Geyh - 2000 - VOLUME IV - Groundwater

ENVIRONMENTAL
ISOTOPES
in the
HYDROLOGICAL CYCLE
Principles and Applications
W. G. Mook
editor
VOLUME IV
GROUNDWATER
SATURATED AND UNSATURATED ZONE
by
Mebus Geyh
Niedersächsisches Landesamt für Bodenforschung
Hannover
UNESCO/IAEA Series on
Environmental Isotopes in the Hydrological Cycle

Principles and Applications
÷
Volume I Introduction: Theory, Methods, Review
Volume II Atmospheric Water
Volume III Surface Water
Volume IV Groundwater: Saturated and Unsaturated Zone
Volume V Man's Impact on Groundwater Systems
Volume VI Modelling
Ar
H He
C Kr
ENVIRONMENTAL
C ISOTOPES
in the
HYDROLOGICAL H
CYCLE O
C
N
S
He Ar
Contributing Authors
F.DÁmore, G.Darling, T.Paces, Z.Pang, J.Šilar
PREFACE
The availability of freshwater is one of the great issues facing mankind today - in some ways
the greatest, because problems associated with it affect the lives of many millions of people. It
has consequently attracted a wide scale international attention of UN Agencies and related
international/regional governmental and non-governmental organisations. The rapid growth of
population coupled to steady increase in water requirements for agricultural and industrial
development have imposed severe stress on the available freshwater resources in terms of
both the quantity and quality, requiring consistent and careful assessment and management of
water resources for their sustainable development.
More and better water can not be acquired without the continuation and extension of
hydrological research. In this respect has the development and practical implementation of
isotope methodologies in water resources assessment and management been part of the
IAEA’s programme in nuclear applications over the last four decades. Isotope studies applied
to a wide spectrum of hydrological problems related to both surface and groundwater
resources as well as environmental studies in hydro-ecological systems are presently an
established scientific discipline, often referred to as “Isotope Hydrology”. The IAEA
contributed to this development through direct support to research and training, and to the
verification of isotope methodologies through field projects implemented in Member States.
The world-wide programme of the International Hydrological Decade (1965-1974) and the
subsequent long-term International Hydrological Programme (IHP) of UNESCO have been an
essential part of the well recognised international frameworks for scientific research,
education and training in the field of hydrology. The International Atomic Energy Agency
(IAEA) and UNESCO have established a close co-operation within the framework of both the
earlier IHD and the ongoing IHP in the specific aspects of scientific and methodological
developments related to water resources that are of mutual interest to the programmes of both
organisations.
The first benchmark publication on isotope hydrology entitled “Guidebook on Nuclear
Techniques in Hydrology” was realised in 1983 through the activity of the joint
IAEA/UNESCO Working Group on Nuclear Techniques established within the framework of
IHP, and it has been widely used as practical guidance material in this specific field.
In view of the fact that the IHP’s objectives include also a multi-disciplinary approach to the
assessment and rational management of water resources and taking note of the advances made
in isotope hydrology, the IAEA and UNESCO have initiated a joint activity in preparation of
a series of six up-to-date textbooks, covering the entire field of hydrological applications of
natural isotopes (environmental isotopes) to the overall domain of water resources and related
environmental studies.
The main aim of this series is to provide a comprehensive review of basic theoretical concepts
and principles of isotope hydrology methodologies and their practical applications with some
illustrative examples. The volumes are designed to be self-sufficient reference material for
scientists and engineers involved in research and/or practical applications of isotope
hydrology as an integral part of the investigations related to water resources assessment,
development and management. Furthermore, they are also expected to serve as “Teaching
Material” or text books to be used in universities and teaching institutions for incorporating
the study of "isotopes in water" in general into the curriculum of the earth sciences.
Additionally the contents can fulfill the need for basic knowledge in other disciplines of the
Earth Sciences dealing with water in general.
These six volumes have been prepared through efforts and contributions of a number of
scientists involved in this specific field as cited in each volume, under the guidance and co-
ordination of the main author/co-ordinating editor designated for each volume. W.G.Mook
(Netherlands), J.Gat (Israel), K.Rozanski (Poland), W.Stichler (Germany), M.Geyh
(Germany), K.P.Seiler (Germany) and Y.Yurtsever (IAEA, Vienna) were involved as the
main author/co-ordinating editors in preparation of these six volumes, respectively. Final
editorial work on all volumes aiming to achieve consistency in the contents and layout
throughout the whole series was undertaken by W.G.Mook (Netherlands).
Mr.Y. Yurtsever, Staff Member of the Isotope Hydrology Section of the IAEA; and Ms. A.
Aureli, Programme Specialist, Division of Water Sciences of UNESCO, were the Scientific
Officers in charge of co-ordination and providing scientific secretariat to the various meetings
and activities that were undertaken throughout the preparation of these publications.
The IAEA and UNESCO thank all those who have contributed to the preparation of these
volumes and fully acknowledge the efforts and achievements of the main authors and co-
ordinating editors.
It is hoped that these six volumes will contribute to wider scale applications of isotope
methodologies for improved assessment and management of water resources, facilitate
incorporation of isotope hydrology into the curricula of teaching and education in water
sciences and also foster further developments in this specific field.
Paris / Vienna, March 2000

PREFACE TO VOLUME IV
The interpretation of isotope hydrological data is not straightforward. Many field studies lead
to a conclusion that the origin of groundwater and the chemical and isotopic processes in
groundwater systems can only be studied successfully, if a composition of isotopic, chemical,
geological and hydrogeological data is available for interpretation.
Following the previous volumes on isotopic principles, precipitation and surface waters, this
volume is dealing with the application of isotope hydrological methods in groundwater
studies. It conveys basic knowledge in geohydraulics and hydrogeology required for a
consistent interpretation of isotope hydrological data.
This volume starts with a brief discussion of the characteristics and behaviour of groundwater
as a medium of mass transport for gases, dissolved constituents and colloids. The
geohydraulic aspects of groundwater flow under steady-state conditions are described in
combination with an explanation of the most important terms related to isotope hydrology
(e.g. transit time, turn-over time, mean residence time, water age). Non-steady state flow
conditions caused by palaeoclimatic variations and anthropogenic activities such as overex-
ploitation or groundwater mining seriously affect the interpretation of isotope hydrological
data. Also water-rock interactions may modify the isotope composition of a carbonate rock
environment, especially in high-temperature systems.
Environmental isotope techniques are pre-eminently suitable for studying the unsaturated and
saturated zone, the latter particularly concerning the stable and radioactive natural isotopes.
Stable isotope data preferentially yield information on the origin of groundwater. Radioactive
isotopes allow groundwater to be "dated" in support of geohydraulic investigations. In
undisturbed high-temperature systems isotopic geothermometry, i.e. the study of the
temperature effect of stable isotopic abundances, is applied for gaining information on water
mixing as well as the origin and history of fluids. Anthropogenic changes due to steam loss,
underground liquid-vapour separation and the impact of re-injection of waste water are also
traced by the isotopic composition of geothermal fluids. Last but not least, a brief outline is
given on the planning and performance of environmental multi-isotope studies, as well as the
interpretation of the corresponding results.
Sincere thanks are due to my co-authors F. DÁmore, G. Darling, T. Paces, Z. Pang, J. Šilar,
T. Paces and A. D'Amore providing draft manuscripts and figure scetches as the fundaments
of this volume. Yuecel Yurtsever gently guided us to reach a uniform set of volumes. The
final critical and substantial reading overtook Wim Mook which was highly appreciated.
Hannover, February 2000

Mebus A. Geyh
CONTENTS
1 HYDROGEOLOGY AND AQUIFER CHARACTERISTICS 1

1.1 Definitions............... ................... .......................................................................... 1
1.2 Occurrence of groundwater in rocks ...................................................................... 1
1.3 Geohydraulic parameters............. .......................................................................... 2
1.3.1 Porosity .... ................... .......................................................................... 2
1.3.2 Storage, storage coefficient..................................................................... 4
1.3.3 Permeability and hydraulic conductivity ................................................ 5
1.3.4 Flow nets.. ................... .......................................................................... 5
1.4 Hydrogeology.......... ................... .......................................................................... 8
1.4.1 Hydrogeological properties of rocks....................................................... 8
1.4.1.1 Igneous rocks ........................................................................ 8
1.4.1.2 Metamorphic rocks ............................................................... 9
1.4.1.3 Consolidated sedimentary rocks ........................................... 9
1.4.1.4 Unconsolidated sediments ....................................................10
1.4.2 Hydrogeological structures – groundwater regimes ...............................10
1.4.3 Crystalline regions ....... ..........................................................................11
1.4.3.1 Volcanic rocks ......................................................................11
1.4.3.2 Folded sequences of sedimentary rocks................................11
1.4.3.3 Karstified rocks.....................................................................12
1.4.3.4 Platform sediments................................................................12
1.4.3.5 Alluvial plains, fans, river deltas, glaciofluvial, sediments ..13
2 TRACERS AND TRANSPORT 15

2.1 Types of tracers ....... ................... ..........................................................................15
2.2 Types of tracer experiments ........ ..........................................................................16
2.3 Isotopes in groundwater .............. ..........................................................................17
2.3.1 Stable isotopes ............. ..........................................................................17
2.3.2 Radioactive isotopes .... ..........................................................................18
2.3.3 Chemicals. ................... ..........................................................................20
2.3.4 Colloids.... ................... ..........................................................................21
2.3.5 Noble gases .................. ..........................................................................22
3 GEOHYDRAULIC ASPECTS 25
3.1 Steady-state groundwater flow.... ..........................................................................26
3.1.1 Darcy velocity and tracer velocity ..........................................................26
3.1.2 Principle groundwater flow models ........................................................27
3.1.3 Considerations about modelling .............................................................32
3.1.4 Groundwater discharge ..........................................................................32
3.1.4.1 Springs ....... ..........................................................................33
3.1.4.2 Production wells ...................................................................34
3.1.4.3 Well construction and sampling of water from wells ...........35
3.2 Non-steady state groundwater flow........................................................................36
3.2.1 Palaeoclimatic causes... ..........................................................................36
3.2.2 Anthropogenic causes .. ..........................................................................37
4 WATER-ROCK INTERACTIONS 41
4.1 Anion exclusion-adsorption: physical absorption ..................................................42
4.2 Chemical absorption ................... ..........................................................................42
4.3 Exchange of ions ..... ................... ..........................................................................43
4.4 Chemical interaction between solutes ....................................................................43
4.4.1 Carbonate-CO2 system. ..........................................................................43
4.4.2 Reactions with organic matter ................................................................44
4.4.3 Fate of dissolved sulphur compounds.....................................................45
4.4.4 On the isotopic composition of strontium...............................................48
5 APPLICATIONS TO LOW-TEMPERATURE SYSTEMS 49

5.1 Unsaturated zone ..... ................... ..........................................................................49
5.1.1 Principal soil parameters of the unsaturated zone...................................49
5.1.2 Geohydraulic aspects ... ..........................................................................50
5.1.2.1 Steady-state flow...................................................................50
5.1.2.2 Movement of solutes.............................................................51
5.1.2.2.1 Convection and advection ................................51
5.1.2.2.2 Dispersion.........................................................51
5.1.2.2.3 By-pass flow (dual flow)..................................53
5.1.3 Solute transport ............ ..........................................................................53
5.1.4 Application .................. ..........................................................................54
5.1.4.1 Recharge rate determination by mass balance ......................54
5.1.4.2 Recharge rate determination by tracer peak displacement....55
5.1.4.3 Evaporation rate....................................................................59
5.1.4.4 Water loss by plant extraction ..............................................65
5.2 Saturated zone ......... ................... ..........................................................................65
5.2.1 Origin of groundwater . ..........................................................................65
5.2.1.1 Oxygen (18O/16O) and hydrogen (2H/1H) ..............................65
5.2.1.2 Carbon (13C/`12C)...................................................................72
5.2.1.3 Nitrogen (15N/14N).................................................................75
5.2.1.4 Sulphur (34S/32S) ...................................................................79
5.2.1.5 Chlorine (37Cl/35Cl) ...............................................................89
5.2.1.6 Boron (10B/11B) .....................................................................89
5.2.1.7 Strontium (87Sr/86Sr) .............................................................93
5.2.2 Groundwater dating ..... ..........................................................................95
5.2.2.1 Tritium ....... .......................................................................... 96
3
5.2.2.2 H/3He and 3He methods ....................................................... 99
5.2.2.3 Radiocarbon ..........................................................................100
5.2.2.4 Silicon-32... ..........................................................................107
5.2.2.5 Chlorine-36 ..........................................................................107
5.2.2.6 Argon-39.... ..........................................................................110
5.2.2.7 Krypton-81. ..........................................................................111
5.2.2.8 Krypton-85. ..........................................................................111
5.2.2.9 Iodine-129.. ..........................................................................113
5.2.2.10 Uranium/Helium and K/Ar methods.....................................113
5.2.2.11 Radium/radon dating method................................................114
234
5.2.2.12 U/238U dating method........................................................115
6 APPLICATIONS TO HIGH-TEMPERATURE SYSTEMS 119

6.1 Natural processes..... ................... ..........................................................................121
6.1.1 Water-rock interaction at high temperature ............................................123
6.1.2 Isotopic geothermometry ........................................................................125
6.1.3 Tracing the origin and history of fluids ..................................................130
6.1.4 Mixing with geothermal fluids ...............................................................130
6.2 Anthropogenic processes............. ..........................................................................134
6.2.1 Steam loss ................... ..........................................................................134
6.2.2 Underground liquid-vapour separation processes...................................138
6.2.3 Isotope techniques in re-injection studies ...............................................141
6.2.4 Variability of the isotopic composition in geothermal fluid ...................143
7 PLANNING AND PERFORMANCE OF MULTIPLE ISOTOPE STUDIES 151
REFERENCES 155
LITERATURE 175
IAEA PUBLICATIONS 177
CONSTANTS 180
GLOSSARY 181
SYMBOLS 189
SUBJECT INDEX 191

1 HYDROGEOLOGY AND AQUIFER
CHARACTERISTICS
1.1 DEFINITIONS
Groundwater is one of the smallest components of the hydrosphere. Groundwater flow and
the inherent hydrochemical processes belong to the hydrological cycle which depends on a)
the geological-ecological structure and b) the petrological composition of the lithosphere. The
latter influences the geochemical processes and the hydrochemical composition of the
groundwater. Both factors explain the relative low flow velocity of groundwater, its usually
long residence time and the wide range of the time scale occupied by groundwater, compared
to that of surface water in the hydrological cycle (Volume II).
Most groundwater is of meteoric, i.e. atmospheric origin (Volume II). Rain water directly
infiltrates into the ground or indirectly via inflow of surface water (bank storage in streams).
A very small part of the groundwater (juvenile water) may have its origin from the magma in
the Earth′s interior.
1.2 OCCURRENCE OF GROUNDWATER IN ROCKS

Groundwater occurs in interstices in rocks which have various shapes, sizes and origin. The
ability of rocks to transmit water through its interstices is called permeability. This depends
on the physical properties of the rock and its genetic history (geological factors and
processes). The rock interstices as pathway of groundwater flow and circulation (aquifer) may
be classified as follows:
Pores are intergranular interstices between the grains of unconsolidated as well as of
consolidated clastic sediments or of loose volcanic tuffs (Fig.1.1a),
Fissures are fractures or cracks in the rocks (Fig.1.1b), and
Cavities are present in carbonate rocks (Fig.1.1c) and lava tubes in volcanic rocks.
The spatial arrangement of an aquifer controls the shape and hydrodynamic type of flow, the
transit time and residence time of groundwater. In fissured zones dual-flow pathways are
developed, which may substantially contribute to the groundwater recharge or may
interconnect aquifers across leaky aquicludes. The petrological (lithological) composition of
the aquifer and the water-rock interface control the hydrochemical reactions and behaviour of
the constituents dissolved in groundwater. The most important carbonate – CO2 system of
1
Chapter 1
14
groundwater is one example which has to be taken into account for C dating of DIC in
groundwater (Sect.5.2.2.3; Volume I; Clark and Fritz 1997).
A B C
Fig.1.1 Types of rock interstices and their relation to texture and porosity. (A) Sedimentary
deposits with high porosity, (B) porous rocks due to dissolved fractures, and (C) porous
rocks with fissuration.
1.3 GEOHYDRAULIC PARAMETERS
1.3.1 POROSITY
A soil element has a the total volume Vtot and a total mass Mtot, a solid phase volume Vsol with
a mass Msol, a liquid phase represented by the water and dissolved salts, a volume Vliq and a
mass Mliq and finally the volume of the gas phase Vgas (air and water vapour) with a negligible
mass (Fig.1.2).
The relative volume of pores in the rock is the total porosity ntot defined by
Vpor
n tot =
Vtot
where Vpor is the volume of the pores, filled with gas (Vgas) and with liquid (Vliq):
Vtot = Vgas + Vliq .
Only part of the pore water (Vliq) is free and mobile (Vmob), the rest (Vret) is bound by
capillary and hygroscopic forces and has a high retention time. Accordingly, free (or gravity
or gravitational) water and bound (capillary and hygroscopic) water have different retention
times which may be estimated by using isotope analyses.
The pore volume available for gravitational water movement (Veff) related to the total volume
is the specific yield (also effective porosity or kinematic porosity):
Veff
n eff =
Vtot
The pore volume containing water bound by capillary forces (Vret) related to the total volume
2
Aquifer Characteristics
(Vtot) is the specific retention (also capillary porosity)

Vret
n ret =
Vtot
The total porosity is the sum of the effective and capillary porosities. With increasing grain
size of the clastic sediments, the total porosity ntot usually decreases, the effective porosity
neff somewhat increases and the capillary porosity nret decreases (Fig.1.3). The effective
porosity is a fundamental parameter for geohydraulic calculations (mass transport modeling),
while the total porosity combines the mass transport and tracer flux.
In the saturated zone, solid and liquid phases exist. In the unsaturated zone the pores in the
rock are partly filled with water and partly with air (three-phase medium).
Vgas Vgas
Vmob neff
Vpor Vliq ntot
Vret
Vtot Vsol Vsol
Fig.1.2 Saturation of the pores with water. Vtot - bulk volume of the rock, Vsol - volume of the
solid material (matrix), Vpor - volume of pores, Vliq – volume filled with water, Vgas –
volume filled with gas, Vmob - volume of pores free for gravitational flow of mobile
water, Vret – volume of pores filled with water which is bound by capillary and
hygroscopic forces.
The volumetric humidity or volumetric water content is the ratio of the volume of the water to
the total volume of the rock:
Vliq
φ=
Vtot
3
Chapter 1
The maximum volumetric humidity which can be retained against gravity is termed field
capacity.
porosity (%)
60
50 total
poro
sity
40 well-sorted aquifers
30 spe
cific
yie
ld
20
specific retention
well-sorted aquifers
0 0.001 0.01 0.1 1 10 100

grain size (µm)
clay silt sand gravel cobbles
well-sorted aquifer
Fig.1.3 Relation between median grain size and water-storage properties (total porosity, specific
yield and specific retention) of alluvium from large valleys (after Davis and DeWiest
1966).
1.3.2 STORAGE, STORAGE COEFFICIENT

There are two kinds of aquifers: the phreatic aquifer has an open water surface, the confined
aquifer has a confining bed. If the hydrostatic pressure of a confined aquifer is reduced, e.g.
by abstraction of groundwater, the aquifer load increases and the resulting compression expels
some water from the aquifer. At the same time, the lowering of the pressure causes a small
expansion and subsequent release of water. The water-yielding capacity of a confined aquifer
is expressed in the term of the storage coefficient.
The storage coefficient S is defined as the volume of water that an aquifer releases or takes
into storage per unit area of aquifer per unit change of head. It equals the volume of water
released from the aquifer when the piezometric surface declines by one metre. It is
dimensionless and expressed as
S = g ⋅ d (n eff ⋅ β liq + β rock )
4
where g is the acceleration due to gravity, d is the thickness of the aquifer, neff is the effective
porosity; ßliq and ßrock are the coefficients of compressibility of the water and rock,
respectively.
In most confined aquifers, values of S are in the range of 5 × 10-5 to 5 × 10-3. This indicates
that large pressure changes over extensive areas are required to produce a substantial water
yield. S is determined by pumping tests of wells. In unconfined aquifers, the storage
coefficient S equals the effective porosity neff as almost all water is released by the declining,
unconfined (“free”) water table due to gravitational drainage. In unconfined aquifers
consisting of alluvial sediments in alluvial plains S ranges from 0.15 to 0.25, much higher
than that of confined aquifers (Fig.1.3).
1.3.3 PERMEABILITY AND HYDRAULIC CONDUCTIVITY

Permeability is the property of a rock or soil to transmit water or other fluids. It determines
the relation between the velocity and the hydraulic gradient, under which water flows through
the rock or soil medium.
1.3.4 FLOW NETS

Groundwater flow in large aquifer systems can be presented as a flow net. In the three-
dimensional space, the flow lines extent perpendicularly on the equipotential surface; in the
two-dimensional case the flow lines are perpendicular to the equipotential lines and form a
flow net of curvilinear rectangles (Fig.1.4). Equipotential lines are often called groundwater-
surface contours or hydroisohypses.
The course of hydroisochrons representing the same groundwater age is usually similar to that
of the piezometric contour lines. There are, however, methodical deviations which may reflect
spatial peculiarities of the groundwater flow system or geohydraulic disturbances due to
groundwater abstraction. Equipotential lines deviate from hydroisochrons in regions where
the equipotential lines are very dense, i.e. the hydraulic gradient is high and thus the water
velocity higher than elsewhere (Fig.1.5). This is also the case if the present groundwater flow
is different from that of the past. For instance, an accelerated increase of the groundwater age
towards the discharge area may indicate an increased groundwater recharge rate in the past.
Flow nets are meaningful only for steady-state conditions of the groundwater flow (Fig.1.5).
Any change in the geohydraulic situation modifies the flow net. This fact has to be taken into
account if isotope data from groundwater recharged in the past has to be related to the present
flow net which might also be modified by groundwater abstraction (Sect.3.2.2).
5
Chapter 1
gravel sand
v
t1 t4
t5
v
t2
v
t6
v
t3
Fig.1.4 Equipotential lines (long-dashed lines), flow lines (lines with arrows – v) and
hydroisochrons (bold short-dashed lines – t1 to t6) at the boundary of and within an
aquifer of differing hydraulic conductivity (after Seiler and Rodriguez 1980).
Equipotential lines and flow lines run perpendicularly to each other.
A flow net is usually constructed through vertical sections of the groundwater system or as a
vertical projection to a horizontal plane (e.g. to illustrate the horizontal groundwater flow on a
regional scale in a map). In a homogeneous and isotropic rock environment, the shape of the
flow net is controlled by the groundwater level which, in humid regions with direct
groundwater recharge by precipitation, usually conforms the morphology shape.
Tóth (1963) used flow nets to illustrate groundwater flow on a regional scale. Many local
shallow groundwater systems may be overlain by an intermediate and a deep regional ground-
water flow system. The equipotential lines for an isotropic aquifer show that the hydrological
potential under surface depressions decreases in the upward direction. Therefore, such
depressions discharge groundwater. In deep piezometric boreholes, the hydraulic pressure at
the bottom of the borehole is larger than that at the top (artesian groundwater flow) which
may not necessarily be related to a geological stratification of a system of aquifers and
aquicludes.
6
regional
local recharge
recharge local
area
area discharge
area
regional
discharge
area
Fig.1.5 Flow net in a vertical section through a dissected area. Full bold lines: flow lines; dashed
lines: equipotential lines (after Tóth 1963).
The hydraulic conductivity of aquifers is by several orders of magnitude higher than that of
the confining bed (aquitard). Thus, for a given flow rate the head loss along a flow line per
unit of distance is much lower in an aquifer than in a confining bed. Consequently, lateral
flow in confining beds is geohydraulically negligible while the isotope composition might
become affected due to the long-lasting contribution of slow seepage to the groundwater
recharge of a confined aquifer (Geyh et al. 1984). In aquifers the flow lines tend to narrow
and to be parallel to the aquifer boundaries. Hence, the flow net of an anisotropic aquifer
system may be very complex. As the groundwater flow net is controlled by recharge and
discharge, its appearance for arid and humid regions is principally different (Fig.1.6).
R
R
Fig.1.6 Groundwater flow net in humid and in arid regions. Groundwater recharge in humid
regions is reflected by equipotential lines (dotted lines) following the morphology. In arid
regions the groundwater table is flat; R = discharge to rivers in humid regions; B
discharge into basins or oasis in arid regions (after Seiler and Rodriguez 1980).
7
Chapter 1
The presentation of the flow net in hydrogeological maps mirrors the groundwater flow on a
regional scale and may help to solve practical problems of groundwater exploration and
exploitation. It is only reliable if the hydraulic potential of a large number of piezometers in the
particular aquifer was measured. Mathematical modeling can facilitate the construction of a
flow net.
1.4 HYDROGEOLOGY
1.4.1 HYDROGEOLOGICAL PROPERTIES OF ROCKS

