produced in nuclear reactions
between the nucleonic component of cosmic radiation and the atmosphere. Anthropogenic
radioisotopes are produced in nuclear bomb tests and nuclear reactors. The concentrations of
all these radioisotopes in groundwater are very low and usually measured by counting their
decay rate A in a given sample. The number of atoms N in a sample can be derived from A by
the relationship:

𝐴 = 𝑁 .𝜆……………………………………………2
where λ, the decay constant, is related to half-life T1/2 by the equation λ = ln 2 / T1/2. For long-
lived radioisotopes such as 36Cl and 129I, the decay rate becomes immeasurably small. In these
cases the number of atoms has to be measured directly, which is possible by the accelerator
mass spectrometry (AMS) technique. The AMS technique is superior to the conventional decay
counting for 14C, since AMS requires a very small sample size (up to 1000 times less than
conventional requirement) for analysis.

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Table 3: Environmental Radioisotopes and their Applications. (After Archana et al.,

2014)

Isotope Half life Type Energy (MeV) Applications in hydrology

(years)
Tritium (3H) 12.3 𝛽 0.019 Young groundwater dating
Carbon (14C) 5730 𝛽 0.156 Old groundwater dating
Chlorine 36 3.1 x 105 𝛽 0.714 Very old groundwater dating
(36Cl)
*Cesium – 30 𝛽 0.661 Sediment dating
137 (137Cs)

Table 4: Radioactive Isotopes in water resources studies (After Yurtsever and Araguas
1993)

Isotope Half-life (years) Source (origin) Present Limitations

85Kr 10.8 Nuclear reactors Sampling, counting
3H 12.43 Cosmic rays
Thermonuclear
Nuclear reactors
32Si 100 Cosmic rays Initial activity
Thermonuclear Sample size
Crustal (?) counting time
39Ar 269 Cosmic rays Sample size
Crustal counting time
14C 5730 Cosmic rays Complex
Thermonuclear geochemistry
Crustal Isotope exchange
processes
81Kr 210000 Cosmic rays Analytical
234U 250000 Decay chain Initial activity
interactions
36Cl 306000 Cosmic rays Initial activity (?)
Nuclear tests Sources and in-situ
Crustal (?) production (?)

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3. Overview of Application of Isotope Geochemistry in Hydrological Studies.

Application of isotopes includes tracing the evolution of a water mass from its origin as
precipitation, through its recharge processes, and ending at its appearance in an aquifer.
Besides this, isotopes can be used to determine the origin of specific solutes in groundwater.
This type of application commonly involves stable isotopes. The other main class of isotope
applications was derived from the decay of radioisotopes. Unlike stable isotope applications
that shed light on geochemical evolution in aquifers, radioisotopes are primarily used to define
the relative or absolute age of water in an aquifer. Methodologies based on the use of isotopes
in a full spectrum of hydrological problems encountered in water resource assessment,
development, and management activities are already scientifically established and are an
integral part of many water resource investigations and environmental studies. The concept of
“Tracing” is applied for these methodologies, in which either naturally occurring isotopic
species (environmental isotopes) or intentionally introduced tracers are employed. A variety of
well-established and field-verified isotopic techniques offer useful tools, with proven
technological and economic benefits for water resource assessment, development, and
management.

3.1 Groundwater Origin, Recharge, and Mixing Processes (Groundwater

movement)
One of the most typical applications in isotope hydrology is the identification of recharge areas
of underground aquifers by comparing the isotopic signatures of precipitation and with those of
groundwater collected from springs and/or wells.

Spatial variability of the δ2H or δ18O values in precipitation reflects the combination of source-
region labeling, rainout, and recycling effects that affect air masses bringing vapor to different
geographic regions. The isotopic compositions of precipitation have been mapped at several
scales: global distribution (Bowen, and Revenaugh, 2003), regional scale (Longinelli, and
Selmo, 2003), and detailed scales (Liotta et al, 2013; Minissale and Vaselli, 2011) and
references therein proposed an alternative method based on indirect measurements using karst
springs as natural pluviometers in Italy. They recalculated the average elevations of their
recharge areas by shifting the original altitude values of spring waters along the 0.2 δ‰m1
line, proposed by Longinelli and Selmo, as representative of the mean isotopic altitude gradient
(Δδ18O) for the Italian meteoric precipitations.