Rocks can be classified according their hydrogeological, geohydraulic (storage of water,
hydraulic permeability) and pedological properties.
The Darcy equation (Sect.3.11) is only valid for laminar groundwater flow which occurs in
more or less homogeneous and isotropic aquifers, e.g. in clastic (granular) sediments and
sedimentary rocks (sand, gravel or sandstone). In fissured rocks, the spatial arrangement of
fissures is usually discrete, although often a preferential spatial orientation may cause an
anisotropic rock permeability. Due to this, the rock medium can only be considered
homogeneous and isotropic on a very large scale. Hence, the terms porosity and hydraulic
permeability cannot easily be applied to the geohydraulics of fissured rock systems.
The permeability of fissured systems reflects the geological history of the rocks, especially
tectonic exposure to stress. Changes may also be due to weathering and/or other geological
processes during the geological past. Younger fissure systems of late tectonic events are often
more permeable than the old ones that may be sealed by secondary minerals. Uranium
analyses (Sects.5.2.2.10 to 5.2.2.12) can help to distinguish young and old fissures.
In karstified rocks and in lava tubes, groundwater flow is seldom laminar; the arrangement of
rock cavities is randomly distributed. Hence, the use of the Darcy law of groundwater flow
may yield erratic results. Due to hydraulic interconnections of karst cavities, the results of
tracer experiments are sometimes ambiguous but always yield the minimum transit time of
groundwater at the time of the tracer experiment. Environmental isotope studies allow
estimates of much longer mean residence times of the base flow of groundwater (Sect.5.2.2).
1.4.1.1 IGNEOUS ROCKS

Igneous rocks (plutonic and volcanic) are permeable along open fissures. Usually, the width
of the fissures and therefore the permeability decreases with increasing depth.
Hard plutonic rocks (e.g. granite) rich in quartz are prone to fissuration. By mechanical
weathering they produce sandy alluvia that are permeable at the surface, while rocks poor in
quartz are prone to chemical weathering, thus disintegrating to clay minerals, which are less
permeable and often clog the fissures in the underlying bedrock.
8
Volcanic rocks often contain fractures that arising from the chilling of lava. In lava flows,
horizontally extended permeable fractured zones occur at the surface and bottom. They often
are important aquifers and occur in extensive lava flow systems of basalt plateau's.
1.4.1.2 METAMORPHIC ROCKS

Metamorphic rocks are usually permeable along open fissures which are formed by
weathering down to a certain depth. Acid quartz-containing gneiss as granite is prone to
weathering into sandy alluvia. Metamorphic crystalline limestones are subject to karstification
so that they often contain karst groundwater.
1.4.1.3 CONSOLIDATED SEDIMENTARY ROCKS

According to their hydrogeological properties, there is a great variety of sedimentary rocks,
but they form the most important aquifers. They can bear several types of interstices and have
a wide range of permeability. The permeability may be anisotropic; that is why modeling of
the regional groundwater flow and the motion of pollutants and tracers is very difficult of not
impossible. Dual-porosity has to be taken into consideration when evaluating the groundwater
flow and the movement of pollutants and tracers in such rock medium (Sect. 5.1.2.2.3). It
considers fast and a slow moving components.
Groundwater flow in sedimentary rocks depends on the composition of the rock, on the
lithology and facies of the entire sedimentary sequence, i.e. on the grain size and composition
in horizontal (lateral) and vertical directions. Usually the permeability of sediment in the
horizontal (lateral) direction is orders of magnitude higher than in the vertical direction. In
consolidated sedimentary rocks the groundwater flow also depends on fissuration due tectonic
disturbances and on secondary exogenous alterations (weathering, karstification, etc.). In
summary:
Sedimentary rocks rich in carbonates and sulphates may be divided into several groups.
Geochemical processes may influence the isotope composition of the groundwater (e.g. 14C).
Sandstones are usually important aquifers while arkose and graywacke are not.
Claystones, marlstones and shales have usually a very poor hydraulic permeability. This is
the reason why they are often aquicludes between aquifers and determine the spatial
arrangement of the flow system.
Carbonate rocks (limestones and dolomites) are excellent aquifers as they are usually
karstified. Carbon dioxide in water dissolves the rock, widens fissures and creates karst
cavities with often very large cross sections. As the filtration capacity is low, groundwater is
often polluted and its flow very fast.
Easily soluble sedimentary rocks (evaporites) include gypsum, anhydrite, sodium chloride
(halite), and other salts. In contact with groundwater large karst cavities are rapidly formed,
causing subsidence of the surface and creating serious problems such as bursts of water into
9
Chapter 1
salt mines. Stable isotope analyses allow to identify the origin of groundwater as well as of
brines, and to support measures against such catastrophic events.
Organic sediments of biolite type (coal, lignite, peat, coal argillites) form insignificant
aquifers, but are important for influencing the chemical and isotope composition of
groundwater in supplying organic carbon components. The application of 14C for groundwater
dating might be disturbed (Sect.5.2.2.3).
1.4.1.4 UNCONSOLIDATED SEDIMENTS

Unconsolidated sediments consist of various kinds of gravel, sand and clay, sometimes with
admixed organic matter. They occur as alluvia in river valleys, lacustrine sediments in lake
basins, or shelf sediments along the coast. They are also found as delta sediments, sediments
of alluvial cones of intermountain depressions, and glaciofluvial sediments washed out from
moraines. Usually, unconsolidated sediments are excellent and the most efficient aquifers.
Their porosity and permeability are usually high, unless clay is admixed, and depend on the
grain-size distribution (Fig.1.3) rather than the absolute size of the grains. The decisive factor
is the presence of the very fine clay particles. With increasing effective porosity the
permeability increases. Thick deposits may subside considerably if the hydraulic pressure
decreases due to intensive groundwater abstraction.
In humid regions, wind-blown fine and well-sorted dune sands form significant aquifers with
excellent filtration properties.
1.4.2 HYDROGEOLOGICAL STRUCTURES - GROUNDWATER REGIMES

The hydrogeological structure describes the configuration of aquifers and aquicludes within
the geological environment. It determines the groundwater circulation from the recharge
area, along the percolation and circulation pathways (groundwater reservoir) to the drainage
area. Water divides, determined by the orography or the geology of the region, separate
groundwater recharge areas of neighbouring hydrogeological systems. Thus, a
hydrogeological structure has fixed limits set by both the geomorphology and the geological
structure.
The drainage rate in a hydrogeological system depends on the hydraulic gradient or the slope
of the piezometric surface. The latter usually changes due to the seasonally variable
groundwater recharge (as the fluctuation of groundwater level is controlled by precipitation)
or due to anthropogenic influences (e.g. due to pumping of water from the aquifer;
Sect.3.2.2).
Under favourable conditions, a hydrogeological structure contains a usable resource of
groundwater. The economic value depends on the yield (discharge rate of usable
groundwater) and the storage volume (water reserve or storage).
The complex of conditions which govern the change of the quantitative and qualitative factors
10
of groundwater flow in time and space is called the groundwater regime. Such groundwater
regime may be studied by analyses of environmental isotopes, supplementing classical
hydrological approaches such as:
Radionuclide dating (Sect.5.2.2) in combination with analyses of stable isotopes (Sect.5.2.1)
may clarify the period and climatic conditions during groundwater recharge (groundwater
dating and palaeohydrology; Sect.3.2.1). In particular, isotope studies help to determine the
origin of the groundwater, to clarify ecological problems related to the hydrological cycle, and
to provide information needed for sustainable groundwater management and protection. For
the interpretation of isotopic data the actual hydrogeological structure and the groundwater
flow system have to be simplified in order to develop a model that may describe the
hydrodynamic behaviour (Sect.3.1.2; Volume VI). For this task, basic knowledge on the main
types of hydrogeological structures is necessary.
1.4.3 CRYSTALLINE REGIONS

Hydrogeological structures in crystalline regions (in plutonic and metamorphic rocks) are
characterised by shallow groundwater circulation in the zone of weathering and fissuration,
which only reaches a depth of some tens of metres. These shallow groundwater flow systems
may be considered as completely mixed reservoirs. In the discharge area numerous small
springs and wet spots are present at the surface along faults or tectonic lines. Their spatial
distribution reflect the geological structure and morphology as tectonic zones and faults act as
regional groundwater drainage systems. Any deep-reaching groundwater circulation,
separated from the shallow local flow system, is characterised by long residence times (e.g.
thermal groundwater).
1.4.3.1 VOLCANIC ROCKS

Abundant and significant groundwater resources (e.g. in the Columbia Basin in the NW of the
USA, and in some parts of the Dekkan Plateau in India) may exist in basin-like structures,
which are sometimes developed in volcanic regions with extended basalt-lava flows.
Particular bodies of volcanic effusions provide usually only small groundwater resources. In
deeper parts piston-like lateral groundwater flow may occur. High groundwater abstraction
from deep artesian aquifers may lower their piezometric level resulting in an admixture of
shallow groundwater. In morphologically dissected terrains, such local shallow groundwater
flow prevails in the upper parts of the aquifers.
1.4.3.2 FOLDED SEQUENCES OF SEDIMENTARY ROCKS

In folded sequences of sedimentary rocks (e.g. limestone, sandstone), the groundwater flow
depends upon the type, thickness and extension of the aquifers and aquicludes. In tectonic
structures deep-reaching, extended circulation systems may exist beside shallow ones
(Fig.1.7) indicated by temperature anomalies in spring waters and a high concentrations of
11
Chapter 1
dissolved solids. Groundwater often consists of components of different residence times

complicating the evaluation of isotope data (Maloszewski and Zuber 1993, 1996, 1998; Zuber
1986; Volume VI). Each system has to be considered individually.
1.4.3.3 KARSTIFIED ROCKS

In karstified rocks, the spatial arrangement of the groundwater flow systems differs from
locality to locality and is controlled by the continuously changing geological and
morphological evolution. Groundwater flow occurs as large underground streams and springs,
on the one hand providing excellent conditions for the exploitation of groundwater. On the
other hand, the high permeability of the cavities bears the risk of groundwater contamination
from the surface. In hydraulic engineering, karst systems often cause problems of reservoir
leakage (Dreybroth 1984). The geochemical processes affecting the karstification have to be
taken into account when evaluating isotope results.
Groundwater flow responds quickly to precipitation. The flow velocity of the short-term
component is high (in the range of hundreds of metres per day), and consequently the
residence time of this karst groundwater is usually short. The base flow, however, may have
mean residence times of years or even decades. For the interpretation of isotope data, the
reservoirs are assumed to be completely mixed (exponential model) (Volume VI). In shallow
groundwater systems, the fluctuation of the recharge by precipitation is propagated through
the system, while it is equalised in large and deep systems.
The geological and morphological evolution of the rock environment in the past determine the
stage and depth of karstification of the present flow system. Karstification of carbonate rocks
started usually from the surface and continued into the depth. A deep drainage network might
had become developed similar to a surface river network.
In basin-shaped structures, under thick volcanic flows or along deep-reaching faults, karstified
carbonate rocks may be confined.
1.4.3.4 PLATFORM SEDIMENTS

In platform sediments (sediments deposited on the flat surface of the previously folded and
consolidated bedrock), extended basin-shaped structures might be developed which pass over
to tablelands and escarpments on their margins. According to the lithological development
and geological structure, often large and rich groundwater resources exist (Fig.1.7). Examples
are the Dakota Basin, the Great Artesian Basin in Australia, the Nubian Sandstone Basin in
North Africa, the Siberian Basin and the Paris Basin. The quality of groundwater depends on
the lithological composition of the rocks and on geochemical processes. In zones of moderate,
humid climate, the groundwater is usually of good quality and continuously recharged. In
confined aquifers, the groundwater is protected against contamination. In deep aquifers of arid
regions, also highly mineralised old groundwater is present which was recharged in the
12
geological past under more humid climatic conditions. Such non-renewable groundwater
resources are mined when they are abstracted. Isotope hydrological methods allow identifying
such old resources (Sect.5.2.1). Under such non-steady state recharge-discharge conditions,
groundwater dating or estimating the groundwater flow velocity is no longer possible
(Sect.3.1.2).
recharge area recharge area
Teutoburger
Forest Münster Soest Ruhr m a.s.l
"Emscher" marl
1000
us
Cr etaceo
pre- 0 10 20 30 km
2000
Fig.1.7 Schematic hydrogeological cross-section through the confined Basin of Münster (after
Michel and Struckmeier 1985), an example of a deep-seated basin. The pre-Cretaceous
rock and the "Emscher" marl are aquitards. The arrows mark the groundwater flow.
1.4.3.5 ALLUVIAL PLAINS AND FANS, RIVER DELTAS, GLACIOFLUVIAL SEDIMENTS

Alluvial plains and fans, river deltas, and glaciofluvial deposits usually of Quaternary age
consist of unconsolidated sediments and often contain large groundwater resources. Gravel
and sand dominate with intercalations of silt, mud and clay. The grain size composition
depends upon the evolution of the riverbed and of the sedimentation basin. In humid regions
such aquifers are often covered by flood loam which prevents pollution. Extended Quaternary
alluvia, often several hundreds of metres thick, are located in areas of tectonic subsidence as
e.g. in the alluvial plains of the rivers Amazon, Ganges and Danube.
Alluvia usually offer excellent conditions for groundwater development. During rainy periods
the river level is high and water indirectly recharges the groundwater reservoir. If the river
level is low, the river is replenished from groundwater (Fig.1.8). The response of the
groundwater table to precipitation is fast, and the residence time of the groundwater is short.
On a large scale, alluvial plains are considered as open reservoirs.
In arid regions, occasionally floods occur in channels filled with sediments (wadi, oued)
which are often unsorted, sometimes of low permeability, due to the admixture of muddy
material. Permeable zones develop where stream flow persists long enough to sort the coarser
debris in the stream channel. They extent only over small parts of the channel, are difficult to
locate and are responsible for run-off recharge, which is the dominant recharge process in arid
regions.
13
Chapter 1
well 1 river well 2
e s
l
e - early summer
l - late summer
s - static level
Fig.1.8 The geohydraulic interrelation between the groundwater in alluvial sediments and the
water in a stream. The static water level reflects the mean geohydraulic situation without
abstraction during the year. Well 2 pumps groundwater of the alluvial sediments and
lowers the static level (dotted lines). Bank infiltration may be induced from the river after
the snow melt and high river level (early summer). In autumn the river is low and
groundwater feeds the river. Well 1 pumped groundwater and river water (dotted lines).
14
2 TRACERS AND TRANSPORT
Groundwater contains a larger or smaller amount of inorganic and organic substances, mainly
in solution but also in colloidal or even suspended form. Suspended matter is not a usual
feature of groundwater, because such particles are effectively filtered out due to the generally
slow rate of movement through the interstices in aquifers. It may be, however, a noticeable
component in fast-flow systems such as those typically developed in karstic terrain.
Dissolved and to some extent colloidal contents of groundwaters have been studied
extensively. The subject of groundwater chemistry in relation to water quality prediction is far
from being simple - adsorption, desorption and dispersion can change concentrations during
transport (Chapter 4; Clark and Fritz 1997).
The dissolved and colloidal tracers may be of natural or anthropogenic origin. These two
origins tend to provide information on different aspects of groundwater movement.
2.1 TYPES OF TRACERS

There are general attributes for any tracer. Tracers need to be mobile, soluble and should not
be strongly retarded by the soil or aquifer matrix. That means, the tracer should be non-reac-
tive (conservative) and, of course, needs to be easily measurable.
We distinguish historical tracers and environmental tracers.
A historical tracer is one for which high concentrations resulted from some historical event. It
has long time to move and is used to determine the rate of movement or to estimate the
recharge rate. The historical events could be anything from a change of farming practice to
factory pollution. The most important historical tracers for isotope hydrological studies are
those that are commonly used are bomb tracers (3H, 14C, 36Cl, 137Cs); for these the peak
injection occurred in 1963/1964 (Fig.2.1).
An environmental tracer exists naturally; its spatial pattern or overall mass balance is used to
infer recharge and discharge rates. The major drawback is that it is usually difficult to define
their exact input function (time and amplitude). Furthermore, the spatial distribution of the
tracer input is not well defined. Examples are the cosmogenic radionuclides 14C, 3H, and 36Cl
(Volume I; Geyh and Schleicher 1990), but also the stable isotope abundance ratios of oxygen
and hydrogen, which vary over the year (Volume I; Gat and Gonfiantini 1981).
15
Chapter 2
2.2 TYPES OF TRACER EXPERIMENTS

The specific choice of application of environmental isotopes depends on the geometric and
time scale.
Field parameter techniques are dealing with small areas as e.g. lysimeters. With these the
effects of precipitation recharge and evapotranspiration can be determined under natural
conditions. A limitation is that refilled lysimeters may not reconstitute the real structure of the
soil. Usually the stable isotope composition is monitored.
On a regional scale the natural variation of the environmental isotope composition has a high
potential for hydrogeological studies. Elevated tritium levels resulting from thermonuclear
bomb tests are used to understand young groundwater systems (Sect.5.2.2.1 and 5.2.2.2).
Studies with stable isotopes (Sect.5.2.1) are based on regionally different flowpaths or
circulation patterns of storms and their differing stable isotope compositions (Volume II).
Monitoring the natural tracer concentration in the water of rivers, springs, wells and the
unsaturated zones allows to estimate the contribution of different recharge processes to the
groundwater recharge (Behrens et al. 1979).
3
H 14
C
(TU) (pMC)
85
Kr
(dpm/ml Kr)
2000 200 60
TU
Kr
85
45
1500 150 45
40
14
C 35
1000 100 30
30
3
H
25
H
3
500 50 15
20
15
0 0
1950 1955 1960 1965 1970 1975 1980 1985 1990 1995 2000
Fig.2.1 Input curves of the radioactive tracers (14C, 3H) from nuclear weapon tests with a peak
injection at 1963/1964 and from the continuous emissions of the nuclear industry (85Kr).
16
Tracers and Transport
2.3 ISOTOPES IN GROUNDWATER

Tracing groundwater by means of environmental isotopes offers unique and supplementary
information on the origin and movement of groundwater and its dissolved constituents, as
well as allows a quantitative evaluation of mixing (Sect.3.2.1; Volume VI) and other physical
processes such as evaporation and isotopic exchange in geothermal systems (Chapter 6).
Often secondary water-rock interactions can be studied (Chapter 4; Volume I), of which the
occurrence is decisive for whether or not isotopes act as conservative or non-conservative
tracers. Under suitable geochemical and hydrochemical conditions dating of the groundwater
is possible (e.g. by the 14C method; Sect.5.2.2.3).
A comprehensive introduction in the physics, chemistry and measurement techniques of
isotopes and the applied standard substances is given in Volume I. Various textbooks are
recommended for reading (e.g. Moser and Rauert 1980, IAEA 1983, Mazor 1991, Clark and
Fritz 1997).
2.3.1 STABLE ISOTOPES

Isotopes of the same chemical element have almost identical physical and chemical
properties. However, because of their small mass differences, they have different reaction
rates and different abundances in two chemical compounds or phases that are in isotopic
exchange. Also physical processes such as diffusion, evaporation, condensation, melting, etc.
produce isotopic differentiation. All these variations in the isotopic composition, produced by
chemical or physical processes, in compounds or phases, present in the same system, are
called isotopic fractionation (Volume I).
The atomic ratio R of the less frequent to the abundant isotope changes of a sample (spl) is
usually determined by mass spectrometer and expressed as delta value referring to a certain
reference material (standard, std):
R spl
δ= −1 (× 1000 ‰) (2.1)
R sdt
The most important atomic constituents of the water molecule are 16O and 18O (⇒ δ18O) and
1
H and 2H (⇒ δ2H). These have the widest field of application in groundwater studies, for
instance, tracing the origin of the water, the mode of recharge of groundwater, determining
the age (short-term due to the seasonal variation and long-term due to the distinction between
Holocene and Pleistocene groundwater (Sect.5.2.1.1.; Volume I).
One has to keep in mind that the δ18O value is very small and ‰ is no unit. ‰ means 1 over
1000. Hence, the delta value are always smaller than 1, although numbers in connection with
per mill, e.g. 25‰, are large: 25‰ is equivalent to 0.025.
13 12
The carbon isotopes C and C (⇒ δ13C) play an important role in quantifying water-rock
17
Chapter 2
interactions in the case of 14C age determination of groundwater (Sect.5.2.2.3). Their ratio
also allows to identify the proportion of biogenic and carbonate CO2 in water and to
determine initial geological settings of the groundwater recharge (Sect.5.2.1.2).
The nitrogen isotopes 15N and 14N (⇒ δ15N) are useful anthropogenic tracers. The biogenic
isotopic fractionations are complex, but often allow to determine the source of organic
pollution in groundwater (e.g. Heaton 1984, 1986; Sect.5.2.1.3).
The stable isotopic ratio of the sulphur isotopes 32S and 34S (⇒ δ34S) allows to differentiate
between marine, evaporitic and volcanic sources of dissolved sulphate in groundwater
(Krouse 1980). Biochemical processes change the isotopic composition and may thus be
recovered (Sect.5.2.1.4).
Recently, the isotopic ratios 37Cl/35Cl (Sect.5.2.1.5) and 10B/11B (Sect.5.2.1.6) have been used
in pollution studies of groundwater (Eggenkamp 1994; Frape et al. 1995). The strontium
isotopic ratio (87Sr/86Sr; Sect.5.2.1.7) is a valuable tracer for mixing and source studies of
mineralised groundwater.
2.3.2 RADIOACTIVE ISOTOPES

The other important group of isotope hydrological methods is related to radioactive
environmental isotopes (Sect.5.2.2). Their main field of application is isotopic dating. The
clocks begin ticking as soon as the radionuclide enters the groundwater i.e. at the time of
recharge. The time unit is given by the half-life Τ1/2 during which any activity of a specific
isotope decays by 50%. After 10 half-lives the activity has decreased to only 1‰ of the
original activity. The range of half-lives for the various environmental isotopes is large: from
300 000 yr (36Cl), to 5730 yr(14C) and 12.43 yr (3H).
There are two main principles of groundwater dating: in the case of cosmogenic radionuclides
the initial specific activity Ainit of any given radionuclide in the infiltrating groundwater is
known or can be estimated. It then declines according to the radioactive decay law, from
which the age of the sample t follows as
ln 2  A init 

t= ⋅ ln (2. 2)
T1 2  A spl 
 
where T1/2 is the half-life of the given radionuclide (Fig.2.2).

The most important representative of this class of tracer applications is the 14C method. It
provides an age of old groundwater by dating the dissolved inorganic carbon content (DIC;
Sect.5.2.2.3). The application often comes to complex recherches on the water-rock
interactions of the carbon isotopes (Volume I; Sect.4.4). Much older groundwater in very
extended basins may be dated by 36Cl (Sect.5.2.2.5), 81Kr (Sect.5.2.2.7) and 129I (Sect.5.2.2.9)
(see also Volume I). Groundwater ages up to 1000 yr are determined by the 39Ar method
(Sect.5.2.2.6), if the geological setting of the aquifers excludes underground production of
18
this isotope. Uranium isotopes are useful for mixing studies and are also promising for
groundwater dating (Sections 5.2.2) . Still in an experimental stage is the groundwater by
means of 32Si (Sect.5.2.2.4). Multi-isotope studies together with hydrochemical analyses are
recommended in any case study.
110
specific activity (pM#)
100 reservoir effect =

-20% of initial value
90
80
70
60
50
40
30
reservoir
20 correction
10
0
0 1 2 3 4 5
half-life
Fig.2.2 Decrease of the specific activity Aspl of a sample by radioactive decay in units of the half
life and for two materials with deviating initial activities Ainit: 100 pMX and 80 pMX. It is
obvious that the apparent age for the material with the lower Ainit is higher. The relative
differences of the activities of both materials (reservoir effect) just as the age difference
(reservoir correction) remains constant and independent of the age.
The most important representative of this class of tracer applications is the 14C method. It
provides an age of old groundwater by dating the dissolved inorganic carbon content (DIC;
Sect.5.2.2.3). The application often comes to complex recherches on the water-rock
interactions of the carbon isotopes (Volume I; Sect.4.4). Much older groundwater in very
extended basins may be dated by 36Cl (Sect.5.2.2.5), 81Kr (Sect.5.2.2.7) and 129I (Sect.5.2.2.9).
Groundwater ages up to 1000 yr are determined by the 39Ar method (Sect.5.2.2.6), if the
geological setting of the aquifers excludes underground production of this isotope. Uranium
isotopes are useful for mixing studies and are also promising for groundwater dating (Sections
5.2.2) . Still in an experimental stage is the groundwater by means of 32Si (Sect.5.2.2.4).
Multi-isotope studies together with hydrochemical analyses are recommended in any case
study.
19
Chapter 2
The second principle of dating groundwater is based on tracing of groundwater with isotopes
with variable input functions in time. There are suitable anthropogenic radionuclides prod-
uced by nuclear weapons tests (Fig.2.1) such as 3H (Sections 5.2.2.1), 3H/3He (5.2.2.2), 14C
(Sect.5.2.2.3), and 36Cl (Sect.5.2.2.5). Some others are produced by the nuclear energy
industry (85Kr; Sect.5.2.2.8).
As in tracer experiments, for this kind of groundwater dating the so-called input function
must be known or determined, i.e. the change of the specific activity of a certain radionuclide
in precipitation or the atmosphere at the moment of groundwater recharge. Depending on the
atmospheric medium from which the given radionuclide is derived, the input function is re-
lated to precipitation (for 3H), atmospheric carbon dioxide (for 14C), and air (for 85Kr;
Fig.2.1). Through the use of appropriate geohydraulic models (Volume VI; Sect.3.1.2) it may
be possible to estimate the age or mean residence time of a groundwater sample from its
isotopic composition. The precision of the results depends significantly on the reliability of
the input function and the validity of the applied model.
When evaluating isotope data by mathematical models, besides radioactive decay, there may
be other processes, which affect the spatial and temporal change of the radionuclide content in
groundwater. These processes are mainly hydraulically controlled mixtures (Volume VI;
Sect.3.2.1). When only two components are involved, the measured values of several samples
will fall on a mixing line, from which the properties of the original components (end–mem-
bers) can be determined (Fig.2.3) Hydrochemically controlled changes occur of isotopes as
radiocarbon are bound in dissolved compounds (in the case of carbon mainly as bicarbonate
and carbon dioxide) which may react with the aquifer rock. Such a process affecting 14C
would be precipitation or re-dissolution of aquifer carbonates proceeding under stationary
equilibrium (Clark and Fritz 1997).
2.3.3 CHEMICALS
Chemical compounds have to be shortly discussed as they are often needed for an
unambiguous interpretation of isotope results. The simplest natural chemical tracing of
groundwater movement tends to rely on measuring the chloride concentration. Cl- is a
conservative tracer, which is subject, neither to adsorption or desorption during transport.
Hence, the relation between chloride concentration and δ18O or δ2H values illustrates the
effect of various processes such as groundwater mixing (Fig.2.3), the dissolution of halite or
the admixture of saline water, seawater or brine (Sect.3.2.1.1; Fig.5.16).
During hydrochemical evolution the concentration of individual ionic species either increases,
remains constant or decreases. For example, in the case of water-rock interaction a Na+
increase along the aquifer flowpath, associated with a decrease in Ca2+ and Mg2+, is attributed
to ion exchange with clay minerals (e.g. Clark and Fritz 1997); changes in Ca2+, Mg2+ and
SO42- are due to anhydrite dissolution and dedolomitisation (e.g. Plummer et al. 1994). The
process of incongruent dissolution can have quite different effects on groundwater chemistry
20
depending on the rock type involved (e.g. Gislason and Eugster 1987). In other cases
bacterially-mediated redox reactions may occur, commonly resulting in an increase in
dissolved Fe2+ and Mn2+ along the flowpath, and not especially sensitive to the aquifer
lithology (e.g. Edmunds et al. 1987; Mariotti et al. 1988). The identification of the processes
14
is essential for C groundwater dating. These reactions also modify the δ13C, δ34S and δ15N
values.
δ18OSMOW
-5 -4 -3 -2 -1 0 +1 +2 +3 +4 +5 +6 ‰
δ2HSMOW
+30
r
ate
W
L
un dw +20
M
r/ gro
wate
sea +10
ter
dwa ±0
un
gro
ep
/ er / de -10
ater wat ter
dw nd a wa
r oun grou se groundwater - northern Qatar -20
g ep
de groundwater - southern Qatar
sea water -30

deep groundwater (artesian)
-40
Fig.2.3 Three-component mixing triangle: three mixing lines of two-components each between
see water/deep groundwater, sea water/groundwater and deep ground/groundwater for
Qatar (Yurtsever and Payne 1979). The concept of three-component mixing is confirmed
as most of the data point fall into the triangle.
2.3.4 COLLOIDS
Colloidal particles have diameters of less than 10 µm and may have an organic or mineral
origin. They may result from breakdown of larger particles or, more commonly, from the
aggregation of smaller particles. Owing to their relatively large and reactive surface area, they
are able to absorb heavy metals, radionuclides and organic compounds. In addition they may
be hydrophobic or hydrophilic, and tend to flocculate as ionic strength increases (Drever
1997). Colloids may influence the isotope compositions of various isotopes by adsorption,
though no studies of this are known. In groundwater of crystalline rocks and some sandstones,
colloidal complexation of the heavier metals results from silica and clay minerals, affecting
also the uranium isotope composition.
Colloids are more abundant near sources of recharge, and also in karstic systems where they
21
Chapter 2
may reflect storm-driven changes in chemistry or flow rates.

While many investigations have centred around the impact of colloids on radionuclide
migration in low-permeability formations (e.g. Grindrod 1993; Degueldre et al. 1996), much
less is known about colloids in aquifers containing potable water (Stagg et al. 1997).
The extent to which colloids are present in groundwaters varies, but concentrations are
unlikely to exceed 100 ng L-1 except under extreme conditions (Degueldre et al. 1996). This
implies that their presence is only of concern if we are dealing with highly toxic contaminant
species, in principal certain radionuclides and possibly some organic compounds.
2.3.5 NOBLE GASES

Noble gases have attracted attention in hydrogeological studies, particularly where older
groundwaters are involved. The noble gases are chemically inert. They are used for
hydrogeological investigations in two quite different ways:
Assessment of recharge temperature: the aqueous solubilities of Ar, Kr and Xe change
individually with temperature with the result that any particular ratio of Ar/Kr/Xe can be
interpreted to give the absolute recharge temperature with a precision of about ± 1.5°C
(Andrews 1991, 1992; Volume I, Sect.2.3.5). Excess Ar produced by radioactive decay of 40K
and the presence of atmospheric Ar can be corrected for by the 40Ar/36Ar ratio.
The noble gas temperature of groundwater reflects the climatic conditions under which a
particular groundwater was recharged and gives a rough estimate of the age (Fig.2.4). Some
knowledge of groundwater mineralisation is necessary, because high salinities have a
significant 'salting out' effect on the gases (e.g. Suckow and Sonntag 1993). The noble-gas
recharge temperature and the δ18O and δ2H values of the groundwater are linearly correlated
(Deak et al. 1987).
Sampling for noble gas analyses is relatively simple but only few laboratories have the
specialised mass spectrometers required to make precise measurements.
Estimation of residence time depends on the decay of short-lived isotopes like cosmogenic
39
Ar (Sect.5.2.2.6) or the long-lived 81Kr (Sect.5.2.2.7), and on the production of a long-lived
isotope such as 4He (Sect.5.2.2.10). The radioactive noble gas radon (222Rn) with a half-life of
only 3.8 days is used to study short-term mixing of surface and groundwater (Sect.5.2.2.11).
The main disadvantage of applying these gaseous isotopes is that sampling is laborious
(Lehmann et al. 1991; Cook and Solomon 1997), measurement facilities are limited, and the
in situ production rates are not yet well characterised.
Chlorofluorocarbons like CFC-11, CFC-12 (CCl3F and CCl2F2) and SF6 have been the most
widely used gases in the refrigeration and air-conditioning industries. Although their use
started as far back as 1931, the major build-up has occurred in the post-war period. They are
well mixed in the atmosphere (their effect on ozone in the upper atmosphere are well
22
3
documented) and therefore have a significant tracer potential instead of H (Busenberg and
Plummer 1992; Cook and Solomon 1997).
40 000
C age (yr BP)
35 000
30 000
14
25 000
20 000
15 000
10 000
5000
0
noble gas temperature (°C)
22
°C
21
20
2.5°C
19
18
5.2°C
17
16
15
14
0 10 20 30 40 50 60 70 80 90 100
distance (km)
Fig.2.4 Absolute recharge temperature of groundwater in the Budapest Basin during the last
30,000 yr determined by analyses of the noble gases dissolved in groundwater (Stute and
Deak 1989).
23
Chapter 2
24
3 GEOHYDRAULIC ASPECTS
Gravitation is the most important from the external forces which controls groundwater flow in
the interstices of rocks. The flow may be laminar or turbulent. Laminar flow has distinct
streamlines, while the flow direction at every point remains unchanged in time. In turbulent
flow, the flow lines are confused and heterogeneously mixed.
Under natural conditions laminar flow prevails in unconsolidated sediments which are
considered to be a homogeneous and permeable medium, though partly anisotropic. Laminar
and/or turbulent flow occurs in fissured rocks, karst cavities and lava tubes. There are three
principal geohydraulic conditions of groundwater flow schematically shown in Fig.3.1.
precipitation
PISTON FLOW
DISPERSION
EXPONENTIAL MIXING
fast
slow
Fig.3.1 Three cases of groundwater movement by piston-flow without and with dispersion in
confined aquifer and flow in an open aquifers where different fast flowing water is mixed
in the well or spring.
25
Chapter 3
3.1 STEADY-STATE GROUNDWATER FLOW
3.1.1 DARCY VELOCITY AND TRACER VELOCITY

In 1856 Darcy empirically found for laminar flow in small pores and at low gradients that the
specific discharge Qdis/A (filtration velocity = DARCY velocity = v) is proportional to the
hydraulic gradient ∆h/z (Fig.3.2). A is the cross section of the aquifer.
Q dis ∆h
v= = q dis = K ⋅ (3.1)
A ∆z
where K is the hydraulic conductivity.
Q
∆h
∆z
Q
Fig.3.2 Pressure distribution and head loss (∆h) through flow in a sand column in order to
demonstrate the Darcy law (after Todd 1959) (Eq.3.1).
The hydraulic conductivity K or coefficient of filtration has the dimension of a velocity as

the hydraulic gradient is dimensionless (e.g. m/s, m/d). K covers a wide range (Fig.3.3)
In a porous and permeable rock environment, groundwater flows along curved pathways with
an actual velocity or tracer velocity vtrac. The tracer velocity of groundwater changes with the
width of the pores in the rock.
Between two flow cross sections of the distance z, the tracer (travel) velocity vtrac is given by
z
v trac =
t
t is the time necessary for a water particle to pass this distance. The tracer velocity is
determined by dye experiments or by environmental isotope dating. It describes the transport
of any tracer (or contaminant) in an aquifer.
26
Geohydraulic Aspects
pure gravel
sandy gravel
coarse sand
medium grained sand
find sand
very fine sand
silt
clayey silt
clay
10-8 10-6 10-4 10-2 100 102

hydraulic conductivity (m/s)
Fig.3.3 The range of hydraulic conductivity (Eq.3.1; coefficient of filtration) in various sediments
(after Dürbaum 1969).
The filtration velocity v (Darcy velocity) and the tracer velocity vtrac are related to each other
by the total porosity ntot
v
v trac = (3.2)
n tot
The filtration velocity and tracer velocity have to be distinguished from the speed of a
hydraulic pulse in a aquifer which may be caused by a storm event. This velocity cannot
simply be deduced from the time lag of the discharge peaks of springs and artesian boreholes
behind the peak of precipitation.
Example:
The filtration velocity is calculated to be 6.3 m yr-1 for a hydraulic conductivity of 10-3 m s-1,
and a gradient of the water table of 2 m over a distance of 1000 m. This means that 2 ×
10-6 m3 are passing per m2 and second or 6.3 m3 per square meter and year. The tracer velocity
is 63 m yr-1 for a total porosity of 10%. In case of mass transport e.g. for tracer experiments
the total porosity is crucial rather than the effective porosity as there is usually sufficient time
for an hydrochemical and isotopic exchange between the bound and free mobile groundwater.
For an aquitard with a K value of 10-10 m s-1, a total porosity of 50% and a vertical gradient of
4 m/50 m the filtration and tracer velocities are much smaller than 1.6 × 10-9 m s-1 or
5 cm yr-1, respectively.
3.1.2 PRINCIPAL GROUNDWATER FLOW MODELS

For any quantitative hydrological evaluation of the results of a tracer study (e.g.
environmental isotopes) the groundwater flow in the geohydraulic system must be idealised
taking account the physical properties of the isotopes employed (e.g. radioactive decay) and
the flow characteristics of the carrier, i.e. that of the groundwater. For the use of isotope
27
Chapter 3
hydrological data, conceptional and lumped-parameter models have specifically been

developed. A detailed description is given in Volume VI for young groundwater (Zuber 1986;
Maloszewski and Zuber 1993, 1996, 1998). In this section only a short summary can be
given.
The simplest hydrogeological situation is represented by the piston-flow model (Fig.3.1). In
this case the groundwater flow in the aquifer is similar to that through a tube and is described
by the Darcy law (Eq.3.1; Fig.3.2). Both stable isotope and dissolved chemical compositions
do not change. The activity of the radioactive environmental isotopes decreases with time or
with the distance of flow according to the law of radioactive decay. The amount of
groundwater in the system remains constant as recharge and discharge are balanced.
The piston-flow model usually well describes the flow in confined aquifers. When the
groundwater recharge lasts longer than the maximum residence time of the groundwater in the
aquifer the tracer velocity is proportional to the DARCY velocity, and the regional total
porosity can be estimated by Eq.3.2.
In natural groundwater systems, that have more than one aquifer or is subject to interactions
with surface water, mixing of groundwater of different age and origin is common. The most
simple cases are described by two- and three-component mixing models. In the plot of two
parameters of two end members straight lines allow to read the proportions of the two end
members. In the case of mixing of three components a triangle is obtained bordered by three
two-component mixing lines (Fig.2.3). As an example, a plot of chloride and δ18O values
allows to recognise whether or not salt is dissolved, or fresh water is mixed with brine or sea
water. Another example is the admixture of irrigation return flow (Sect.5.2.1.1).
Two end-members I and II with the properties XI and XII are mixed with the proportions
xI and xII. The mass balance equation yields
x I ⋅ X i + x II ⋅ X II = Y with x I + x II = 1 (3. 3)
The proportion xI of the end-member I is calculated from the properties of the end-members I
and II and that of the sample Xspl by
X spl − X I
xI = (3. 4)
X II − X I
The precision of the determined proportions of two mixing components is better than ± 10%
for sea- and freshwater as end members, but worse than ± 25% for mineralised and freshwater
using isotope and hydrochemical data (Geyh and Michel 1981). If a system is monitored over
long periods or within very short time intervals, several groundwater and surface water
components can be separated from each other (Behrens et al. 1979).
A modification of the piston-flow model also considers dispersion (Fig.3.1; Sect.5.1.2.2.2).
This process describes the mixing of different old groundwater components moving over
short distances with different velocity within the aquifer. The isotope signal becomes
28
smoothed. This process is important for the interpretation of the isotope composition, if the
groundwater has a high velocity as in karst water systems but it is usually negligible for
slowly moving groundwater which can be dated by the 14C method (Sect. 5.2.2.3).
Mixing of many different old groundwater components is assumed for pumped shallow
groundwater and particularly for spring water from fissured aquifers (e.g. karst springs). The
age distribution may be approximated by the exponential function (exponential model;
Volume VI). The corresponding exponential model is based on the assumption of mixing of a
theoretically infinite number of different old components, of which the proportions decrease
exponentially with increasing age. Each component has its specific isotope composition
according to the input function (Fig.3.4A). The 3H input function for karst groundwater in
southern Germany is shown in Fig.3.4B. This conception has been currently confirmed
especially for karst springs.
percentage
MRT = 2 yr
50
A
40
30
20
10 MRT = 5 yr
MRT = 20 yr
0
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15
years before recharge
H value (TU)
B
3
1 yr
1000
5 yr
10 yr
20 yr
50 yr
100
100 yr
10
1954 56 58 60 62 64 66 68 70 72 74 76 78 80 82 84 86 88 90 92 94 96
Fig.3.4 (A) Composition of karst groundwater as mixture of different old water components and
(B) relationship between the isotopic composition (e.g. 3H) of the mixed water and the
mean residence time (MRT).
29
Chapter 3
For extended phreatic aquifers with a direct diffuse recharge rate Qrec, the average water age
was calculated by the exponential model (Vogel 1970), assuming a constant porosity and
aquifer thickness d:
n tot ⋅ d
t avg =
q rec
For a hard rock aquifer with constant thickness and an exponentially decreasing porosity we
obtain
n tot (0) ⋅ d char

t avg =
q rec
ntot(0) is the total porosity at zero depth and dchar is the characteristic depth where the porosity
has decreased by a factor of 2.72 (= e).
Examples: Black-Box Models
Theoretically the piston-flow model, the dispersion model and the exponential model can be
described by the black-box model (Zuber, 1986; Maloszewski and Zuber 1996).
The so-called lumped-parameter or black-box models (Zuber 1986, Maloszewski and Zuber
1996) use the residence time function f ( t , P) with t as mean residence time (turnover time)
of a groundwater volume element and P as hydrogeologically relevant parameters describe the
tracer (isotope) concentration (specific activity). Cin(t) is the specific activity of the mixed
components of differing transit times. The specific activity of the mixed sample Cout (t) is
given by It is given by the convolution integral
∞
C out ( t ) = ∫ C in ( t − t´) ⋅ f ( t , P) ⋅ e −λ⋅t´ dt´ (3. 5)
0
t is the time of sampling; λ = ln2/T1/2 is the decay constant of the environmental isotope (for
stable isotopes λ = 0); t´ is the time span between the entry of the environmental isotope from
the atmosphere into the unsaturated zone and its arrival of the saturated zone. The input
function Cin(t – t´) represents the concentration or activity at which the relevant environmental
isotope becomes involved in groundwater recharge (e.g. input distribution in precipitation of
3
H). Geochemical processes are not considered.
The different lumped parameter models are characterised by their residence-time distribution
function f ( t , P) (Zuber 1986; Maloszewski and Zuber 1996). For the piston-flow model
(PFM) (Fig.3.1)
f(t´, P) = δ(t´− t )
δ(t´-t) as Dirac function. The solution of Eq.3.5 yields for a constant Cinit
C out ( t ) = C init ⋅ e − λ⋅t (3.6)
30
The residence-time response function f(t , P) of the exponential model (EM) (Fig.3.1) is
given by
t´
1
f ( t´, P) = e t (3.7)
t
When Cinit is invariant with time (e.g. cosmogenic 14C, 3H, 32Si) and t is the seepage time of
the water from the groundwater surface to any point in the aquifer, the exponential model
yields for an isotope with the decay constant λ:
C init ⋅ e − λ⋅t
C out ( t ) = (3.8)
1 + λ ⋅ t avg
The response function f (t , P) of the dispersion model (DM) is given below:
 