The determination of the origin of groundwater as well as the manner and the rate of recharge
and discharge is of major importance for its management especially in waterless areas (Chen et
al., 2012 and Yin et al, 2010). The development of tracer techniques using stable isotopes
enables approaches to groundwater movement in many regions (Lorenzen, et al., 2011).

3.2 Groundwater Salinization (Water Quality)

Groundwater salinization in coastal regions is frequently observed in confined aquifers as well
as in unconfined aquifers. In the case of unconfined aquifers close to coastal regions, water

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salinization is, as previously mentioned, usually induced by seawater intrusion relative to a

decline in the piezometric level, which is commonly associated with excessive pumping
(overexploitation) of groundwater. In the case of coastal confined aquifers, the groundwater
system is generally isolated from seawater by confining bed of clay-rich sediments, which
were mostly deposited in the latest transgressions. Yamanaka and Kumagai (2006) used a
combination of δ34S-SO4 values (ranging from +1.2 to +79.5‰) and chemical compositions of
brackish groundwater to examine the provenance of salinity in a confined aquifer system in the
SW Nobi Plain (central Japan). They highlighted that water chemistry was explained by sulfate
reduction in combination with the mixing of two types of seawater: (i) present seawater and (ii)
SO4-free seawater, with the fresh recharge water. In particular, the δ34S-SO4 values showed that
present and fossil seawaters were responsible at most of 10.7 and 9.4% of the brackish
groundwater volume, respectively. Deterioration of the quality of groundwater in urban areas
has become a major environmental concern worldwide. In this respect, researchers have
applied δ34S-SO4 and δ18O-SO4 since they have a distinctive isotopic composition to identify
pollution sources. Cortecci et al. (2002) investigated the δ34S-SO4 isotopic signature of the Arno
river (northern Tuscany, Italy) and its main tributaries in order to constrain the areal
distribution of the anthropogenic contribution across a heavily industrialized and densely
urbanized territory, where the human load increases downwards from the Apennine ridge to the
Tyrrhenian sea coast. These authors observed that the δ34S-SO4 values from natural inputs were
ranging approximately between 15 and +4‰, likely related to the oxidation of pyrite
disseminated in bedrocks, and δ34S-SO4 values between +15 and +23‰, as a result of
dissolution processes of evaporitic rocks. Conversely, the sulfur isotopic signature associated
with anthropogenic sources (possibly in the chemical forms of Na2SO4 and FeSO4) was
characterized by δ34S-SO4 values varying between 1 and 8‰.

Urban groundwater contamination problems are becoming increasingly recognized in all Asian
megacities (Hosono, T., et al. 2011). In the Taipei (Taiwan) urban area, one of the most
densely populated areas in the world, the investigation of the hydrogeochemical groundwater
characteristics and the causes of pollution are subjects of prime importance for water resource
preservation in the Pacific island. Hosono et al., explored the δ34S-SO4 and δ18O-SO4 isotope
variability with the aim of understanding the subsurface nature and environmental status of
such area. Importantly, they isotopically recognized possible sources, which were affecting the
Taipei groundwater system. Within the analyzed data, the sulfate isotopic compositions of
waters reacted with chemical fertilizers showed that the δ34S-SO and δ18O-SO4 values were
ranging from 5.0 to +14.4‰ and from +13.1 to +25.7‰, respectively.