 (1 − t´ ) 2 
1
f ( t´, P) = exp  t  (3.9)
D t´  4D t´ 
t ' 4π  
v trac ⋅ z t  v trac ⋅ z t 
where z is the travel distance (Sect.3.1.1). Another approach to interpret isotope hydrological
results are system-specific compartmental models or multi-box models. In this approach the
groundwater system is divided in geohydraulically plausible boxes with an assumed uniform
(well-mixed) tracer concentration and well-defined geohydraulic parameters. The volumes,
the parameters, etc. are adapted iteratively until the input and output curves fit best with the
obtained data points. Adar (1996) optimised this approach by a quadratic optimisation
procedure in order to determine geohydraulic parameters applying isotope and hydrochemical
data. These approaches are most valuable if geohydraulic knowledge of a groundwater system
to be studied is scarce.
It is essential that we apply time-series of environmental isotope data with differing half-lives
and that we try to interpret the data by various models. Apparently, contradictory ages or
mean residence times may be obtained. The deviations will, however, allow to decipher the
investigated groundwater system. In any case agreement between empirical and modelled
results does not automatically mean that the model applied describes the natural reality
(Oereskes et al. 1994; Maloszewski and Zuber 1993, 1998).
Conceptional models are individually developed for geohydraulically more complicated
systems e.g. leaky aquifers. As an example Geyh et al. (1984) modelled the seepage of
groundwater from a phreatic aquifer into a confined aquifer. Applying 14C dates of DIC, the
hydraulic conductivity K of the separating aquitard and the diffuse recharge rate of the
confined groundwater could be estimated. Another conceptional model was developed for the
interpretation of environmental isotope data describing the seepage of water from the Nile
River into the phreatic aquifer (Verhagen et al. 1991).
31
Chapter 3
3.1.3 CONSIDERATIONS ABOUT MODELLING

The evolution of the isotopic composition within a geohydraulic system can be modelled
using the equations for the movement of solutes, provided the initial and boundary conditions
and other appropriate parameters are known. This is called forward modelling. The opposite
process of interpreting field data to estimate parameters is called inverse modelling. The aim
of isotope methods is to invert field data in order to estimate recharge rates, water ages, tracer
velocities or mean residence times.
When inverting field data, it is necessary to consider two types of errors. The first is the
measurement error. It is associated with the sampling and the spatial variability of field data,
the errors involved in the chemical and isotopic analyses, those of the estimation of the input
function and other parameters. Most of these errors are quantifiable.
The second type of error is associated with the model assumptions. If for a model steady-
state, one-dimensional piston-flow is assumed and dual-pathway flow is excluded but all or
several of these assumptions are wrong in some aspect, there will be an error in applying the
model to field data. Generally, this second type of error is more difficult to quantify and can
only be assessed by experiments under controlled conditions or by comparing estimates
obtained by various methods.
If inverse modelling is done, the error of estimating recharge rates will depend partly on two
types of error, but also on the model sensitivity of the measured data to the recharge rate. If
the final profile of a tracer is only weakly dependent on the water fluxes, the inversion of the
tracer profile will be very sensitive to measurement and model errors. In these cases, the
inversion is said to be ill-posed. The aim of all isotope methods is a design of models which
are sensitive to obtain recharge rates, water ages and geohydraulic information.
3.1.4 GROUNDWATER DISCHARGE

Groundwater is discharged to the surface where the zone of saturation reaches the surface.
The groundwater may percolate, effluently flow into streambeds or discharge at springs.
Groundwater discharge or surface runoff usually occurs at the outlet of a drainage basin
long after the recharge event.
Interflow (also subsurface flow or hypodermic flow) is created by seeping precipitation but
does not enter the groundwater. It occurs in the soil at shallow depth and lasts only shortly
after the storm event. It is clearly distinguished from the surface runoff (Volume III).
Discharge of groundwater can only be detected or even measured if it is accessible at the
surface e.g. as spring water. Large quantities of groundwater are discharged, however, in
streambeds and becomes part of the total runoff of the discharge of streams. This is reflected
by a perennial flow also during long periods of drought (base flow). The proportion of
groundwater in the total discharge of a stream is determined by component separation
techniques (Fig.3.6). The classical way is hydrograph separation evaluating the variation of
32
the discharge in time. Techniques using environmental isotopes are a very powerful tool (Fritz
et al. 1976).
discharge Q
Qsurf
base flow Qbase
time
Fig.3.6 Hydrograph of the total runoff of a basin. The white and grey areas represent the highly
variable surface runoff Qsurf and the groundwater runoff (base flow) Qbase, respectively
(after Fritz et al. 1976).
3.1.4.1 SPRINGS
A spring is a location where groundwater is discharged naturally from the rock or soil forming
a superficial flow. Discharge happens into a pool, river, lake, and the sea (effluent flow). The
discharge of springs in humid regions usually fluctuates with the rate of precipitation during
the year.
Springs are distinguished and classified according to their seasonal discharge behaviour
(magnitude and fluctuation), the duration of flow during the year, the hydraulic conditions,
geological and topographic features, chemical and isotopic composition, and water
temperature.
According to the duration of flow, three categories of springs are distinguished:
1) perennial springs with a continuous flow,
2) periodic springs with periodically changing flow rates. They have to be distinguished
from geysers of which eruptions are caused by periodic expansion of vapour, and
3) intermittent springs with a flow which is interrupted a certain time during the year e.g.
during the dry season.
33
Chapter 3
The largest springs usually occur in karstified limestone terrain, in fissured lava flows, porous
sandstone structures, and in large gravel and sand deposits. The discharge rate of a spring
allows an estimate of the size of the recharge area, if the geological situation is known. The
isotopic composition of the issued groundwater provides information on its origin and mean
residence time.
Ascending or artesian springs issue from a level below the spring or from below the
erosional base along permeable groundwater pathways, e.g. along fissures or faults. Often the
discharge can be increased by tapping a borehole. Then, the isotope composition of the
pumped spring water deviates from that of the naturally discharged spring water as it contains
a higher proportion of old groundwater.
Descending springs drain above the base level of erosion. They issue from perched aquifers
and partial hydrogeological structures with a limited recharge area. Their discharge is low and
fluctuating (e.g. contact springs).
Overflowing springs (barrier springs) issue at places where the prevailing lateral component
of groundwater flow in an aquifer is dammed behind an aquiclude and directed toward the
surface. This may occur along an inclined contact of an aquifer with an underlying aquiclude,
and along outcrops of faults and synclinal structures. Barrier springs sometimes drain
groundwater basins with large groundwater resources. The water has a long residence time,
while the discharge is damped with respect to fluctuations in the precipitation. The isotopic
compositions cannot be interpreted with the simple well-mixed model (exponential model;
Sect.3.1.2; Volume VI). Short- and long-lived isotopes as 14C and 3H will deliver
considerably deviating mean residence times.
3.1.4.2 PRODUCTION WELLS

The construction of wells has to be considered when interpreting isotope hydrological results.
Detailed information are found in Clark (1988). Wells are shafts or holes which were sunk,
dug or drilled into the earth to extract water (International Glossary of Hydrology 1974).
Dug wells are usually shallow, have a large diameter and were constructed manually. They
usually catch shallow groundwater.
Drilled wells are constructed as boreholes and have usually small diameter. They may be
several hundred to more than 1000 metres deep. They pump water from a defined layer if
screens are present in the well shaft.
Artesian wells tap confined aquifers (Bates et al. 1980). The water head is above the level of
the phreatic groundwater or even above the ground level.
If groundwater is pumped from wells, for dewatering of mines or the construction of tunnels,
the natural hydrodynamics of the groundwater system is changed and adopts only slowly to
the anthropogenically disturbed state of drainage. This process is often accompanied by the
34
disappearance of springs and always by a decline of the piezometric level. Groundwater from
various parts of the aquifer may become mobilised and mixed. Even the groundwater regime
may change. Such interferences are usually reflected in changes in the chemical and isotopic
compositions of the water. This may also be due to the admixture of surface water from a
streambed (bank infiltration) or of shallow groundwater from an alluvial plain (Volume III).
In arid regions without or with a limited groundwater recharge, pumping of groundwater often
means groundwater mining and depletion of groundwater resources (Sect.3.2.2; Volume V).
The stable isotope compositions of oxygen and hydrogen (Sect.5.2.1.1) of the groundwater
are a good tracer for new hydraulic connections. The admixture of very young water is
detected by tritium (Sect.5.2.2.1 and 5.2.2.2). Radiocarbon values (Sect.5.2.2.3) are modified
after many years of pumping (Sect.3.2.2). As a consequence, isotopic monitoring of short-
term changes in the hydraulics of an aquifer system, due to pumping tests or groundwater
abstraction, should start with δ18O, δ2H and 3H determinations before the first hydraulic
disturbance.
3.1.4.3 WELL CONSTRUCTION AND SAMPLING OF WATER FROM WELLS

Various techniques are used for the sinking of a well: percussion drilling, rotary drilling,
auger drilling, and manual construction. During rotary drilling, drilling fluids are used to
remove cuttings from the borehole, to cool and lubricate the drilling bit, and to support the
borehole wall by hydrostatic pressure in order to prevent caving. A common drilling fluid in
hard rocks is water. It is usually removed after completion of the borehole by well
development, i. e. by removing the bentonite mud with water or the polymer by
biodegradation. In spite of this, water samples from newly constructed wells often contain
remains of the drilling or cleaning fluids which may falsify the natural isotopic composition
of the groundwater. Bacterial decomposition of organic stabilisers used in the fluids may
change the 14C value of DIC, while using surface water may change the tritium activity.
During or after drilling of a well a metal pipe (casing) is lowered into the borehole in order to
prevent the walls from collapsing. Only in consolidated and crystalline aquifers, the boreholes
may be left without support. The casing is perforated or provided with a metal screen or
gravel filter within the water-bearing section.
Production wells are constructed for maximum water yield. The perforated sections stretch
over the entire thickness of the aquifer and even many aquifers. In this case groundwaters of
different isotope compositions may be mixed. Well logs may help to identify the positions of
groundwater inflow. Stratified water samples are collected using packers or depth samples.
Depth samplers are cylinders that are lowered to the wanted position before opening and
filling with water and closing. The samples are not representative if vertical water flow exists
in the well shaft. In this case the use of packers is recommended. These are rubber tubes that
are filled with air to seal the shaft above and below the section of water. Instead of this costly
35
Chapter 3
technique, submersible small-diameter pumps may deliver representative samples from the
wanted depth. The electrical power is delivered from a generator or a car battery.
Isotope sampling of artesian wells is not problematic. The samples are free of any secondary
contamination because the elevated piezometric pressure protects the aquifers. Production
wells are sampled under operation. Treated water (e.g. chlorinated) should not be collected.
Wells with a significant drawdown may also pump groundwater from overlying aquifers.
Observation wells should be pumped before sampling until the EC and pH values approach a
constant level or at least three times of the well volume is abstracted.
3.2 NON−STEADY STATE GROUNDWATER FLOW

In most isotope hydrological case studies it is assumed that the recharge and discharge of the
groundwater system are balanced as usual in humid regions. Then the groundwater flow
velocity, the flow direction and regional values of the porosity and hydraulic conductivity as
well as boundary conditions for numerical modelling can be determined by means of the
isotope hydrological results. The often cited problem of the uncertainty of the correction of
the 14C time scale of DIC is overestimated for common fresh groundwater resources. The
resulting age corrections are often constant.
For hydrogeologists the recognition of hydraulic non-steady state conditions is an important
task. In short-term studies the annual periodicity of meteorological and climatic processes
results in a continuous disturbance of the hydrological processes. The periodicity of the
groundwater recharge and related hydrodynamic phenomena as fluctuations of the
groundwater level, the discharge of springs can be used to evaluate geohydraulic parameters.
They are reflected in the variation of the isotopic compositions of the surface water and
shallow groundwater (Volume III). In long-term studies climatic changes might have
interrupted the groundwater recharge during pleniglacial periods in the present humid region.
In arid and semi-arid regions, non-steady-state hydraulic conditions dominate. The present
groundwater discharge exceeds recharge and a large proportion of such resources are fossil.
The palaeowater was recharged during former pluvial periods. Non-steady-state hydraulic
conditions are also created by intensive groundwater abstraction.
3.2.1 PALAEOCLIMATIC CAUSES

In arid and semi-arid regions isotope hydrologists distinguish between steady-state and non-
steady recharge/discharge conditions. In non-steady-state systems groundwater recharge was
interrupted in the past as result of changing palaeohydrologic conditions, e.g. after the
termination of the humid periods in the Late Pleistocene and Early Holocene (Fig.3.7; Geyh
1994). After each cessation of groundwater recharge the water head started to decline (Burdon
1977). The groundwater gradient, the groundwater velocity and the discharge rate decreased.
14
Groundwater ages from such regions, e.g. determined by the C method (Sect.5.2.2.3), still
36
reflect steady-state conditions of the former pluvial period when groundwater was recharged.
The difference between 14C water ages of two wells are related to the past tracer velocity and
direction and is not related to the actual velocity (Fig.3.8). In contrary, the present piezometric
surface does not. The slopes between hydraulic heads are larger than those expected from the
actual groundwater recharge. The latter gradient superimposes the gradient of the fossil relict
groundwater body. However, the periods of groundwater recharge can be accurately
evaluated, which is essential for numerical modelling of groundwater resources and for
palaeohydrological studies. If erroneously steady-state conditions are assumed and limited
periods of groundwater recharge in the past are not taken into account modelled groundwater
recharge rates are very much overestimated (Verhagen et al. 1991; Geyh et al. 1995).
12
frequency
10
0
35,000 30,000 25,000 20,000 15,000 10,000 5000 0
conventional 14C age of DIC [BP]
Fig.3.7 Palaeohydrological situation in the Arabic Deserts of the Hamad region (Geyh 1994).
3.2.2 ANTHROPOGENIC CAUSES

Non-steady state hydraulic conditions may also be caused by intensive groundwater
abstraction. Leakage of reservoirs, artificial recharge and other processes may disturb the
natural hydrodynamic conditions. As long the piezometric conditions are not adapted to the
disturbed geohydraulic conditions, the system remains in a non-steady state. Indications are
e.g. a steadily declining water table or changing hydrochemical and isotopic compositions of
the pumped groundwater. As a result groundwater percolation through aquitards, separating
adjacent aquifers, may become increased. Changes in the 14C water ages for production wells
are strong indications of overexploitation and sometimes "groundwater mining" (Fig.3.9;
Geyh and Backhaus 1979; Verhagen et al. 1991).
37
Chapter 3
pluvial intensity
30 20 10 0
A B C D
yr B.P.
C age of DIC (yr BP)
35,000
A-B: 2
30.000 m yr -1
=(26-2
2 km)/(2
8-26 k
yr
25.000 C-D: 4 m y -1)
r =(18-6 km)/(23-18
kyr)
14
20.000
15.000
10.000
Erratic result
A-D: 2.5 m yr-1=(26-6 km)/(28-18 kyr)
5000
0
30 25 20 15 10 5 0
distance from the catchment [km]
Fig.3.8 Scheme to estimate the tracer velocity of groundwater for the arid Near East in the past
(Geyh 1994). Erratic results are obtained if a tracer velocity is calculated from 14C dates
of from different pluvial periods (e.g. for the wells A and D). The tracer velocities A–B
and C–D corresponds to those during the past pluvial periods.
Under simple geohydraulic conditions, the temporal change of the conventional 14C dates of
groundwater can be used to quantify the resulting changes in the mixing of different old
groundwater as shown for the Azraq area, Jordan (Verhagen et al. 1991).
A long-term trend in 14C ages of groundwater in a heavily exploited aquifer reflects a complex
age stratification. It is not yet understood which pumping parameters (e.g., abstraction rate,
total abstraction, meteorological conditions, depth of filter and of the pump) are crucial for the
38
observed 14C changes and for what information can be derived from any similarity of
long-term 14C trends. They may contain valuable information for optimising groundwater ab-
straction in well fields and for preventing groundwater pollution by admixture of young or old
groundwater.
36
specific 14C activity (pMC)
operation of the
32 AWSA well field
28 DS
24 QS
20
Etwall
16
12 AZ8
8 UM 2
4 AZ1
0
1973 1975 1977 1979 1981 1983 1985
Fig.3.9 Changes of 14C water ages as result of groundwater overexploitation within the Azraq
area (Verhagen et al. 1991). The proportion of young basalt groundwater has increased
and that of the Cretaceous groundwater has decreased.
39
Chapter 3
40
4 WATER-ROCK INTERACTIONS
Isotope exchange between groundwater and minerals at temperatures of common, non-

thermal groundwater bodies is slow (O'Neil 1987). Heterogeneous reactions between water
and minerals with complex kinetics are usually irreversible at low temperatures. Therefore,
cold groundwater rarely reaches chemical and isotopic equilibrium with minerals of the
aquifer. There are, however, exceptions. The reaction between water, CO2 and calcite is one
example. Others examples are the oxidation of organic material as peat, and microbial
metabolic processes which do not only change the chemical composition and oxidation state
of dissolved nutrients (O2, C and S), but are also accompanied by large shifts in the isotope
compositions (isotope fractionation) (Volume I).
The isotopic and chemical compositions of groundwater reflect the mineralogical composition
of the rocks in the aquifer and can be used to localise recharge areas, and to determine the
origin of groundwater (meteoric, marine, fossil, magmatic and metamorphic water) and of
individual chemical components (e.g. carbonate, sulphate, nitrate and ammonium). The water
compositions can also give information about processes of water-rock interaction and
microbial processes in the water.
There are three major processes which are accompanied by isotope fractionation of water
molecules and dissolved components in groundwater systems within the time scale of
groundwater percolation:
1) evaporation and condensation leading to the fractionation of 2H/1H and 18
O/16O
(Sect.5.2.1.1) between vapour and liquid water,
2) chemical reactions between gaseous CO2, dissolved carbonate species and precipitated
carbonate minerals leading to the fractionation of 13C/12C (Sect.5.2.1.2), and 14C/12C
(Sect.5.2.2.3).
3) microbial metabolic processes such as desulfurication (Krouse 1980), denitrification and
nitrification (Hübner 1986), leading to the fractionation of 15N/14N (Sect.5.2.1.3), 34S/32S
(Sect.5.2.1.4) and 18O in anions between solution and organic matter.
In geothermal systems significant isotope exchange of hydrogen and oxygen occurs between
rock and water (Chapter 6), due to membrane filtration through layers of semi-permeable
clays as well as hydration or dehydration of secondary minerals.
Because of the slow exchange of isotopes between cold groundwater and its surrounding rock,
groundwaters of different origin can preserve their isotopic compositions over geological
times. Therefore, mixing of different types of groundwater and the origin of dissolved
41
Chapter 4
components can be evaluated using δ2H, δ18O, δ34S values and the 87Sr/86Sr ratio
(Sect.5.2.1.7), acting as conservative tracers like chloride and bromide ions. In case of mixing
of more than three components it may be difficult to determine the isotopic and
hydrochemical compositions of the corresponding end members.
There are various processes in the unsaturated zone which determine the qualitative change of
the pore water.
4.1 ANION EXCLUSION-ADSORPTION: PHYSICAL

ABSORPTION
Anions and other solutes do not move through soils similar to water because of the interaction
between the ionic charge and the charge found on the surfaces of the clay minerals (and
organic matter) that make up the soil or aquifer. The charges found on different minerals vary
greatly. In many cases they may depend on the pH as well as the constituents and
concentrations of the soil solution. Within a soil both positively and negatively charged
surfaces can exist simultaneously on different parts of the same mineral as well as on different
minerals.
Generally, clay minerals exhibit a negative charge, effectively excluding anions from near the
mineral surface. The excluded volume is dependent on both the water content and the
concentration of the soil solution. The anions are pushed out of the matrix in the main
porosity, while the cations are absorbed. This phenomenon can lead to a delay in the
restitution curves between anionic as well as isotopic tracers.
Significant adsorption of anions has also been found for soils containing hydrous oxide sur-
faces. The main compounds involved are aluminium and iron oxides (including hydroxides
and oxyhydroxides) as well as the edges of layer-silicates. The surface charge of these
minerals depends on the pH of the soil solution. The positive charge increases with decreasing
pH. Kaolinite is one mineral that displays this behaviour. Adsorption of anions will cause the
anions to be retarded with respect to the movement of water in the soil or aquifer. This may
also have an effect on the environmental isotope compositions.
Johnston (1988) showed that ignoring adsorption of chloride at low pH in one profile made
the concentration to be overestimated by a factor of two.
4.2 CHEMICAL ABSORPTION

The distinction between chemical and physical absorption is difficult to access in the case of
clay. A distinction could be made by studying the possibility of desorption and the kinetics of
the reaction.
42
Water-Rock Interactions
4.3 EXCHANGE OF IONS

The phenomenon is linked with the crystalline structure of clay particles, that have a negative
charge at the surface. The potential capacity of ion exchange depends on the nature of clay.
4.4 CHEMICAL INTERACTION BETWEEN SOLUTES

The chemical processes may be divided into two principal phenomena:
1) chemical precipitation controlled by the solubility of a substance, and
2) chemical alteration by e.g. oxydo-reduction and complexation processes.
These interactions may be intensified by the presence of micro-organisms such as bacteria,
microscopic algae or fungi. The metabolisms may lead to absorption or destruction of the
dissolved matter.
4.4.1 CARBONATE-CO2 SYSTEM

Determinations of the carbon isotopic composition (14C and 13C) (Sect.5.2.1.2 and 5.2.2.3;
Volume I), of the temperature and chemical conditions such as pH and alkalinity as well as a
knowledge of associated minerals and gases may allow to decipher the chemical reactions in
the carbonate systems, their mass and isotopic balance. Finely the groundwater age may be
determined by the 14C method (Sect.5.2.2.3; Volume I; Mook 1980; Clark and Fritz 1997).
This is not a simple and straightforward procedure. Gaseous and dissolved CO2, organic and
inorganic carbon constituents, individual minerals and the fossil organic matter (Sect.4.4.2)
involved in these reactions between groundwater and rock may have different isotopic
compositions. Moreover, chemical and isotopic equilibrium may not be approached in defined
closed or open system conditions.
The isotope composition of DIC of inorganic carbonate systems containing multiple sources
and sinks of carbon, and in which chemical and isotopic equilibrium prevails can be exactly
modelled applying the computer program NETPATH (Plummer et al. 1994). The preset of
these conditions occurs during groundwater recharge. Atmospheric precipitation infiltrates in
the soil, chemical and isotopic equilibrium is established between soil carbon dioxide,
dissolved carbonate species H2CO3, HCO3-, CO32- in water and marine carbonate in the soil.
Experimentally determined fractionation factors and thermodynamic equilibrium constants as
function of temperature are used (Chapter 6 and Volume I). Complications arise if magmatic
CO2, CO2 from fluid inclusions, organic CO2 and CH4 participates. Moreover, terrestrial and
hydrothermal carbonate minerals rather than marine carbonate may be components of the
carbonate-CO2 reaction in freshwater. Another complication of hydrochemical modelling
arises if carbonate formed by feldspar decomposition is involved (Vogel and Ehhalt 1963).
This carbonate is generated by atmospheric CO2 and contains 14C and an isotopic composition
of carbon considerably deviating from that of marine carbonate.
43
Chapter 4
Under the conditions just mentioned modelling is often not possible, due to the lack of
reliable data. The interpretation of the stable isotope data of carbon may, however, still allow
a qualitative evaluation of the constraints of water-rock interaction.
4.4.2 REACTIONS WITH ORGANIC MATTER

The chemical interaction of groundwater and organic matter has an important influence on the
carbon isotope composition of the dissolved inorganic carbon compounds in groundwater.
The main processes are
1) oxidation of organic matter, with the formation of CO2 and successive chemical reactions
with carbonate in the aquifer rock matrix, and
2) methane genesis.
The oxidation of organic matter (plant remains, coal, peat, lignite) may occur with the
dissolved oxygen of freshly recharged groundwater or by sulphate reduction. The CO2 –
HCO3− system behaves as a closed system, so that the δ13C and 14C values are changed.
Organic carbon in the soil or deeper underground is being oxidised according to
CH2O + O2 ⇔ CO2 + H2O (4.1)

This CO2 may dissolve carbonate increasing the concentration of dissolved carbon (CO2 and
HCO3−) by up to a factor of two through:
CO2 + CaCO3 + H2O ⇔ 2 HCO3− + Ca2+ (4.2)

Under organic matter containing soils fresh groundwater typically contains 12 to 24 mg C per
litre in the form of dissolved inorganic carbon (Volume I).
Sulphate reduction may occur according to
2 CH2O + SO42− ⇔ 2 CO2 + S2− + 2 H2O (4.3)

100 mg/L SO4 may form 91 mg/L CO2 corresponding to an maximum increase of bicarbonate
by a factor of 3. A detailed description of a quantitative evaluation of the isotope balance is
given in Volume I and in Clark and Fritz (1997).
In the first step oxidation increases DIC due to the formation of CO2 while HCO3− remains
constant. The 14C and δ13C values decrease and the 14C age increases. In the next step the CO2
concentrations decreases and DIC rises. The 14C value decreases while the 14C age and the
δ13C value increases (Fig.4.1). A detailed description of these processes is given in Volume I.
A correction scheme proposed in 1972 by Oeschger is a suitable solution for this problem.
The calculation of the 14C age is done by the product of the 14C activity and the DIC
concentration rather than by the 14C activity ). That means 14C activity per litre of water is
used rather than 14C activity per gram carbon.
The process of methane genesis from organic matter is more complicated. It follows the
44
reaction (Clark and Fritz 1997)
2 CH2O ⇔ CO2 + CH4 (4.4)

CO2 and methane are formed of which the latter may develop similar reactions as described
before. The concurrent shift in δ13C is large but rather uncertain, as there is a strong but
variable kinetic isotope fractionation involved. Usually the CO2 becomes isotopically
enriched in 13C which qualitatively allows the identification of this process.
Admixture of thermocatalytic, abiogenic or mantle fossil methane is often associated with the
admixture of fossil CO2. Gas will expel after exchange with the dissolved CO2, resulting in an
uncontrolled loss of 14C. In any case, methane is rarely found in resources of fresh
groundwater (Geyh & Künzl 1981).
δ13C
-12 12000 4
C age of DIC (yr BP)
DIC concentration (mmol/l)

calcite saturation Corg oxidation lime dissolution
-14 10000
3
-16 8000
14
C
δ13
-18 6000 C 2
DI
-20 4000
IC 1
ofD
-22 2000 e 2 CH2O +SO 2-
CO2 + H2O + CaCO3
ag
4
-
14 C H2S + 2 HCO3- Ca++(HCO3-)2
-24 0 0
1 2 3
reaction step
Fig.4.1 Simplified scheme of the changes of CO2 and HCO3- (DIC) concentrations as well as of
the 14C age and δ13C value during the hydrochemical reactions until calcite saturation of
the groundwater. Three reaction steps of the groundwater recharge, the oxidation of
organic matter and the succeeding approach of secondary calcite saturation has to be
distinguished (after Geyh and Kantor 1998).
4.4.3 FATE OF DISSOLVED SULPHUR COMPOUNDS

Sulphur is found in groundwater as sulphate anion, SO42-. Under reducing conditions such as
in peat bogs, organic bottom sediments, oilfield aquifers and in regions of active volcanism,
groundwater may also contain appreciable concentrations of sulphide (HS- or H2S).
45
Chapter 4
The most common sources of sulphur are the atmospheric wet and dry deposition of SO22- and
H2SO4, the admixture of seawater sulphate in seawater, oxidation of pyrite and other sulphide
minerals, the dissolution of gypsum, anhydrite and other sulphate salts in marine and
terrestrial evaporites, the introduction of sulphur from petroleum and coal, and finally the
infiltration of sulphate from surface water bodies. The isotopic composition of sulphur in
these sources, with the exception of seawater, varies in a wide range (Fig.4.2).
When sulphur from various natural and anthropogenic sources dissolves in cold groundwater,
no appreciable fractionation takes place unless dissolved sulphate is microbially reduced.
Through the isotopic composition dissolved sulphur can be used as a tracer for its origin.
Simple mixing concepts are sometimes sufficient to interpret the data (Schaefer and Usdowski
1992). In more complicated cases the dissolved sulphates are distinguished by the δ34S and
the corresponding δ18O(S04) values of the sulphate oxygen. The exchange of oxygen between
SO42- and H2O is extremely slow at the low temperature of groundwater (Chiba and Sakai
1985). Therefore, the isotopic composition of oxygen in sulphate reflects either mixing or
microbial reduction to sulphides.
meteorites
basic sills
volcanic rocks
sedimentary rocks
ocean today
evaporites
Pb-Zn deposits
H2S (Devonian, Alberta)
petroleum
air
surface water (SO42-)
coal
soil
-40 -20 0 +20 +40 ‰

δ34S
H2S, sulphides organic S sulphates, SO2
Fig.4.2 Sulphur isotope abundances in nature (after Krouse 1980)
Sulphur isotope fractionation is caused by various geochemical and biochemical processes

as the formation of evaporites, microbial reduction of sulphate ions to hydrogen sulphide,
inorganic oxidation of sulphide minerals and to a less extend by the adsorption of sulphate
ions on colloidal particles in aquifers and soils (Krouse 1980). Changes in δ34S caused by
those processes can be even several tens of per mill. Sulphide mineral that originate from the
released H2S have very negative δ34S. On the other hand, sulphate minerals originating from
the isotopically heavy residual sulphate ions have positive δ34S (Smejkal 1978).
46
‰
δ34S (SO4) +30
+25
4.9
+20
+15
anhydrite
4.0
+10
1.1
+5
rain
3.2
-5
0 +5 +10 +15 +20 ‰

δ O (SO4)
18
Fig.4.3 Change of both the δ34S and δ18O values of sulphate dissolved in groundwater from the
Bohemian Massive by mixing and microbial reduction of sulphides (data from Smejkal
and Jetel 1990).
Example
The plot of δ18O(S04) versus δ34S (Fig.4.3) represents the distribution of the δ34S of dissolved
groundwater in the Bohemian Massif of central Europe (Smejkal and Jetel 1990).
The data represent four different types of groundwater. There are groundwaters tapped by a
uranium mine, Vitkov II. The δ34S and δ18O(S04) values represent shallow groundwaters and
point to mixing between sulphate derived from oxidation of sulphide minerals (pyrite and
sfalerite) and sulphate in rainwater. The isotopically heaviest sulphur was found in Ca-Cl-SO4
brines tapped at a depth of 500 m in the mine. This brine was sampled twice in 1972 to 1980
and in 1986 to 1989, respectively. Sulphur and oxygen became isotopically enriched. This
47
Chapter 4
may be due to two stages of oxidation of reduced sulphur of volcanic origin which was
preserved as a fossil brine in a volcanic playa lake of Miocene age. The existence of this lake
was documented geologically, palaeontologically and by hydrochemical and isotopic data
(Paces 1987). The connection between the recent groundwater and the brine represented by
the line with a slope of 3.2 (Fig.4.3) is probably accidental. These two types of groundwater
probably do not mix and are not genetically related.
4.4.4 ON THE ISOTOPIC COMPOSITION OF STRONTIUM

Strontium isotopes (Sect.5.2.1.7) do not fractionate during dissolution, whereas biological
enrichment is not known. However, due to the low strontium concentration in groundwater,
water-rock interaction may approach isotopic equilibrium with respect to strontium. This
process can sometimes be quantified by comparing the 87Sr/86Sr values of the primary
minerals of the host rock, those of the secondary minerals on the surface of fractures, joints
and pores with those of the strontium constituents dissolved in the groundwater.
The strontium isotopic ratio 87Sr/86Sr in saline water and those of the associated rocks and
minerals from deep bore-holes and surface samples in the Precambrian Shield of Canada are
similar (McNutt 1987), indicating isotopic equilibrium. On the contrary, the 87Sr/86Sr ratio of
oil-field water found in sedimentary rocks differs from that of the host rock. This indicates
that this organic matter may not be old enough to permit the establishment of isotopic
equilibration.
Example
There is a wide range of values for the 87Sr/86Sr ratio of the granite minerals in the Stripa mine
in Sweden, of the local groundwater and of the hydrothermal minerals on the surface of the
fractures. The 87Sr/86Sr ratio reaches from 1.8958 to 0.74529 in microcline with plagioclase of
the host granite and in a fracture coating with quartz, microcline, plagioclase and chlorite,
respectively. The lowest value of 0.74056 is found for the shallow groundwater (Fritz et al.
1987). Since the isotopic ratio in seawater is 0.70906 and the Rb/Sr ratio (= 0.007) in ground-
water is half of the ratio of seawater (= 0.0145) the groundwater can be of meteoric rather
than oceanic origin. It reacted more intensively with the coating of the fractures than with the
minerals of the host rock. Knowledge of water-rock interactions on the surface of fractures is
important in a rock environment which is being considered as a potential site for radioactive
waste disposal.
48
5 APPLICATIONS TO
LOW-TEMPERATURE SYSTEMS
Applying environmental isotope methods we have to distinguish between low-temperature

(<90°C), medium-temperature (90<T<150°C) and high-temperature (>150°C) systems. In
low-temperature systems many reactions and processes changing the isotopic compositions
are too slow to have detectable effects. Low-temperature systems offer a wide field of appli-
cations in hydrogeology and hydrology:
• identification of the origin of groundwater and of its geogenic and anthropogenic con-
stituents (e.g. pollution),
• tracing hydrochemical processes in groundwater and mixing processes (leakage of aqui-

fers, mixing of groundwater with surface water from lakes or rivers (Volume III), brine,
ocean water), and
• groundwater dating for the study of groundwater movement (flow pattern).

There are different aspects to be considered for the unsaturated and saturated zones.
A detailed description of the sampling for the various kinds of isotopic analyses of various
kinds of water samples is given by Clark and Fritz (1997) and in Volume I.
5.1 UNSATURATED ZONE

Environmental isotope studies in the unsaturated zone have been carried out to obtain infor-
mation on special aspects of the hydrological cycle. Special attention has been given to iden-
tify:
• the groundwater recharge rate (applying tritium and stable isotopes),
• the rate of evaporation from soils and shallow groundwater (by means of hydrogen and
oxygen isotopic compositions), and
• the sources of the water used by plants.
5.1.1 PRINCIPAL SOIL PARAMETERS OF THE UNSATURATED ZONE

Three types of water are distinguished in the unsaturated zone:
1) mobile water (free water or gravity water), circulating through the macropores of the ma-
trix mainly subject to gravity. The drainage of such water corresponds to the state of the
49
Chapter 5
field capacity
2) retentive water or absorbed water remaining bound by capillary forces after drainage of
the mobile water. This binding is strongly linked to the soil matrix by electrostatic forces
and molecular attraction
3) constitutive water, an integrated part of the chemical compounds in the matrix and theo-
retically non-exchangeable, at least during the time of percolation. It resists a heating up
to about 105°C apart from gypsum for which dehydration begins at 60°C. Some of the
absorbed water in clay also resists heating above 105°C.
Qualitative parameters to describe the unsaturated zone and to investigate the movement of
soil water are based on the characteristics of the sediment matrix. The most important are
1) the texture describing the grain size distribution of the soil particles
2) the structure describing the construction on aggregates or isolated or cemented particles
3) the specific surface considers the phenomena of surface absorption of water and solutes;
it is defined as the total surface of the particles per unit of mass
4) the mineralogic composition of the soil.
5.1.2 GEOHYDRAULIC ASPECTS
5.1.2.1 STEADY-STATE FLOW

Steady-state mass balance models are fairly robust for the application to intermediate depths.
This is the part of the unsaturated zone below the depth where water flow in preferred path-
ways (Sect.5.1.2.2.3) and water uptake by roots affect the flux of tracers, and above the water
table where flow is no longer vertical.
Steady-state solute tracer techniques completely depend on the estimate of the solute flux in
the profile or region of interest. In many situations, however, redistribution of water and sol-
ute fluxes within the profile may cause uncertainties in this estimate. Surface runoff and hori-
zontal saturated flow perched on low-permeability layers in the profile may disturb the flux
into the deep profile. Vertical piston flow (water advances down the profile completely dis-
placing older water) can be described by the convection–dispersion equations of solute trans-
port. A particular situation arises in the unsaturated zone as the permeability and the hydraulic
charge are dependent on the moisture content.
Difficulties arise if the tracer distribution at any time does not represent the long-term average
conditions. In those cases water fluxes may be many orders of magnitude larger than the long-
term average (steady-state). Dispersive-diffusive fluxes of solutes are probably grossly under-
estimated if the long-term average water flux is used in those parts of the profile where du-
alflow pathways regulate the tracer flux.
50
Low-Temperature Systems
5.1.2.2 MOVEMENT OF SOLUTES

The conceptual model of mobile-immobile water has been used to encapsulate those proc-
esses in which one part of the water phase is relatively immobile compared to the other.
Hence, any solute which enters the immobile phase will cause the solute to be retarded rela-
tive to the water movement in the mobile phase. Processes that can be included in this model
are anion exclusion, mixing with water in dead end pores and aggregate dispersion
(Sect.5.1.2.2.2). The interaction between mobile and less mobile phases has been approxi-
mated by being proportional to the difference in the concentrations of the mobile and less mo-
bile phases. In the event of strong interaction, the concentrations of the two phases will be
equal, while for weak interaction there is virtually no time for mixing or exchange. A com-
plete mixing may be assumed of slowly moving groundwater with ages of more than 1000 yr.
This is why the total porosity is valid rather than the effective one (Sect.1.3.1; Eq.2.1).
An example of a secondary modification of the isotopic composition of water can be expected
by retardation/anion exclusion (Sect.4.1). Most clay surfaces are negatively charged. This
means that there is a certain volume of water near the clay surfaces in which there are few
anions. This water is generally considered to be immobile. Thus, there will be a difference in
the behaviour of isotopes of water. The isotopes of water will exchange with water molecules
in this excluded volume and hence will be retarded relative to the movement of the retentive
and bound water. Hence, the isotopic composition in the mobile phase will differ from that of
the mean soil water (Fig.5.1).
5.1.2.2.1 Convection and advection

An instantaneous injection of tracer, either isotopic or chemical, in a laminar steady-state flow
at point A at the starting time to (Fig.5.1) results in a peak displacement at a distance l (loca-
tion B) at the time t. The flux J between these points is the product of the tracer concentration
c multiplied by the mean tracer velocity vtrac
l⋅c
J = v trac ⋅ c =
t − t0
If the relative water volume (< field capacity) Φ, present in the profile, changes during the
movement of the water, the conservative equation becomes
∂J ∂ (Φ ⋅ c) ∂ ( v trac ⋅ c)
= = (5. 1)
∂t ∂t ∂z
5.1.2.2.2 Dispersion
There is always an attenuation of the breakthrough curve with time and distance due to dis-
persion (Fig.5.1). In that case the tracer velocity is obtained by the mean transit time t in-
stead of t. Dispersion by molecular diffusion, occurring even in a less mobile liquid, is pro-
51
Chapter 5
portional to the concentration gradient ∂c/∂z and is described by Fick's law

∂c
J = − D diff ⋅
∂z
where J is the vertical tracer flux and Ddiff [× 10-5 cm2 s-1] is the molecular diffusion coeffi-
cient. Ddiff depends on the nature and the concentration of the solution and soil type.
The kinematic dispersion is controlled by
1) differing velocities of water particles (Fig.5.1) in the same pore stream ranging from even
zero near the particle surface to the maximum in the middle of the canal,
2) different sizes of pores and canals, and
3) trajectories deviating from the main direction of flow due to the tortuosity. This means
that the actual velocity is higher than the mean tracer velocity.
main
main channel
concentration at B
fast
A B
fast channel
A
time
multiple channels
response to
concentration at B
individual channels
response at B
A
B
time
Fig.5.1 Scheme of tracer displacement by advection for dual flow as well as for multiple channels
demonstrating the effect of dispersion.
Considering both the convective and diffusive tracer transport and assuming that anion exclu-
sion, macropore flow and immobile water is negligible, we obtain instead of Eq.5.1.
∂c ∂c ∂ ∂c
Φ⋅ = − v trac ⋅ + (Φ ⋅ D diff ⋅ ) (5. 2)
∂t ∂z ∂z ∂z
The first and second terms on the right-hand side describe the convectional and the diffusive
transports, respectively.
52
5.1.2.2.3 By-pass flow (dual flow, marcopore flow)

Dual-flow pathways (dual porosity) are the routes of water flow and solute movement (Black
et al. 1983), arising from structures and discontinuities imbedded within the soil or aquifer
matrix. These highly permeable structures are of a much larger scale than the usual represen-
tative elementary volume, that is used to average processes at the microscopic pore scale and
to derive the continuum description of water and solute transport. The number of macropores
connected to the surface decreases with depth, so that the role of macropores generally dimi-
nishes with depth over the top 6 m. Root channels and the pedal structure of the materials
have been identified as important dual-flow pathways.
Macropores and other structures need to be in contact with a saturated zone or other source of
free water to act as preferred pathways. Therefore, perching layers in the profile or pounding
on the soil surface are necessary for preferred flow to occur.
A critical feature of dual-flow pathways is that they allow groundwater and solute to by-pass
the matrix of the soil or aquifer (dual flow) with little or no interaction (Fig.5.1). The dual-
porosity flow may be up to two orders of magnitude larger than that through the matrix. A
large proportion is discharged as interface flow. This reduces the groundwater recharge on the
one hand, and diminishes the influx of pollution from the surface on the other.
Flow of groundwater and solute in the profile is essentially multi-dimensional. The con-
vection–dispersion equations of solute transport for piston flow (Volume VI) do not longer
describe the tracer flux. This means that transient techniques which rely on measuring the rate
of displacement cannot be applied to such situations.
Dual-flow pathways can be identified by directly applying tracers that mark the flow path and
allow them to be visualised. However, the presence of non-piston flow processes can be infer-
red from discrepancies between travel times estimated from transient and steady-state tracer
techniques.
5.1.3 SOLUTE TRANSPORT

In principal there are two quantitative approaches to describe solute transport:
1) the tracer balance method and
2) the tracer peak-displacement method.
Tracer studies are done to determine recharge rates rather than water fluxes. They allow re-
charge estimates especially by means of isotopes via the long-term observation of the soil-
water flux. Classical techniques are dealing with much shorter time scales and are less sensi-
tive.
The choice of tracer depends on the time of the passage of the root zone. This time t can be
estimated by
53
Chapter 5
Φ
t = z⋅ (5. 3)
q rec
with z – depth of the root zone of around 1 m, Φ - volumetric water content (ca. 0.1) and
qrec - recharge rate. For qrec between 10 – 100 mm yr-1 the time of the necessary observation
becomes 1 – 10 years.
The choice of tracer depends on the likely range of recharge rates. For high recharge rates, in
which the time scale associated with leaching through the root zone (Eq.5.3) is less than one
year, an artificial tracer method is the most appropriate.
Soil tracer techniques usually involve soil sampling without the use of drilling fluids. In the
case of Auger sampling each soil sample is weighed, preferably at the site, and immediately
sealed in boxes or plastic bags and carefully labeled. The soil moisture is measured in the
laboratory with gravimetric methods on an aliquot of the soil. The tracer position is usually
detected by core sampling of interstitial water at different positions. If possible, comparative
measurements by a neutron probe are helpful. Granulometric, mineralogic and other para-
meters of the soil should also be determined.
For stable isotope analysis the soil moisture must be extracted quantitatively to avoid any iso-
topic fractionation (Sect.5.2.1.1; Volume I), though it is very time-consuming. Even only
some percent of water lost may falsify the isotopic composition. Azeotropic vacuum distilla-
tion of the soil samples with toluene is the most appropriate technique. Direct moisture extrac-
tion with ceramic cups or by suction probes are an alternative technique (Saxena and Dressie
1984). The soil water vapour is pumped through the probe, trapped in a molecular sieve, and
extracted in the laboratory by heating to 400°C in a vacuum system. Allison et al. (1987) also
tested a method to use soil CO2 instead. δ18O and δ2H are measured mass spectrometrically.
Complementary tritium (3H) measurements allow to differentiate between transport of the va-
pour (followed by 3H) and transport of the liquid phase (followed by stable isotopes). This
technique is especially useful for case studies in arid regions.
Vegetation has little impact on the isotopic composition of soil water. Apart from this, pore
water from different depth may be isotopically differently enriched due to a variable evapora-
tion during the year. In any case, for reliable estimates of the recharge rate, soil samples for
isotopic analysis should be taken from beneath the zone where water extraction by roots is oc-
curring.
5.1.4 APPLICATION
5.1.4.1 RECHARGE RATE DETERMINATION BY MASS BALANCE
The first estimation of groundwater recharge rates was done with a balance study of anthro-
pogenic 3H (Münnich 1983). The HETP model (Height Equivalent Theoretical Plates) was
54
developed for a better modelling of the 3H profile in the unsaturated zone. It is a simple one-
dimensional multi-box model which describes the unsaturated zone as a series of soil layers
with internally well-mixed soil water. The main parameter of this model is the layer thickness
on the theoretical height plate controlling the simulation of the longitudinal dispersion of the
tracer displacement. The initial water content is usually assumed to be constant and equal to
the field capacity along the soil profile. In numerical calculations admixing of new water is
assumed to be complete and instantaneous. The mixing balance is modelled for all boxes.
This model can predict tracer movement in the unsaturated zone under natural conditions
(Datta et al. 1973; Thoma et al. 1979).
Example:
Bomb 3H measurements (Thoma et al. 1979) of percolated water samples collected monthly
from a lysimeter showed that the 3H response is on average delayed by 5 months in a sand ly-
simeter and by 2.5 years in a loess-loam lysimeter. The HETP model, adapting a variable field
capacity, applied in combination with an evaporation/infiltration balance based on meteoro-
logical data showed good agreement between predicted and observed 3H concentration of the
percolated water.
5.1.4.2 RECHARGE RATE DETERMINATION BY TRACER PEAK DISPLACEMENT