3.3 Tritium (3H) and Carbon-14 (14C) (Water Quality and Pollution).
The environmental radioisotopes of 3H and 14C have transient concentrations in the
hydrological system due to both their radioactive decay properties (which is a function of time)
and also variable input - concentrations. This facilitates the study of water movement dynamics
in the "time" domain. In general, the basic information to be obtained from these isotopes
refers to "travel time" of water within a given system and/or to its distribution. In the case of
tritium, it can be readily used for qualitative (or semi-quantitative) assessment of the presence
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of recent recharge to groundwater systems, since the history of the tritium concentrations in the
precipitation is fairly well defined. Groundwater containing measurable tritium concentrations
provides clear evidence of recharge occurring into the system during the last three to four
decades. The case of absence of tritium, however, could be indicative of either recharge being
not significant during the above cited period, or the travel times involved in the system being
longer than the time required for the decay of the isotope during its transport. One of the most
important contributions of environmental tritium has been the study of moisture movement in
the unsaturated zone as a means of estimating the amount of direct rainfall recharge to
unconfined aquifers. The basic principle underlying this application is to detect the 1963
tritium peak in the vertical moisture profile in the unsaturated zone so that the moisture stored
above the location of the peak would be direct measure of the replenishment rate. One of the
earlier applications of the method was in a sand dune area at Dahna, Saudi Arabia (Dinçer,
1974). The radioactive isotope 14C, is also naturally produced in the atmosphere by cosmic
radiation. It is readily oxidized to carbon dioxide and enters into the carbon cycle. Its natural
production is rather constant and its input to hydrological systems can be assumed to be steady-
state for practical purposes. The concentration of C is expressed as "percent of the 14C of
Modern Carbon" (pmc). It has a half-life of 5730 years. Unlike tritium, 14C is not a
conservative tracer providing direct indication of the travel time, due to complex chemical
reactions involved during the transport process. The concentration of this isotope in water is
often measured as the 14C activity in the Dissolved Inorganic Carbon (DIC), which is altered
due to interactions of water with the aquifer matrix. Various chemical and isotopic models
have been suggested to account for these chemical reactions as to arrive at true travel time
estimates of the water, rather than the apparent value (Fontes, 1983). One of the simplest
approaches is based on the use of ^C content of the DIC, so that the chemical dilution of C
activity due to water-matrix interaction is accounted for, and the initial 14C activity (C0) is
estimated (Salem et al, 1980). Furthermore, physical retardation processes which may possibly
occur due to diffusion into aquitard porous matrix in such slow moving systems, may also add
uncertainty to the estimates of groundwater travel times based on 14C isotope (Sudicky and
Frind, 1981). Most of the other environmental radioactive isotopes are of potential use in
determination of the groundwater travel times over different time scales, but their routine
applications are presently hindered due to either analytical efforts required or to lack of
understanding of their natural production rates in different hydrogeological conditions.

3.4 Organic Contaminants (Water Quality)

Groundwater contaminations with organic pollutants have become a global environmental
problem, especially in industrialized countries. Organic compounds are released into the
subsurface in various ways (e.g. accidental spills, improper disposal methods, leaking
underground storage tanks). The fate and behaviour of these compounds in the soil and
groundwater media depends on a number of physicochemical and biological processes. Each
process defines an independent set of compositional and isotopic changes. The fact that stable
carbon and chlorine isotope compositions of organic chemicals vary depending on the
manufacturer and time-frame that they were produced (factors include the conditions and the
pathways used to synthesize the compound) allows to identify sources of a chemical or to trace
the time of contaminant release in the environment. This has been found for polycyclic
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aromatic hydrocarbons (PAHs) (O‟Malley et al, 1996), polychlorinated biphenlys (PCBs)

(Drenzek et al, 2001) methyl tert-butyl ether (MTBE) (Smallwood et al, 2001), chlorinated
ethenes (Jendrzejewski et al, 2001) and BTEX (Benzene, Toluene, Ethyl-benzene, Xylenes)
compounds (Dempster et al., 1997). In order to reliably determine that two field samples are
isotopically distinct, differences in isotopic values of not less than 1.0 ‰ (or ±0.5 ‰ precision
on each δ13C) are required. Isotopic composition of a contaminant fractionated during (bio)
chemical transformation has been used to assess in situ biodegradation of organic contaminants
in groundwater, since the isotopic enrichment of the residual pollutant is the best evidence to
demonstrate (bio)degradation of these compounds. Isotope data are usually evaluated using the
Rayleigh equation to estimate the extent of contaminant biodegradation or the first-order rate
constants, assuming that the change in the average isotopic signature is subject to very robust
fractionation. However, the Rayleigh equation is developed for homogeneous systems while in
the subsurface, contaminants can migrate at different velocities due to physical heterogeneity.
This approach leads to a systematic underestimation of the actual value due to the fact that it
does not accommodate for the subsurface physical heterogeneity of field sites. A substantial
systematic effect occurs especially for the quantification of the first-order rate constants (up to
50 % underestimation of actual rate), while it is relatively small for the quantification of
biodegradation (<5 % underestimation of actual degree of biodegradation) (Abe and Hunkeler
2006). Further implications for practical application of isotope studies in contaminated aquifers
are the processes of natural attenuation that involve small isotope fractionation, such as mixing,
sorption (Slater et al., 2000) or evaporation (Harrington et al, 1999), and may confound
quantification of a fractionating degradation processes using a simple streamline-Rayleigh
approach (Kopinke et al., 2005). Although measured isotope ratios may, under special
circumstances, overestimate the extent of degradation, they will not overestimate the extent of
net removal from the aquifer. Thus, isotopic analysis can offer definitive demonstration of the
degradation.