The assumption of the piston-flow model is that the tracer and all water in the soil move si-
multaneously. The tracer peak at the position z and the time t is the integrated result of the
downward (infiltration) and upwards (evaporation) movement that occurred during the period
t - to (to - starting time). The amount of water stored in the soil section between z and zo repre-
sents the actual recharge (or the actual evaporation loss if z is above the initial position zo).
Although the piston-flow model is an oversimplification, it has been often successfully ap-
plied.
A complication may arise by common flow through dual-flow pathways (Sect.5.1.2.2.3).
Foster and Smith-Carrington (1980) determined the interstitial piston-flow rate by the position
of the bomb-tritium peak in the unsaturated chalk in various locations in England (Fig.5.2).
The low infiltration rate derived from the peak-displacement velocity is explained by an unde-
tected rapid bypass flow through macro fissures of the chalk.
In practice, groundwater recharge must have been very low and the unsaturated zone very
deep that the anthropogenic bomb-3H peak did not yet reach the saturated zone. Because the
time since the injection of bomb-tritium into the hydrosphere in 1963 is too long, it is unlikely
that a tritium peak can still be recognised in the unsaturated zone (Carmi and Gat 1992). Un-
der special conditions, the specific activity of bomb 14C (Ousmane et al. 1983) may deliver
valuable supplementary information to estimate the groundwater recharge rate, though possi-
ble water-rock interactions with the matrix (Sect.4.4) have to be taken into account.
55
Chapter 5
Example:
Dincer et al. (1974) determined the position of the 3H peak of 1963 in a drilled core from the
arid Dahna Sand Dune area, Saudi Arabia, and estimated a recharge rate of 23 mm yr-1. This
is relatively high compared to the annual rainfall of 60 – 70 mm in Riyadh. Further drilling at
the same location (Sonntag et al. 1980a) confirmed, however, this result applying an infiltra-
tion–evaporation model.
It was assumed that the tracer-displacement methods also can be applied to stable isotopes. In
temperate regions the stable isotopic composition of precipitation varies seasonally and may
serve as environmental tracer for changes of the infiltration rate during the year. Presupposi-
tion is that this variation is conserved within the unsaturated zone (Fig.5.3). Changes of the
isotopic composition can also be caused by infiltration of rainfall of different origin, by con-
densation, partial evaporation or partial freezing of soil water although isotope fractionation
during freezing is small.
H value (TU)
3
0 100 200 300 400 500 600

0
depth (m b.g.)
1968
5
1970
10 1977
15
20
Fig.5.2 Successive bomb-tritium displacement in the unsaturated zone (after Foster and Smith-
Carrington 1980).
56
Example:
Recharge studies have been most successful with seasonal changes of the stable isotopic com-
position when the recharge rate is relatively high (>200 mm yr-1; Saxena and Dressie 1984)
(Fig.5.3). This makes this technique most applicable for temperate humid areas. Infiltration
studies in the sand dunes of Pelat, Israel, also applied the seasonal variations of the δ18O val-
ues. The results were confirmed by the investigation of the natural 3H profile. A recharge rate
of 800 mm yr-1 through the dunes were found, almost the total amount of rainfall (Thoma et
al. 1979).
In arid and semi-arid regions the stable isotopic composition does usually not vary season-
ally, though precipitation with depleted heavy isotopes may enter after short, but heavy rain
events (amount effect; Volume I, Sect.5.2.1.1). Such rains more effectively contribute to
groundwater recharge than the many rain events of low intensity. Soil water evaporation dur-
ing the long dry season produces isotopically enriched pore water even below the evaporation
front. It was assumed that repeated downward displacement of the enriched peak during the
rainy season should lead to a sequence of heavy isotope peaks conserved in the unsaturated
zone (Sonntag et al. 1985). These peaks would represent a certain amount of water equivalent
to the recharge contribution of the individual years and should trace the groundwater move-
ment during infiltration after the rain events. Such peaks are, however, not found. Hence, the
stable isotopic composition of pore water has not been found to be a useful tracer of recharge
in dry regions.
-14 -13 -12 -11 -10 -9
depth (m b.g.)
0.6
1.2
1.8
2.4
3.0
3.6
4.2
4.8
Fig.5.3 Depth profile of the δ18O value of pore water. The annual change of the isotope composi-
tion allowed to estimate the recharge rate to approximately 260 mm yr-1 (after Saxena and
Dressie 1984).
57
Chapter 5
Allison et al. (1983a) showed that in areas of limited vegetation where transpiration is rela-
tively unimportant and where the rate of recharge is low (<10 mm yr-1), there is a linear rela-
tionship between the shift in isotopic composition from the meteoric water line (deuterium
excess) and the inverse of the square root of the recharge rate. This relationship has, however,
not yet been further tested (Fig.5.4). Limited field data pointed to agreement with this rela-
tionship.
20
diplacement of d in ‰ from MWL
16
12
0
0 0.2 0.4 0.6 0.8 1.0
1/recharge rate (mm-1/2)
Fig.5.4 Correlation between the displacement of the delta values from the Meteoric Water Line of
deep pore water and independent estimates of the recharge rate for four dune sites in
South Australia (Allison et al. 1983a).
Case study: Comparison - 3H balance and displacement methods

Sukhija and Shah (1976) found that 3H–peak displacement method gave drainage estimates 20
- 40% higher than the 3H mass balance method, at field sites in northern India. This suggests
either: a) that 3H fallout has consistently been overestimated, b) that 3H is being lost from the
soil profiles, or c) that too much water is being counted in the peak-displacement method. The
latter could be due to either i) the presence of immobile water, or ii) including water in the
plant root zone, which may not become drainage.
Example: 3H-peak displacement, 3H and chloride mass-balance methods
At recharge rates greater than approximately 20 mm yr-1 the results of the 3H mass-balance,
peak-displacement and chloride mass-balance studies, all appear to agree within 30 - 50%.
The results of peak-displacement methods using artificial 3H tagging also compare well with
those of the chloride mass-balance method. The comparison with corresponding piezometric
data showed qualitative agreement in the arid area of Botswana (Beekman et al. 1996).
58
5.1.4.3 EVAPORATION RATE

The isotopic compositions of oxygen and hydrogen in soil water of the unsaturated zone vary
mainly as a result of changes in the isotopic compositions of the rainfall and by evaporation.
Zimmermann et al. (1967) first showed that if sand saturated with water is subject to evapora-
tion, δ18O and δ2H values of the pore water decrease exponentially downwards from a maxi-
mum at the surface. Barnes and Allison (1988) presented their mathematical models describ-
ing the shape of the δ18O and δ2H profiles in saturated sand profiles for steady-state isother-
mal evaporation, under unsaturated, non-isothermal conditions and finally for non-steady state
evaporation. This includes the isotope effects of partial evaporation of pore water from dry
soil. The air temperature, the relative humidity and the isotopic composition of the atmos-
pheric moisture control the enrichment process of the heavy stable isotopes. Steady-state and
kinetic isotope fractionation contribute to both.
The soil profile is usually divided into two parts: in the upper shallow part down to the enrich-
ment peak (evaporating front) only vapour moves to the surface against the diffusive flux of
isotopically depleted atmospheric moisture. In the part below liquid transport is significant.
The δ values decrease approximately exponentially until the corresponding value of the
groundwater of the saturated zone is approached (Fig.5.5). Under steady-state conditions the
ascendant flux of moisture supplied by capillary rise equals the flux of water vapour lost by
evaporation. Hence, the isotopic composition of the vapour released into the atmosphere must
be the same as that of the evaporated groundwater in the saturated zone.
In the evaporation front (or dry–wet interface) liquid water is converted into vapour. It re-
mains at the same position below the soil surface. The isotopic composition at the evaporating
front deviates from that of the atmospheric moisture and that of the groundwater, and depends
on the following parameters:
1) temperature of the atmosphere (assumed to be equal to that of the water),
2) equilibrium fractionation between liquid and vapour,
3) the moisture deficit of the atmosphere,
4) the isotopic composition of the atmospheric vapour,
5) the kinetic fractionation in the dry soil layer above the evaporation front,
6) the isotopic composition of the reservoir water below the capillary fringe.
Above the evaporation front (eva) in the vapour transport region the delta value is given by
 z 
δ eva = α −1 δ atm + ε + [η ⋅ (1 + δ res ) + (δ res − δ atm ) ] ⋅ 
 z + H atm ⋅ z 
59
Chapter 5
with the subscript "res" for input groundwater (reservoir water), the diffusion ratio excess η =
(Dliq/Disot)n – 1 (n = 1 under steady-state conditions) with Dliq and Disot as diffusion coeffi-
cients of the water and that of the corresponding isotope, Hatm as relative humidity of the at-
mosphere with Hatm = 1 – zeva/z and zeva as the depth of the evaporation front (enrichment
peak) and the penetration depth z
ρ sat (n tot − Φ ) ⋅ τo ⋅ D vap

z=
ρ liq q eva
with Dvap as actual diffusity of water vapour in the air, ρliq as density of the water and qeva as
evaporation rate.
δ2H
-40 -20 0 +20 +40 +60 ‰
0
depth (m b.g.)
40
80 non-isothermal
isothermal
120 temperature profile
160
200
240
280
10 20 30 40 50
temperature (°C)
Fig.5.5 Comparison of theoretical isothermal and non-isothermal steady-state deuterium profiles

(after Barnes and Allison 1988).
60
Below the evaporation front where the upwards transfer of liquid is predominant, the heavy
isotopes become enriched by evaporation and diffuse downward into the liquid phase. This
results in an exponential relationship between isotopic composition and depth.
The δ values along the soil profile beneath the evaporation front are given after Barnes and
Allison (1983) by
ν
(δ 2 H − ∂ 2 H res )  (δ18 O − ∂ 18 O res ) 
= 
(δ18 O eva − ∂ 18 O res )  (δ18 O eva − ∂ 18 O res ) 
D( 2 H )
with ν= ≈ 1.
D(18 O)
D(2H) and D(18O) are the isotopic diffusities of the mentioned isotopes in the liquid phase.
Barnes and Allison (1984) showed that the effect of temperature on real isotope profiles was
reasonably small but could explain a secondary minimum in the profile which is often ob-
served in field situations. A possible explanation for this phenomenon is that under non-iso-
thermal conditions, the isotopically light water vapour produced at the drying front moves
both upwards and downwards in response to humidity and temperature gradients. The deple-
tion observed results from this vapour condensing beneath the drying front. In real soils often
an appreciable temperature gradient exists. It is caused by annual and diurnal surface tempera-
ture fluctuations.
The steady–state conditions of the isotopic profile are a final state after being wetted by infil-
tration from rainfall. In the first period water is freely available at the surface and the evapora-
tion rate is relatively constant. Subsequently, the evaporation rate will decrease. The cumula-
tive evaporation is inversely proportional to the square root of time (Eq.34 in Barnes et al.
1988). Walker et al. (1988) and Barnes and Walker (1989) modelled also non-steady state
conditions. This model is now capable of representing the most general case of water and iso-
tope movement through soils undergoing evaporation and infiltration of water. The character-
istic time t for the development of the steady-state profile is given by
D
t= 2
q eva
For extremely low evaporation rates qeva it results in millennia (Fontes et al. 1986), while at
evaporation rates of qeva = 10 mm d-1 a period as short as a day may be obtained. In the field,
especially in more temperate areas, profiles rarely reach steady state unless the water table is
quite near the surface. However, in more arid areas, if rainfall does not penetrate to significant
depth, this may be all lost by evaporation without disrupting the isotopic profile.
According to Barnes and Allison (1983) three methods exist for determining evaporation rates
using stable isotopes:
61
Chapter 5
1) interpretation of the zone of exponential decay beneath the evaporating front. The lim-
iting factor is the diffusivity of soil water which may exhibit a rather complex behaviour
a low water content
2) use of the position of the maximum in the isotope profile (depth of the evaporating front)
combined with the diffusivity of water vapour. This technique is best for low rates of
evaporation
3) use of the shape of the isotope profile in the region above the evaporating front. It is not
likely to be successful, as there are sampling and analytical problems associated with the
very low water contents usually encountered in this region.
These methods have the disadvantage of being point estimates and are subject to the natural
spatial heterogeneity of the area and the corresponding evaporation rates.
Allison (1982) has experimentally shown that the slope of the relationship between δ2H and
δ18O values can become as low as 2 for soil water in unsaturated sand subjected to evapora-
tion below a dry layer. This is considerably lower than the value of 4 to 5 obtained during
evaporation from a free water table. Barnes and Allison (1983) developed a model for predict-
ing the enrichment. The effect is explained in terms of an increased thickness of the laminar
layer through which evaporating water molecules escape. This work suggests for arid-zones
that groundwater replenished by local recharge, should be characterised by low δ18O – δ2H
slopes.
The slope of the lines is given by
δ 2 H init − δ 2 H ∞
s= (5. 4)
δ18 O init − δ18 O ∞
with δ∞ as
vap
vap atm q eva
ε + h ⋅δ + (1 − h )[η + (1 + )(1 + η) ⋅ δ res ]
∞ q eva
δ = vap
q eva
1+ ( ) ⋅ (1 − h ) ⋅ (1 + η) ⋅ ε vap
q eva
δinit and δres are the delta values of hydrogen and oxygen of the groundwater in the saturated
zone and of the feed water at different depth, respectively, and δatm the delta values of the at-
mospheric moisture. qeva is the evaporation rate at the evaporation front, ε is the isotopic equi-
librium fractionation. h the relative humidity of the free air and η the ratio of the diffusivities
of the isotopically heavy and light water vapour in the gas phase.
There is a relationship between the evaporation rate qeva and the slope s of the evaporation line
in the δ18O – δ2H plot as well as the thickness of the dry layer (Fig.5.6).
62
Whenever evaporation takes place, two types of fractionation give rise to enrichment of iso-
topes at the evaporating surface. These are:
1) the equilibrium effect due to small differences in the chemical potential between the iso-
topic species
2) the kinetic effect due to different rates of diffusion of the isotopic species in the vapour
phase. In this case both isotopic species behave in a similar fashion (Merlivat 1978).
1/evaporation rate (hr/mm)
30
)
98
0.
(r2 =
8)
1.
+
20 (d
62
1.
-1 =
e
10
0 5 10 15 20
thickness of mulch d (mm)
slope
4.5
4.0
3.5
3.0
0 0.10 0.20 0.30

evaporation rate e (mm/hr)
Fig.5.6 Upper part: Relationship between the evaporation rate qeva and the slope of the line in the
δ18O/δ2H plot (Eq.5.4). The solid line is calculated using the data shown. Lower part: Re-
lationship between the thickness of the dry layer and the inverse of the evaporation rate
(after Allison et al. 1983a).
63
Chapter 5
As the evaporating front moves further into the soil profile, the relative importance of the ki-
netic effect increases because of the development of a superficial dry layer where diffusive
transport of water vapour dominates, leading to a reduction in the slope of the δ2H / δ18O rela-
tionship (Eq.5.4; Allison et al. 1983a).
These results were confirmed by Sonntag et al. (1985) who found (Fig.5.7) that:
1) the slope of the δ18O / δ2H line increases with increasing humidity in the climate cham-
ber,
2) and with increasing grain size,
3) the slope of the evaporation line for grain sizes > 1 mm corresponds to that for open wa-
ter bodies.
‰
+80
+60
> 1 mm
+40 MWL
0.7-1.0 mm
0.5-0.7 mm
0
-10 +10 +20 ‰
<0.25 mm
δ 18O
+20
-60
-80
-80
Fig.5.7 Differing slopes of the evaporation lines in the δ18O / δ2H plot for sand of different grain
sizes. The pore water evaporated into dry air (after Sonntag et al. 1985).
Example:
Diffuse discharge is often an important component of the water balance of groundwater sys-
tems - for example, the aquifers beneath the Sahara (Aranyossy et al. 1991) and the Great Ar-
tesian Basin (GAB; Woods 1990). Such discharge may be an important component of the wa-
ter balance and may need to be evaluated to estimate the sustainable yield of some groundwa-
ter systems. Diffuse discharge from a part of the GAB was approximately four times the dis-
charge from springs , the generally accepted outflow points of this aquifer.
64
5.1.4.4 WATER LOSS BY PLANT EXTRACTION

Plant roots are not capable to produce isotope fractionation under saturated and unsaturated
conditions (Allison et al. 1983b; Zimmermann et al. 1967; Volume I). Stable isotopes provide
possibly the only way to determine the source of water used by vegetation in the field. The
isotopic composition of water in small twigs, for instance, is representative of that of the wa-
ter taken up by roots. Usually however the pore water has more positive delta values than
groundwater (Volume I, Sect.5.2.1.1).
Thornburn and Walker (1994) showed that mature Eucalyptus trees took up soil water from
deep rather than water which had infiltrated into the surface soil as a result of flooding, even
though the inundation lasted for several months. Both these data and those mentioned in the
preceding paragraph show that at least for mature vegetation roots must not approach the satu-
rated zone of groundwater.
A quantitative approach was attempted by Adar et al. (1995). He studied two Tamarisk trees
in Israel and surprisingly found that the ratio of the proportions of water drawn off from the
saturated and unsaturated zones remained remarkably similar during the dry and wet seasons,
though the total extraction rate changed by a factor of two.
5.2 SATURATED ZONE

There is a wide field of applications for environmental isotope techniques in the saturated
zone. The best source for corresponding studies are the proceedings of the numerous interna-
tional conferences on the application of isotope hydrological techniques organised by IAEA
since the early sixties (see Recommended Literature).
5.2.1 ORIGIN OF GROUNDWATER

The numerous applications of isotope hydrological methods applying stable isotopes encom-
pass the entire hydrosphere. One of the main fields of application is concerned with the origin
and mixing of groundwater and of its dissolved natural and anthropogenic constituents. Most
comprehensive information is obtained from stable isotope abundances. They can be meas-
ured quickly and cheaply and can be reliably interpreted as a largely conservative tracer (Gat
and Gonfiantini 1981; Volume I).
5.2.1.1 OXYGEN (18O/16O) AND HYDROGEN (2H/1H)

Physical Fundamentals
(See Volume I). The most abundant isotopes of oxygen, 16O (ca 99.7 %) and 18O (ca. 0.2 %),
and those of hydrogen, 1H and 2H (or deuterium; D), combine and produce water molecules of
differing molecular mass between 18 and 22, of which the most abundant are 1H216O,
1 2 16
H H O, and 1H218O. As constituents of the water molecules, they can act as conservative
65
Chapter 5
tracers. The natural atomic ratios are 2H/1H = 2R ≅ 1.5 x 10-4 and 18
O/16O = 18
R ≅ 2 x 10-3.
These ratios are expressed as delta values (Eq.2.1; Sect.2.3.1). Ocean water has δ18O and δ2H
values of ± 0‰, as V-SMOW (Standard Mean Ocean Water) has been chosen as the standard.
Most freshwaters have negative values.
Occurrence
Most cold groundwater resources are of meteoric origin (meteoric groundwater). There is a
strong relationship between the δ18O and δ2H values of precipitation reflected in the Meteoric
Water Line (MWL, Dansgaard 1964). The slope is 8 and the so–called deuterium excess is
+10‰ (Fig.5.8). The deuterium excess (d) is defined as
d excess = δ 2 H − 8 δ18 O
The deuterium excess (d excess) near the coast is smaller than +10‰ and approximately 0 ‰
only in Antarctica. In areas where, or during periods in which, the relative humidity immedi-
ately above the ocean is or was below the present mean value, d is greater than +10 ‰ (Mer-
livat and Jouzel 1979). An example is the deuterium excess of +22 ‰ in the eastern Mediter-
ranean (Gat and Carmi 1970). The value of d is primarily a function of the mean relative hu-
midity of the atmosphere above the ocean water (Merlivat and Jouzel 1979). The coefficient d
can therefore be regarded as a palaeoclimatic indicator.
Processes
Evaporation from surface water may cause the slope to be as low as 4. The slope can be as
low as 2 for soil water in the unsaturated zone (Sect.5.1.4.3). Thus, groundwater that has pre-
viously been subjected to evaporation can be identified on this basis.
There are deviations from the MWL indicating various processes of isotopic exchange and
fractionation. The best know examples are departures due to evaporation observed in brines
from sedimentary marine aquifers, exchange of oxygen between water molecules and silicate
minerals observed in geothermal systems with active exchange of oxygen between water
molecules and silicate minerals (Chapter 6), and mixing between meteoric groundwaters and
fossil residual brines in crystalline rocks (Fig.5.8).
The evaporation effect which results in an enrichment of the heavy isotopes in the liquid
phase with respect to the vapour phase allows to identify quantitatively the admixture of su-
perficial water as lake water and river water to groundwater (e.g. Darling et al. 1996). Water
balance studies of lakes have successfully been applied with a precision of less than ± 20 %
(Zuber 1983). In arid regions it is possible to estimate the evaporation rate through the unsatu-
rated zone (Sect.5.1.4.3).
Temperature effect: As water molecules with differing molecular mass have different vapour
pressure, the lighter isotopes will become enriched in the more volatile phase as opposed to
the less volatile phase during a change of phase (evaporation, condensation, sublimation).
This effect, known as isotope fractionation, is strongly temperature dependent (Volume I).
66
a δ 2H
H2S exchange
sil
sea water
ica
te
δ18O
hy
dr
at
io
n
groundwater
geothermal exchange
L with calcareous rocks
W L
l M W
a M
loc bal cla
glo y
de
hy
palaeowater dr
at
io
n
δ 2H
b
seawater
δ18O
groundwater A g
xin orat
ion
mi vap
e
ng
ixi
m
groundwater B
L
g
W
xin
M
al
mi
b
g lo
palaeowater
Fig.5.8 (a) Various processes which shift the δ18O and δ2H values from the MWL: evaporation
shifts both δ18O and δ2H values; the former are displaced as a result of isotopic exchange
with volcanic CO2 and limestone, the latter due to exchange with H2S and silicate hydra-
tion. (b) δ18O/δ2H plot for continental precipitation (MWL = Meteoric Water Line; local
corresponds to the Mediterranean precipitation) with examples of various mixing lines.
The MWL of Pleistocene palaeowater may be apart from the MWL.
The precipitation in winter is isotopically lighter than that of the summer (Fig.5.10). The tem-
perature coefficient of the δ18O value for continental precipitation is ≈ 0.7 ‰ per °C or less,
that of the δ2H value is about 5.6 ‰ per °C or less. In coastal areas, this gradient may be
much smaller, e.g. 0.2 ‰ per °C for δ18O (Gat and Gonfiantini 1981; Volume II).
67
Chapter 5
‰
δ18 O
-4
-5 mean
-6
-7
-8
-9
-10
-15
temperature (°C)
-11
-12 -10
-13 -5
-14 0
1964 1965 1966 1967 1968 1969 1964-1969
Fig.5.9 Seasonal variation of the δ18O value in precipitation at Groningen and the correlation of
the mean values with the mean monthly temperature (from Mook 1970).
The seasonal isotopic trend in precipitation may be approximated by a sine curve, which can
be observed in very young groundwater, albeit that the response is damped and phase-shifted.
This effect allows to estimate the mean residence time of shallow groundwater and of karst
water up to about 5 years according to the exponential model (Stichler and Herrmann 1983):
1 A in2
t= 2
−1
2π A out
where Ain and Aout are the amplitudes of the sinual δ18O trend of the precipitation and the dis-
charged water (water from a shallow well, spring), respectively. The phase shift of both
curves is maximum 3 months (Fig.5.10).
In tropical regions, a strong correlation exists between low δ18O and intensity of the rainfall
(amount effect), resulting in a seasonal variation of the δ18O values of the shallow groundwa-
ter.
The local and temporal variability of the isotopic compositions of hydrogen and oxygen in
precipitation (temperature effect, altitude effect) may be used to study even more complicated
hydrologic systems. This has been done to separate hydrograph of surface streams and run-
off into individual hydrological components of infiltrated groundwater (Mook et al. 1974;
Fritz et al 1976). Behrens et al. (1979) separated even four different components : base flow =
groundwater, snow meltwater, ice meltwater and longer retained glacier meltwater).
68
The temperature dependence of the isotopic composition for precipitation is preserved in fos-
sil groundwater of Pleistocene and Holocene age (Fig.5.11), recharged under different cli-
matic conditions. During the glacial period the precipitation was isotopically lighter because
of a lower temperature of about 5°C (Stute and Deak 1989). In Europe the δ18O values for
groundwater of these two periods differ by 1.5 to 2.0‰ (Bath et al. 1979). This can be used as
a first glance dating tool.
phase shift
0.6 input
amplitude
τ = 0,5 yr
0 τ = 5 yr
-.6
0 3 6 9 12 15 18 21 24
time (month)
Fig.5.10 Interrelationship between the amplitude of the seasonal change of the δ18O values of both
groundwater and precipitation as input and the mean residence time (MRT) according to
the exponential model. The phase shift rises up to three months with the MRT.
Altitude effect: As temperature usually decreases with increasing altitude, the delta values
will correspondingly drop. Gradients in δ18O of -0.15 to -0.40 ‰/100 m are observed (Gat
and Gonfiantini 1981; Fig.5.12), while -according to Eq.2.1 the gradients for δ2H are about
8 times larger. With the aid of the altitude effect recharge areas of spring water can be local-
ised. The elevation of the recharge areas for springs has been estimated from the orographic
δ18O gradient. It is important to note that the hydrogeologically estimated altitude of the
catchment is compared with the δ18O value of the corresponding spring water rather than the
altitude of the spring-discharge site. An estimate of the altitude effect in a certain region may
be misleading if δ18O values are used of precipitation and spring water from sites located far
from each other. The continental effect may truncate the altitude information (e.g. Kattan
1996a).
69
Chapter 5
Continental effect: On their track across a continent clouds produce rain; the heavier mole-
cules preferentially enter the condensed phase. The δ18O and δ2H correspondingly decrease
towards the interior. Complex isotopic patterns are established (Sonntag et al. 1980b), that re-
flect the morphology of the landscape and the pathways of cyclones. Present-day precipitation
and palaeowater are isotopically different (Fig.5.13), insofar as the climatic situation has
changed (Stute and Deak 1989).
‰
δ18O
-8.5
-8.0
-8.5
groundwater recharge
period without
-9.0 Pleistocene Holocene
-9.5
-10.0
40,000 30,000 20,000 10,000 0
reservoir-corrected C age of DIC (yr BP)
14
Fig.5.11 Deviating of δ18O values of Pleistocene and Holocene groundwaters in southern England
(after Bath et al. 1979).
By the continental effect, diffuse direct recharge of groundwater is distinguished from