3.5 Water Quality and Pollution.

Pollutants in surface water and groundwater come from various sources such as agriculture,
industry, or human waste or may be present naturally due to geochemical processes taking
place in aquifers. Agriculture, industry and households each produce different kinds of
pollutants. By studying the chemical and isotopic composition of a pollutant, scientists can
determine its origins (Laura Gil/IAEA). For example, nitrate ion (NO3-), which is made up of
nitrogen and oxygen, is a common pollutant. Nitrogen has two stable isotopes of different
weight. This difference in weight is not the same in human waste and in fertilizers. Fertilizers
use nitrogen from the air, whereas humans and animals go through a biological process that
changes nitrogen into different forms. As a result, pollutants derived from various sources can
be identified based on these isotopic weight differences (Laura Gil/IAEA).

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3.6 Origin and Transport of Water in the Water Cycle

Every water molecule (H2O) is made of two hydrogen (H) atoms and one oxygen (O) atom, but
these are not all the same: some atoms‟ isotopes are lighter and some are heavier. Scientists use
precise analytical equipment to measure these tiny weight differences in water samples.
As water evaporates from the sea, the molecules with lighter isotopes tend to preferentially
rise, forming clouds with specific isotopic signatures. These clouds have a mix of water
molecules that fall in the form of rain. The water molecules with heavier isotopes fall first.
Then, as the clouds lose these heavy isotopes and move further inland, lighter isotopes fall in a
greater proportion. As water falls to the earth, it fills lakes, rivers and aquifers. By measuring
the ratio between heavy and light isotopes in these water bodies, scientists can decipher the
origin and movement of water.

3.6 Groundwater Age.

Isotopes are the most direct and powerful tools available to estimate the age, vulnerability and
sustainability of water resources. When the groundwater in an aquifer is „old‟, this means that
the water flow is slow and that the aquifer can take a long time to replenish. When young,
groundwater is easily and quickly renewed by rainwater, but can also be easily affected by
pollution and changing climatic conditions. In hydrology, some naturally occurring radioactive
isotopes present in Water, such as tritium (3H), carbon-l4 and (14C) noble gas radioisotopes, are
used to estimate groundwater age. Because these isotopes decay over time, their abundance
decreases as the years go by. Higher values mean „younger‟ water, while lower values mean
„older‟ water. For example, groundwater with a detectable amount of tritium may be up to
around 60 years old, whereas groundwater with no tritium must be older. Carbon-14 is used for
water up to 40 000 years of age and krypton-81 for water that can be up to a million years old.

4.0 Case Histories

4.1 Case History 1
A study on use of environmental isotopes to understand groundwater recharge in Abuja,
Nigeria, Dan-Hassan et al., (2016) found that the water in the acquired are of recent and
similar recharge conditions. The area studied covers an area of about 5,000Km2 in the central
part of the Federal Capital Territory, Abuja, Nigeria, stretching along a NE-SW axis, cutting
across geological, geomorphological and geopolitical boundaries of the territory. The aquifer
systems in the study area are formed by weathered and fractured basement except in the
southwestern part, which is formed by the sandstones of the Bida Basin. Eleven groundwater
and one rain water samples were collected and analyzed for stable isotopes of deuterium (2H)
and Oxygen-18 (18O) and radioactive isotope of tritium (3H), according to standard methods.

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Fig. 1: Geological map of FCT, Abuja (Geological map modified after NGSA, 2004).

Fig.2: Map of the study area within the FCT showing sampling locations (Dan-Hassan et al.,
2016).

Results of the isotope analyses revealed that the measured δ2H values of the groundwater
samples range from -17.1 to -14.3o/oo while that of δ18O range from -3.53 to -2.59o/oo. The
δ2H and δ18O diagram shows that the water types originated from precipitation as the samples
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Vol. 5, Issue 10 (October 2019)

plot around the Global Meteoric Water Line (GMWL) with a deuterium excess in the range of
10 + 2.7. This indicates similar recharge conditions and an isotopic enrichment by evaporation.
Tritium (3H) concentration for the groundwater samples varies from 2.3 to 5.0 TU with a mean
of 3.56 TU while that of the only rainwater sample was 4.85 TU. Applying qualitative age
categorization, the study concluded that the range of tritium values depicts active recharge and
recent groundwater.

4.2 Case History 2

In another related study by Oteze (1989) on the environmental isotope hydrology of the main
Rima Aquifer waters of the Sokoto basin, Nigeria has shown the Rima aquifer is not of modern
recharge. During the study water samples were collected from the main Taloka aquifer from
six sample locations for Tritium, Deuterium and Oxygen-18 analyses. While four samples were
obtained for 13C and 14C analyses. The locations chosen were Jega, Tambawel, Marnona,
Wurno, Goronyo, and Chiadawa. The isotopic studies carried out (14C, 13C, 18O, 2H, and 3H) on
the water samples from the six locations show that waters in the Taloka aquifer were recharged
more than 40,000 years ago.

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Fig. 3: Location map of the Rima Group Formations (Oteze, 1988).

Fig. 4: Hydrogeologic map of the Rima Aquifer (Oteze 1989)

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4.3 Case History 3

Archana, S.D. et al, (2014) in another Groundwater pollution studies: Isotope hydrochemcial
investigations on pollution of groundwater by fly ash dumped in coal open cast mines at
Talcher thermal Power Station of NTPC, Odisha, India. Water samples from mine,
groundwater, surface water and rain water were analysed for environmental stable isotopes (δD
and δ18O), Tritium, trace elements and major cation and anion. Isotope data suggest that hand
pumps in the area are getting recharge from both rain water and the mine water. Tritium values
of a few hand pump samples are 2 – 4 TU and local rain water is 4 TU. Hence some wells are
mixture of both modern water (shallow aquifer) and older water (deep aquifer). Isotopic data
suggest that groundwater in the southern and S-SE part of area near a quarry in the area is
influenced by quarry water. The drainage pattern of the area also substantiates this finding. A
bore well, which is nearby an old abandoned fly ash pond, measured comparably higher
concentrations of Mn and Zn which is above maximum permissible limit (MPL) of drinking
water, may be getting recharge from the old abandoned fly ash pond along with rain water. The
fly ash leachates in these mines are getting well diluted due to continuous fresh water input
from a river (River Brahmini), and hence don‟t pose any threat to groundwater in downstream.
The study concluded that periodical (annual) chemical analysis of groundwater samples are to
be carried out in the area to ensure that the chemical toxicity don‟t exceed MPL for drinking
water. To bring down the higher concentrations of toxic ions in the well, the old abandoned fly
ash pond needs to be fed with continuous supply of fresh water.

5. Conclusions
An increasing threat to groundwater supplies and surface water quality requires that the origin
of specific compounds is determined and the flow of effluents traced in the natural
environment. The use of stable and (subordinately) radiogenic isotopes in water quality studies
is playing an important role to address water resource sustainability issues worldwide. The
possibility to evaluate and quantify effects and modalities of isotopic fractionation affecting the
light elements such as oxygen, hydrogen, carbon, sulfur, nitrogen, and boron provides
outstanding opportunities to identify sources and to trace transformation processes. Stable
isotope applications are nowadays well established approaches in hydrogeochemistry, and
some of them are routinely analyzed to contribute to the understanding of the hydrological
circuits as well as the presence of anthropogenic contamination/pollution. Environmental
isotope geochemistry is a fast-growing discipline as new additional isotopic systems are set up
and applied to different geological and urban, industrial, and agricultural areas. In this work
have some examples of their application have been provided to highlight the potential of
traditional and nontraditional stable isotope systems to trace sources, fate, and behavior of
different solutes and metals in surface water and groundwater. Stable isotopes have
demonstrated to be a powerful tool in order to analyze situations that cannot be faced with
conventional techniques. However, at a large scale, the isotopic signatures can significantly
change and often not enough data are provided to determine the original source, as their
determination is time-consuming and costly. On the other hand, new techniques, particularly
for what regards oxygen and hydrogen isotopes, are presently able to provide a large number of
determinations in a short time.
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