groundwater recharged in restricted recharge areas. In the Sahara Desert diffuse recharge is
reflected), while groundwater recharge in the Great Artesian Basin of Australia is restricted to
the mountain range in the east (Calf and Habermehl 1984).
Meteorological studies: Stable isotope analysis of precipitation and humidity has provided
information on their spatial and temporal distribution, their origin, and the trajectories of wa-
ter vapour in the troposphere (Hübner et al. 1979). Such information has also been obtained
for the past (Rozanski 1985; Volume II).
70
δ18O ‰
-9.0
-8.0
-7.0
hydrogeologically assumed
altitude of the catchment area
confirmed
not confirmed
-6.0 spring site
0 500 1000 1500 2000 2500

altitude [m a.s.l.]
Fig.5.12 Altitude effect in the Antilebanon Mountains, Syria. The altitude of the discharge sites is
lower than that of the corresponding recharge area. In several cases the geologically as-
sumed recharge area had to be revised.
Mixing studies: Groundwater is usually a mixture of two or more genetically and chemically
distinct groundwater components, often of different age. Isotopic combined with hydrochemi-
cal analyses (preferentially with conservative tracers as chloride or the bromide/chloride ratio)
allow to distinguish between different kinds of groundwater and often to set up a mixing bal-
ance (Fig.2.3). Two- or three-component models are applied for obtaining rough estimates. In
the case of time series more complex models can be applied (Zuber 1986; Maloszewski and
Zuber 1993, 1996, 1998).
During pumping tests occasionally the question arises whether or not groundwater bodies,
separated by a horizontal aquitard, are connected via "windows", in other words, whether
leakage plays a role. This question can be answered if the groundwaters in the aquifers have
different δ18O values and are hydrochemically distinct (Bertleff et al. 1985).
The admixture of surface water (dam, lake) to the groundwater (Volume III) was studied on
river alluvions in Cyprus. The isotope signal was provided by isotopically enriched water be-
71
Chapter 5
hind a dam released once a year. The movement of this signal (Fig.5.14) was used to deter-
mine the tracer velocity in this valley and the extension of the artificial discharge (Plöthner
and Geyh 1991).
Leakage from a water pipeline into a local urban aquifer was traced by means of the oxygen
and hydrogen isotopic compositions (Butler and Verhagen 1997).
-60
-50
-20 -40
-30
-50 -60 -70 -80
-30 -40 Ca r p
at h
ALPS -70
ia
Pyren ns
e es -80
-20 -60
-35 -40 -40
-35 -70 -80
-20 -30
-40
-40
ATLAS -40
-20 -20
-20
-30 -70 -80
-40 -50
-60
-85
Fig.5.13 Isolines of equal δ2H values of Holocene groundwater in Europe and those of Pleistocene
groundwater in North Africa. The isotope pattern reflects direct recharge of groundwater
by local rain storms approaching from the Atlantic Ocean (after Sonntag et al. 1980b).
The source of salination of brackish to highly mineralised groundwater and thermal water
can be definitely detected by a δ18O/Cl- plot. Processes as dissolution and leaching of salt, en-
richment by evaporation or mixing of fresh water with saline water or seawater can be clearly
and quantitatively distinguished (Fig.5.15).
5.2.1.2 CARBON (13C/12C)
Physical fundamentals
The stable isotopes of carbon, 13C and 12C, have an average ratio of about 1 : 100. The actual
number plays an important role in quantifying the water-rock interaction for 14C age correc-
tion (Sect.4.4.1; Volume I). Moreover, it allows to identify the sources of CO2 involved in the
carbonate–CO2 system.
72
12.4 m/d 2 .4 m /d 1.8 m /d

δ18O ‰
-3.0
October 1984
May 1985
October 1985
-3.5
-4.0
flow direction
-4.5
0 500 1000 1500 2000 2500 3000

distance from outlet [m]
Fig.5.14 Groundwater movement from an superficial reservoir in a valley of Cyprus (after Plöth-
ner and Geyh 1991) and estimation of the tracer velocity by tracing the δ18O shift of
evaporated dam water.
salinity
a t io n
xi ng
mi
evapor
stable isotope composition
dissolution
leaching
Fig.5.15 Stable isotope composition vs. salinity for the identification of different salination proc-
esses: mixing (gray circles) of fresh (open circles) and mineralised water (black circles),
dissolution of salt and leaching (open squares), and evaporation (open triangles).
CO2 assimilation causes considerable carbon isotope fractionation. Isotope fractionation proc-
esses are also relevant for studying the carbonic acid and calcite system in water. The δ13C
73
Chapter 5
values of CO2 originating from C3 and C4 vegetation differs by 12‰.
Occurrence
The isotopic composition of carbon in the dissolved carbon constituents of groundwater is
very variable. The sources of carbon dissolved in groundwater are soil CO2, CO2 of geogenic
origin or from magmatic CO2 (from deep crustal or mantle sources) or in fluid inclusions, liv-
ing and dead organic matter in soils and rocks, methane, and carbonate minerals. Each of
these sources has a different carbon isotopic composition and contributes to total dissolved
carbon in various proportions. Therefore, the isotopic composition of dissolved inorganic car-
bon compounds in groundwater has a wide range of δ13C values. Soil carbon dioxide usually
has a value of about -22‰, in tropical soils it may be more positive to about -11‰. Carbon
dioxide of an endogenous or magmatic origin has δ13C values of about -6‰, metamorphic
carbon from sedimentary rocks is usually close to zero if it is derived from marine carbonates.
The organic carbon of terrestrial plants has δ13C values between -30 and -20‰. The heaviest
carbon isotopic composition is found in evaporate carbonates with +10‰. Such carbonates
occur sedimentary basins where the δ13C values of DIC of fresh groundwater might have ele-
vated δ13C values (Volume I).
Applications
Measurement of the abundance ratio of the stable carbon isotopes, 13C/12C is indispensable for
14
C dating of groundwater (Vogel and Ehhalt 1963). The δ13C values reflect chemical interac-
tion with the aquifer rock. This has to be taken into account when interpreting 14C values
(Sect.5.2.2.3; Volume I). A prerequisite is that the reactions are restricted to CO2 from the top
soil and the lime in the unsaturated zone. Open and closed systems have to be distinguished
(Fontes 1992).
14
Numerous hydrochemical models have been developed in order to determine the initial C
value Cinit (Eq.2. 2) based on the δ13C value of DIC needed to calibrate the 14C time scale for
groundwater (Mook 1980). The NETPATH model (Plummer et al. 1994) includes the whole
chemistry of the groundwater and delivers the most reliable absolute water ages (e.g. Phillips
et al. 1989; Geyh 1992). Its application is, however, limited as only results of water samples
from the same flow path can be used. Whatever model is used the correction of the 14C water
ages by the δ13C values of DIC introduces large uncertainties (Sect.5.2.2.3).
14
Although theoretically not appropriate the most often used correction procedure of the C
13
value using the δ C value has been introduced by Gonfiantini (Salem et al. 1980):
A init ≈
(δ 13
C DIC − δ13 C lim e ) × 100 pMC (5.5)
13 13
δ C CO 2 − δ C lim e + ε CO 2 −lim e
It takes into account the mixture of soil CO2 and soil lime and the isotopic difference between
CO2 and CaCO3. Closed system conditions are assumed.
74
Geyh and Michel (1982) applied the δ13C values of DIC from groundwater to distinguish be-
tween groundwater recharged in a sandstone aquifer from that of a limestone aquifer
(Fig.5.16). The δ13C value of the groundwater in the sandstone aquifer is commonly more
negative.
14C value (pMC)
40 50 60 70 80 90 100 110
‰
δ13 C
-12
-13
-14
-15
-16
-17 karst water

karst water to be identified
-18
sandstone water
-19
Fig.5.16 Distinction of groundwater pumped from a sandstone and a limestone aquifer in Höxter,
Germany, by the corresponding δ13C and 14C values of DIC (after Geyh and Michel 1982)
and identification of the used groundwater as karst water.
5.2.1.3 NITROGEN (15N/14N)
In nature there are two stable nitrogen isotopes: 14N (≈ 99.6%) and 15N (≈ 0.36%). δ15N values
are referred to air nitrogen as standard (Eq.2.1).
Occurrence
The nitrogen and oxygen isotopic compositions of the three most important nitrogen com-
pounds are summarised in Table 5.1. Nitrogen in groundwater may be from atmospheric ori-
gin and from wet and dry pollution (N2 and NOx pollution), from mineral fertilisers, and from
living and dead organic matter (animal waste and domestic sewage). Water-rock interaction is
usually not involved in the biogeochemical cycle of nitrogen.
Processes
Important microbial processes are nitrification, denitrification, biological fixation and miner-
alisation of organic nitrogen. Because of the complexity of the biogeochemical nitrogen cycle,
75
Chapter 5
a quantitative interpretation of δ15N(NO3), δ18O(NO3) and δ15N(NH4) is rarely possible. It is

always difficult to relate the isotopic composition of nitrate in groundwater to atmospheric
and agricultural inputs without considering nitrification and denitrification processes as well
as mixing of nitrates and ammonium from soil and atmospheric sources. Fig.5.17 shows that
the nitrogen isotopic composition of the nitrate dissolved in groundwater frequently is similar
to that of soil nitrogen rather than with that of fertilisers (δ15N(NO3) < 2.5‰) or of animal and
domestic wastes. Nitrate from fertilisers is consumed by soil biota and isotopically enriched in
15
N (δ15N(NO3) > +5‰). On the other hand, nitrate resulting from nitrification of animal and
domestic wastes is isotopically heavier (δ15N(NO3) > +9‰).
There are three fundamental processes which control the isotopic composition of nitrogen
compounds: isotopic equilibrium fractionation, kinetic fractionation and mixing.
Isotopic equilibrium fractionation controls dissolution of ammonium. Reversible reaction
NH3(gas) + H+ = NH4+ has a isotopic fractionation factor ε(ΝΗ4 − ΝΗ3) of 25 and 35‰
(Mariotti 1984) while the irreversible dissolution of ammonia in water has a negative isotopic
fractionation factor (Freyer 1978).
Kinetic isotope fractionation is not important in fixation of organic nitrogen. Bacterial denitri-
fication (NO3- to N2) fractionates isotopes substantially (ε(N2 - NO3) ≈ -25 to -35‰; Heaton
1986) and can be described by the Rayleigh distillation equation for an open system. The re-
sidual nitrate has a larger δ15N(NO3) value than the initial component. Soil mineralization of
organic nitrogen to nitrate ions proceeds in steps via ammonium and nitrite ions. The overall
isotopic fractionation factor ε(NO3 - Norg) of this complex reaction is between 0 and –35‰,
depending on which of the reaction steps is rate controlling (Heaton 1984, 1986).
Mixing of groundwater with different sources of nitrate can be detected by the δ15N(NO3)
versus δ18O(NO3) plot manifested in straight mixing line between the two end-members. A
hyperbolic function is obtained in the plot of δ15N(NO3) versus the concentration of NO3
(Mariotti 1984). The hypothetical relationships are shown in Fig.5.18 (Heaton 1986). There is
no simple trend other than complex mixing of various sources and microbial denitrification.
The isotope fractionation of nitrogen in soil ammonium is controlled by nitrification, dilution
with atmospheric ammonium and adsorption-desorption processes in the soil-water system
(Fig.5.19, Buzek et al. 1998). Exchangeable ammonium ions in soil are nitrified during which
δ15N(NH4+) increases (fractionation factor ε(NO3− - NH4+) ≈ -10 to -24‰).
The residual ammonium is isotopically diluted by lighter atmospheric ammonium
(δ15N(NH4+) between -12 and 3‰). Since the concentration of adsorbed soil ammonium is
low after denitrification, the δ15N(NH4+) in the residual ammonium drops to negative values
due to the admixture of isotopically lighter atmospheric nitrogen.
76
Table 5.1 Isotope abundances of nitrogen compounds depending on their origin. δ15N values as AIR
standard, δ18O values as SMOW standard. Sources: O2: δ18O = +23.5‰, H2O: δ18O
= −10.5‰, N2: δ15N = 0‰.
Molecule Origin δ15N δ15N δ18O δ18O

expected measured expected measured
N2 Air 0‰ 0‰
Denitrification −3 to +15‰c −5 to +2‰
NOx emission −5 to +5‰
bound N organic soil matter +4 to +9‰
particulate matter in rivers 0 to +3‰
NO3- tech. synth. fertiliser 0‰ −5 to +7‰ +18 ± 2‰a +17 to 23‰
nitrification <−10 – −30 to +10‰ 1‰b −1.5‰
rainwater +10‰ −12 to +2‰ >+23.5‰ +50 to 60‰
surface water 0‰ −4 to +15‰
groundwater +1 to +15‰
animal waste and sewage −4 to +5‰
N20 denitrification/nitrification >0‰ >>0‰ +36 to +5‰
>0‰ 0 to +2‰ +22‰
NH4 rain −15 to 0‰
fertiliser −4 to +5‰
a
) Calculated on the base of: N2 +2.5 x O2 + H2O → 2 HNO3−; b) Basing on H2O as the main oxygen
source; c) Assuming a shift of 18‰ relative to the original NO3−.
Application
Combined isotope analyses of nitrogen and oxygen in NO3− leaves fingerprints on natural and
anthropogenic sources of nitrate, on the microbial denitrification, nitrification and biological
fixation processes and the nitrogen budget in the groundwater (Volume I; Heaton 1986; Böt-
tcher et al. 1990; Aravena et al. 1996). Therefore, the δ15N values of the dissolved nitrates,
ammonium and organic nitrogen in soil water are well distinguished from one region to an-
other one (Fig.5.19).
The isotopic composition of nitrates which percolate to groundwater is the result of complex
processes. Therefore, it is difficult to relate the isotopic composition of the various nitrogen
compounds in groundwater to atmospheric and agricultural inputs without considering the
isotope fractionation caused by nitrification and denitrification processes as well as mixing of
nitrates and ammonium from soil and atmospheric sources.
77
Chapter 5
fertilisers soils animal sewage and waste
NO3- (mg/l N)
200
Kalahari (D)
100
a
50 an
Springbok w
a ts
flats
u th
ph
Ne
Bo
br
20
as
ka
Kalahari (C)
10
Br
Brie (B)
ie -
Be
5
au
(F)
ce
(A
)
2
(E)
1
0 +5 +10 +15 ‰
δ15N
Fig.5.17 Differentiation of various sources of nitrate by its δ15N(NO3) value and its concentration
in groundwater (after Heaton 1986).
15
Fig.5.18 Hypothetical relationship between the δ N value and the concentration of dissolved ni-
‰
δ14N
+15
fertilizer nitrate
soil nitrate during denitrification
end mem ber
+10
A X
ε
=
ε=
-3
-1 0
0
+5 ‰
‰
C
m ixing of soil and
fertilizer nitrate
B Y
0
high concentration
soil nitrate during
m ineralization fertilizer nitrate
end mem ber
-5
0 10 20 30 40
NO 3 (m g/L N)
trate derived from soil and fertilisers (after Mariotti 1984). Solid bars (X and Y) represent
soil and fertiliser mixing end members. The grey area shows the effect of mixing. The
broken lines were calculated and stand for the fractionation during denitrification of fer-
tiliser nitrate (ε(N2 - NO3–) = –30 and –10‰ with the initial point Y) and due to minerali-
zation of soil organic nitrogen (line X – C using ε(NO3– - Norg) = –30‰). A, B, C are hy-
pothetical isotopic compositions of nitrate resulting from mixing and/or nitrogen miner-
alisation (after Heaton 1986).
78
‰
δ15N(NH4) 30
0 - 5 cm
25
0 - 10 cm
2
20 15 cm
15 - 30 cm
15
40 cm
10 3 40 - 85 cm
5
1
-5
0 5 10 15
NH4+ concentration (mg N/500 g of soil)
Fig.5.19 Change of the isotopic composition of ammonium ions in subsurface water as a result of
mixing and denitrification during the downwards passage (1 – 2 – 3) in a forest soil (after
Buzek et al. 1998).
5.2.1.4 SULPHUR (34S/32S)

Sulphur has four stable isotopes: 32S (95.02 %), 33S (0.75 %), 34S (4.21 %), and 36S (0.02 %).
The abundance ratio of 34S and 32S is generally given as a δ34S value, defined analogously to
Eq.2.1. Iron sulphide from the troilite phase of the Diablo Canyon iron meteorite (DCT) (with
a 32S/34S ratio of 22.220) is conventionally used as standard (Volume I).
Occurrence
There are three main reservoirs of sulphur: evaporite sulphate (with δ34S values of +10 to
+30‰, mean +17‰), dissolved sulphate in ocean water (δ34S value of +21‰), balanced by
the largest of the three, the sedimentary sulphides (roughly -12‰). In recent and fossil vol-
canic systems the sources of sulphur are magmatic volatiles. Organic sulphur plays usually a
minor role in common groundwater. The isotopic composition of most important sources of
sulphur is illustrated in Fig.5.20 (Fritz et al. 1994).
During the course of the Earth's history, the δ34S value of the world's oceans, and conse-
quently, of marine evaporite sulphate has varied between +10 ‰ (Permian) and +35‰ (Cam-
brian) (Fig.5.21). Sulphur and carbon isotope fractionation (δ34S and δ13C values) appears to
correlate inversely with one another in the long term.
79
Chapter 5
‰
δ34S(SO4)
30 early
Paleozoic
modern marine SO4
20 Tertiary
magmatic and Cenozoic

hydrothermal SO4
Devonian to
10 Lower Triassic
0 atmospheric SO4
terrestrial evaporites
-10
-10 -5 0 5 10 15 20 ‰
δ18O(SO4)
Fig.5.20 Ranges of δ34S and δ18O values of sulphates of various origin dissolved in groundwater
(after Clark and Fritz 1997).
Groundwater contains dissolved sulphate ions in concentrations from few mg/L in shallow
subsurface waters to tenths of a g/L in fossil brines. These sulphur sources can be divided in
atmospheric contribution, mineral or rock contribution, marine and playa lake sources, vol-
canic sources and biological contributions. Atmospheric contribution includes atmospheric
wet precipitation (H2SO4), atmospheric dry deposition (SO2) and sea-spray aerosols. Mineral
contribution contains recent and fossil evaporite sulphates (gypsum and anhydrite), barite in
veins and fracture fillings in rocks, pyrite and other sulphidic minerals. Their isotopic compo-
sitions expressed in δ34SCDT(SO4) and δ18OSMOW(SO4) are important characteristics when ori-
gin of water and sulphates are discussed.
80
-δ34S δ13C 87Sr/86Sr

Myr Era Period +10 -+20 +30 ‰ -2 0 +2 +4‰ .707 .708 .709
Cenozoic
100 Cretaceous
Mesozoic
Jura
200 Triassic
Permian
300 Pennsylvanian
Missippian
Paleozoic Devonian
400
Silurian
Ordovician
500
Cambrian
600
Pre-
Cambrian
700
Fig.5.21 Composite δ34S curve for sulphate of marine evaporites (after Claypool et al. 1980) and
corresponding δ13C values, as well as 87Sr/86Sr values from carbonate and apatite in ma-
rine sediments (after Holser et al. 1986).
The isotopic composition of the sulphate of atmospheric origin is determined today either by
sea-water spray near cost lines or by the composition of sulphur in burned fossil fuels. δ34S in
oil, natural gas and coal is mostly between −5 and +10‰ while marine sulphur has uniform
δ34S of +21‰. Isotopic composition of oxygen in atmospheric sulphate is a result of mixing
of molecular oxygen in atmosphere (δ18O = +23.5‰), oxygen in water molecules (δ18O is
negative and oriented to the meteoric water line) and marine sulphate (δ18O ≈ +9.5‰). A
complex oxidation of SO2(g) to SO42- may be accompanied by a low oxygen isotopic frac-
tionation. In accordance with the tree sources, δ18O(SO4) in atmospheric sulphates usually
varies from slightly negative values to +10‰ (see also Volume I).
Processes
Stable isotope ratios of sulphate are strongly affected by isotopic fractionation caused by mi-
crobial activity as well as water-rock interactions (Chapter 4).
During complex geochemical and biochemical transformations of sulphate, fractionation pro-
cesses affect the stable isotopic compositions of sulphur (34S/32S) and oxygen (18O/16O).
These processes are: sulphur reduction and oxidation, crystallisation of sulphate minerals
and adsorption of sulphate ions in sediments. The relatively low temperature of groundwater
prevents most of the isotopic fractionation processes to reach isotopic equilibrium and signifi-
81
Chapter 5
cant isotopic exchange of oxygen between SO42- and H2O.

The trends in the isotopic shift due to the fractionation are illustrated in Fig.5.22 (Krause
1987).
Sulphate and H2S formed through oxidation of sulphides or bacterial reduction, respectively,
are isotopically significantly lighter at about +10 ‰. The most effective isotopic fractionation
is caused by microbial reduction of dissolved sulphate to sulphide. The fractionation factor
ε(SO4/H2S) is about +30‰. After major bacterial decomposition to H2S, the residual sulphate
remaining has δ34S values is often far above +20‰.
Terrestrial sulphate as well as sulphate in atmospheric precipitation have δ34S(SO4) <+10‰

and δ18O(SO4) <+4‰. Microbial reduction of sulphate enriches both the residual sulphur and
oxygen with their heavier isotopes. The shift due to the microbial reduction has a slope of
δ 34 S(SO 4 ) residual − δ 34 S(SO 4 ) initial

2< <4
δ18 O(SO 4 ) residual − δ18 O(SO 4 ) initial
in the plot of δ34S(SO4) vs. δ18O(SO4) (IAEA 1987). Newly formed sulphide has δ34S(SO4) <
7‰. Oxidation of sulphide yields sulphate with δ18O larger than that of the oxygen in water
molecules by +4 to +20‰. (Taylor et al. 1984). This reflects the mixing of isotopically light
oxygen in water molecules (δ18O <0‰) and isotopically heavier atmospheric oxygen (δ18O ≈
+23.5‰). During biological oxidation of sulphidic minerals 32S reacts faster and this lowers
δ34S(SO4) by +2 to +5.5‰ (Toran and Harris 1989).
Crystallisation of gypsum favours heavier isotopes of S and O in the precipitate. In oil field
waters the reduction of sulphate by methane and other hydrocarbons will also lead to isotopic
fractionation.
Sulphate in groundwater is diluted by precipitation and removed by crystallisation of
evaporite sulphate minerals, by microbial reduction to volatile or dissolved hydrogen sul-
phide, COS, CS2 or sulphidic amorphous precipitates and minerals. Fine-grained soils and
sediment particles adsorb small quantities of sulphate ions, while vegetation takes up sulphur
as a indispensable nutrient.
Mixing of groundwater with modern seawater, with brines of playa lakes and with fossil for-
mation water, modifies the isotopic composition of sulphate along the lines between the end
members of mixing.
The dissolution of evaporite minerals does not change the isotopic signature. However, sul-
phate reduction may occur and exclude the application of simple mixing models to explain
precisely the observed sulphate isotopic composition.
82
δ34S(SO4)
20
reduction, slope ~ 4
10
adsorption, slope ~ 1.4 ?
0
crystallization, slope ~ 0.5
-10
-5 0 5 10 15 20 ‰
δ O (SO4)
18
Fig.5.22 Trends in the isotopic shift of sulphur and oxygen due to the most important fractionation
mechanisms occurring in nature (after Krause 1987).
Mixing of recent and fossil sea water or fossil playa-lake brines is difficult to interpret, though
the isotopic composition of the recent seawater end-member is well defined (δ34S(SO4) =
+21‰; δ18O(SO4) = +9.5‰). The isotopic composition of fossil seawater depends upon the
complex geological history of the marine sulphate (Fig.5.22).
Application
The isotopic composition of sulphur and oxygen in sulphates helps to differentiate between
marine, evaporitic and volcanic sources of dissolved sulphate (Krouse 1980; Pearson and
Rightmire 1980) and to elucidate its fate in the groundwater. The variety of possible sources
of dissolved sulphates, complex fractionation mechanisms, non–equilibrium state and uncer-
tainties about the degree of openness of the groundwater systems make, however, the interpre-
tation of isotopic composition of the sulphate and the bound oxygen a difficult task.
Example:
The isotopic composition of sulphates in groundwater and its evolution is demonstrated by a
brief discussion of three groundwater systems.
Case study 1: Simple mixing
A simple mixing with negligible fractionation is indicated by groundwater from Zechstein
sediments in the Harz mountain in Germany (Schaefer and Usdowski 1992). Four springs
(FOR 1 to FOR 4) were sampled and δ34S(SO4) measured in the sulphate ions as well as in
83
Chapter 5
gypsum and anhydrite of the associated sedimentary rocks. The evaporites showed a very nar-
row range of δ34S(SO4) values from +9.9 to +12.4‰. Sulphate ions in three of the springs
(FOR 1 to FOR 3) have their isotopic compositions within the limits of the minerals (+10.6 to
+11.6‰) indicating that the dissolved sulphate originates from the rock. On the other hand,
δ34S(SO4) in spring FOR 4 is less positive (+8.3‰), indicating a mixing with sulphate from
an isotopically lighter source. An obvious choice is the mixing with local rain water and snow
melt with δ34S(SO4) equal to +4.5‰. Using those values of δ34S(SO4), the mixing proportions
of the atmospheric and evaporite components in sulphates of the spring FOR 4 are estimated
to be 46 and 54%, respectively.
Case study 2: Mixing of sulphates of different origin and process interference

The isotopic composition of sulphur of the groundwater from the Permo-carboniferous and
crystalline basement of Cretaceous basin in the Bohemian Massif (Central Europe) reflects a
complex fate of the sulphate. The relationship between δ34S(SO4) and δ18O(SO4) is shown in
Fig.5.23. Chloride brines with a low and an elevated concentration of sulphate from the base-
ment of the Cretaceous basin were analysed (Smejkal and Jetel 1990). The data points of the
brines with high sulphate concentration are located along the line between local rain and gyp-
sum and may be interpreted as dissolution of local evaporites. The water of the brines is of
meteoric origin according to the δ2H and δ18O values.
‰
δ34S(SO4)
gypsum in sediments
+30
brines with high SO4
brines with low SO4
+25
+20
+15
+10
+5
rain
-5
0 +5 +10 +15 +20 ‰
δ O(SO4)
18
Fig.5.23 The line connecting the δ34S(SO4) and δ18O(SO4) values indicates mixing of rainwater
with groundwater and brines containing dissolved evaporite sulphate in the Cretaceous
Basin of the Bohemian Massif (Central Europe) (after Smejkal and Jetel 1990).
84
The brines with low sulphate concentration contain isotopically heavier sulphate. A slope of
the δ34S(SO4) vs. δ18O(SO4) diagram of nearly 4 may indicate bacterial reduction and removal
of 32S via H2S. This interpretation is in contradiction with the increase of the sulphate concen-
tration (Fig.5.24). Therefore, a more complex history of sulphate has to be assumed for the
brines with low sulphate concentration. One explanation is dissolution of gypsum and anhy-
drite present in the Permo-carboniferous sediments. The sulphate of brines which came in
contact with organic matter became reduced and its concentration decreased. The isotopic
composition shifted to heavier sulphur and sulphate oxygen.
‰ brines with high SO 4

δ34S(SO4)
+30
brines with high SO 4
+25
gypsum
max
+20
+15
+1 sigma
mean
-1 sigma
+10
min
+5
rain
-5
1 10 100 1000 10 4
concentration of SO 4 (mg/l)
Fig.5.24 Relationship between δ34S(SO4) and the concentration of sulphate ions (log scale) in
groundwaters and brines from the basement of the Cretaceous basin in the Bohemian
Massif, Central Europe. As the mixing line δ34S(SO4) = {[c(SO4)rain × (δ34S(SO4)rain –
δ34S(SO4)evaporite)] / c(SO4)} + δ34S(SO4)evaporite does not fit the data, the sulphate must have
a more complex fate (data from Smejkal and Jetel 1990).
The isotopic composition of sulphate in the groundwater of the Variscian Bor granodiorite in
the Bohemian massif (V. Smejkal, unpublished results) indicates that a fossil brine has re-
mained in fractures of the rock though the sulphate concentration and the isotopic composi-
tion might have been modified by microbial reduction. The data points follow a linear trend
85
Chapter 5
1989
‰
δ34S(SO4)
1984 - 1987
+30
1972 - 1980
2.6
+25
+20
6.1
+15
4.0
+10
+5
2.9
-5
0 +2 +4 +6 +8 +10 +12 ‰
δ O(SO 4)
18
Fig.5.25 Plot of δ34S(SO4) vs. δ18O(SO4) for groundwaters and brines from the Variscian Bor
granodiorite (Bohemian massif) (V. Smejkal, unpublished data).
along lines with a slope between 2.6 and 6.1 which can be explained by a Rayleigh distillation
process in a closed system according to (Fig.5.25; Volume I).
R s (SO 4 ) t
= f s (SO 4 ) α −1
R s (SO 4 ) t =0
with the fractionation factor α = RS(H2S)/RS(SO4) and that of the residual sulphate ε =1−α
(×103‰). fS(SO4) is the residual fraction of dissolved sulphate. Substitution with δ34S(SO4)
yields
δ 34 S(SO 4 ) t = δ 34 S(SO 4 ) t =0 + (α − 1) ⋅ ln f s (SO 4 )

= δ 34S(SO 4 ) t =0 − ε ⋅ ln f s (SO 4 )
Fig.5.26 presents the results of this hydrogeological conception. Two source members were
considered: fossil Tertiary sulphate brine of the Bohemian Massif with 800 mg/L SO42 and
δ34S(SO4)t=0 = 5.4‰ (curve A) and of the Cheb Tertiary basin with a maximum sulphate con-
centration of 54 g/L and δ34S(SO4)t=0 = 5.4‰ (curve B). The enrichment factor of 22‰ corre-
sponds relatively well to the observed isotopic composition of sulphur and the sulphate con-
centration to that of the first end member. The isotopic composition of the second end mem-
ber cannot be explained by sulphate reduction or any other known fractionation process.
86
‰
δ34S(SO4)
A B
+30
+25
+20
+15
+10
+5
1989
0
1984 - 1987
1972 - 1980
-5
0 100 200 300 400 500 600
SO4 (mg/L)
Fig.5.26 Plot of δ34S(SO4) vs. c(SO4) for groundwaters and brines from the Variscian Bor granodio-
rite (Bohemian massif) (V. Smejkal, unpublished data). Curve A represents isotopic frac-
tionation by sulphate reduction in a fossile brine with 800 mg/L SO42+ and δ34S(SO4)
= +5.4‰. Curve B reflects isotopic fractionation after sulphate reduction in a fossile brine
from a neighbouring Cheb Tertiary basin, Czech Republic, with 56 g/L SO42+ and a
δ34S(SO4) = +5.4‰ (after Paces 1987).
Case study 3: Anthropogenic pollution

The isotopic composition of sulphate can also be an indicator of anthropogenic pollution of-
groundwater. Sulphate formed during high-temperature oxidation in technological processes
contain heavy sulphate oxygen derived from the atmosphere. The sulphate isotopic composi-
tion was determined from groundwater collected from a aquifer in the vicinity of a settling
pond with ash from power plants at Sulkov, Czech Republic (Smejkal 1990).
Three sources of sulphate were identified (Fig.5.27):
1) high sulphate concentration enriched with heavy oxygen and sulphur isotopes are derived
from the ash,
87
Chapter 5
δ34S(SO4)
+10
6.9
.7 +
+5
y=3
2
+1.
.4 x
y =0
+5 +10 +15 ‰
δ18O(SO4)
Fig.5.27 Various mixing lines of the isotopic compositions of sulphur and oxygen of sulphate as
indicator of anthropogenic pollutions in groundwater. The area of the squares is propor-
tional to the sulphate concentration in groundwater. The grey area represents samples
from an region with ash deposited in the settling ponds of the power plant in Sulkov,
Czech Republic. The points of samples from different depth but of the same well or drill
hole are connected by broken lines. The regression line y = 0.4 x + 1.2 is a mixing line
between fresh groundwater and water unpolluted with sulphate from the ash. The slope of
the regression line y = 3.7 x – 6.9 indicates microbial reduction of sulphate (after Smejkal
1990).
2) elevated sulphate concentrations enriched with light oxygen and light sulphur isotopes are
derived from oxidised local pyrite,
3) sulphate with low concentrations, enriched light sulphur isotopes and δ18O(SO4) between
+1 and +7‰ belong to groundwater containing atmospheric sulphate. Many of the sam-
ples in Fig.5.27 represent mixtures of these tree types of groundwater.
In conclusion, sulphur and oxygen isotopic analyses of sulphate dissolved in groundwater
may yield information on the origin of water and its constituents. The interpretation requires a
careful consideration of the various hydrochemical and biochemical processes, including mix-
ing of two or more water components. Geochemical and hydrogeological data on groundwater
may be a welcome supplement.
88
5.2.1.5 CHLORINE (37Cl/35Cl)
Chloride has two stable isotopes: 35Cl (≈ 75.7%) and 37Cl (≈ 24.2%). They do not participate
in biological processes and act as conservative tracer. Data are expressed as δ37Cl with respect
to the standard mean oceanic chloride (SMOC). The ratio 37Cl/35Cl is measured by isotope ra-
tion mass spectrometry (IRMS). The precision must be better than ± 0.1‰ (Volume I).
Occurrences
δ37Cl values contain information on the origin of chloride ions in fresh and polluted ground-
water as well as in subsurface brines (Eggenkamp 1994, Frape et al. 1995, 1998; Van
Warmerdam et al. 1995). They are not always well distinguished and scatter within a range of
−1.6 to +2‰ (Fig.5.28). Therefore, major sources of chlorine cannot easily be distinguished
by their isotopic composition (Volume I).
Processes
Isotope fractionation of the chloride isotopes occurs in geothermal systems (Chapter 6) under
crustal temperatures and pressures (Eastoe and Guilbert 1992). Ion filtration, diffusion, geo-
thermal boiling, brine evaporation and salt deposition appear to be the most important physi-
cal processes (Eggenkamp 1994).
Applications
Example:
The chloride concentration increases from shallow groundwater, to deep groundwater and the
brine in the Stripa mine, Sweden (Fig.5.28). Correspondingly the δ37Cl values increase. The
occurrence of transient values indicate mixing of deep and shallow groundwater (Frape et al.
1998). The available data do not yet allow a definitive decision about whether or not the chlo-
ride isotopic composition has a potential in such groundwater studies.
5.2.1.6 BORON (10B/11B)
Natural boron has two stable isotopes 11B (≈ 80%) and 10B (≈ 20%). The variation in the ratio
of these two isotopes is expressed in δ11B (‰) with respect to SRM-951 NBS standard (Ven-
gosh et al. 1998). δ11Β is determined by thermal ionisation mass spectrometry (TIMS) (see
also Volume I).
89
Chapter 5
1000
concentration of Cl-- (mg L-1)

structural mine water, 330 - 400 m
deep mine water, 350 - 1230 m
shallow groundwater, < 150 m
800
600
400
200
0
-1.60 -0.80 0.00 0.80 1.00 ‰
δ37Cl (SMOC)
Fig.5.28 Ranges of chloride concentration and stable isotopic composition of chlorine for fresh
and brackish groundwaters and brine from the crystalline rocks of the Stripa mine area,
Sweden (after Frape et al. 1998).
Occurrence
Boron is a minor constituent of groundwater with a concentration of usually less then
0.1 mg/L, in seawater it is 4.6 mg/L, and in oil-field brines >100 mg/L (White et al. 1963). An
increased concentration of boron in groundwater is usually related to enrichment with sub-
stances of marine and volcanic origin or they are related to anthropogenic pollution. Sodium
perborate is a component of detergents so that boron is present in sewage and in industrial
waste (Hem 1985). It is also a constituent of fertilisers (Vengosh et al. 1998).
Natural sources of boron in groundwater are atmospheric deposition, tourmaline, biotite and
amphiboles in crystalline rocks, colemanite, kernite and borax in evaporites, illite in marine
shales, residual seawater in isolated aquifers and magmatic volatiles in volcanically active and
geothermal areas.
There is a wide range of δ11B values in rain from +0.8 to +35‰ (Vengosh et al. 1998).
Freshwater δ11B is controlled by the atmospheric deposition, consisting of marine aerosols,
volcanic gases, and soil particles. Isotopically heavy boron originates from the sea (≈ +39‰),
isotopically light boron from volcanic sources as well as rock forming minerals (+1.5 to
+6.5‰). Terrestrial dust supplies small quantity and has a δ11B value between -6.6 and
+15.0‰. Brines contain isotopically extreme heavy boron (+25 to +60‰)(Barth 1993). An-
thropogenic sources are characterised by isotopically light boron and allow their differentia-
tion (+10 to –15‰; Vengosh et al. 1998).
90
The isotopic composition of boron in groundwater shows a continental effect. Uncontami-

nated groundwater from coastal plains of Israel has a δ11B of around +30‰, water in Alpine
lakes between +0.9 and +6.2‰ (Juraske 1994). The lowest δ11B is found in groundwater from
Great Artesian Basin in Australia, between -16 to +2‰ (Vengosh et al. 1991).
A generalisation on possible sources of boron in groundwaters is in Fig.5.29. The wide range
of δ11B values from -20 to +60‰ and several orders of magnitude differences in the B/Cl ra-
tio indicate that the isotopic composition of boron has a future potential for identification of
natural sources as well as of pollution sources in groundwater systems (see also Volume I).
‰
δ11B
+60
Dead Sea
salt water
intrusion
seawater
+40
groundwater in
coastal aquifers
+20 sewage effluents

Na-borate fertilizers
sewage-contaminated hydrothermal fluids

groundwater
0
groundwater
in non-marine
Ca-borate fertilizers aquifers
-20
10-4 10-3 10-2 10-1
B/Cl ratiomolar
Fig.5.29 Isotopic composition of boron and B/Cl molar ratio in various sources of boron in
groundwater (after Vengosh et al. 1998).
Processes
The most common dissolved species in groundwater is non-dissociated boric acid (H3BO3).
Polyborate ions and molecules are formed in highly saline solutions. The crystallographic ori-
entation of dissolved boron is trigonal, whereas in crystals the structure is governed by a
tetragonal co-ordination. The transformation in atomic co-ordination symmetry is accompa-
nied by a large isotopic fractionation with a characteristic enrichment factor εtri-tetra of about
-20‰. Heavy isotopes are preferentially partitioned to non-dissociated boric acid in ground-
water. Even adsorption of boron onto clay minerals may remove 10B from solution (Vengosh
et al. 1994). Boron is removed from soil water by biological uptake.
In spite of the wide range of δ11B in groundwater (from –7 to +60‰, Vengosh et al. 1998), a
quantitative interpretation of data is often difficult and uncertain due to mixing of various
91
Chapter 5
sources of boron and isotopic fractionation. A suitable graphical interpretation of mixing is

with the use of a diagram showing δ11B vs. B or B/Cl (see also Volume I).
Applications
Boron stable isotope ratios have a potential to play a role in pollution studies (e.g. Davidson
and Bassett 1993). They have also applications in the characterisation of brines and geother-
mal waters (Eggenkamp and Coleman 1998; Chapter 6).
Case study:
Fig.5.30 shows two mixing lines. One is between fresh groundwater and seawater in the
Coastal Plain of Israel. The second line reflects mixing between fresh groundwater and sew-
age effluent (Vengosh et al. 1998). The high values of δ11B in waters from the saline plumes
in Be’er Toviyya and Shiller, Israel, are explained by adsorption of boron and preferential
fractionation of the heavier 11B to solution.
0.07
concentration of boron (mmol/L)
0.06 Beér Torigya
0.05
anthropogenic
0.04
0.03 tion
ter dilu
wa
0.02 sea
0.01
0.00
0 10 20 30 40 50
concentration of chloride (mmol/L)
‰
δ11B
50
45
40 sea water ratio
35
30
25
20
0.0 0.2 0.4 0.6
concentration of boron (mg/L)
Fig.5.30 Boron and chloride in brackish waters from saline plumes in the coastal aquifer of Israel.
Mixing between boron of terrestrial groundwater and seawater is suggested by the linear
mixing line in the plot of boron vs. chloride concentration and by the hyperbolic relation
of δ11B vs. boron concentration (after Vengosh et al. 1998).
92
5.2.1.7 STRONTIUM (87Sr/86Sr)
The 87Sr/86Sr atomic ratios are measured mass spectrometrically (TIMS) and are given as
atomic ratios. That of seawater is 0.70906 and as reference (Volume I).
Occurrence
Strontium is a minor constituent of groundwater. It readily substitutes calcium ions in cal-
cium, sulphate, feldspar and other rock-forming minerals. Hence it participates in the water-
rock interactions (Chapter 4; Volume I).
Processes
No natural fractionation of stable strontium isotope was observed during natural processes.
This property makes the isotopic ratio of strontium a reliable candidate for tracing strontium
of different origin, for evaluating mixing of ground waters and for studying a state of isotopic
equilibrium between groundwater and strontium bearing minerals and rocks. A precise mixing
balance can be set up for two aqueous end members with different 87Sr/86Sr values. Informa-
tion on this process and on the extend of water-rock interactions is obtained from comparing
the 87Sr/86Sr values in the primary minerals of the host rock with those in the groundwater and
in the secondary minerals on the surface of fractures, joints and pores. Strontium and calcium
have similar geochemical properties. Therefore, the strontium isotopic composition serves to
study the weathering of calcium bearing rocks and the biogeochemical recycling of calcium
(Volume I).
Applications
It is a tracer for the origin of salinity, groundwater movement and water-rock interactions
(Chapter 4).
Case study 1: Source of Sr in spring water
The 87Sr/86Sr ratio of spring water in the Mont-Dore region in Massif-Central, France, de-
pends upon the source rocks and ranges from 0.704408 to 0.714226 (Pauwels et al. 1997).
Granitic rocks contain more radiogenic 87Sr (0.722282 and 0.733804) while basaltic rocks less
(0.703844 to 0.704215). Groundwater with low radiogenic strontium apparently dissolved
strontium from basaltic rocks being richer in the element than the granitic rocks. The fact that
the 87Sr/86Sr ratio of the spring water from granitic rock does not approach the characteristic
value may be explained as isotopic equilibrium with the rock not having been reached, by the
occurrence of mixing or by the possibility that an isotopic equilibrium is related to an un-
known soluble rock-forming mineral.
93
Chapter 5
Case study 2: Weathering studies

In weathering studies (Aberg et al. 1989; Wickman and Jacks 1992) strontium serves as an
chemical analogue to calcium. The weathering rate of release of calcium from rocks is calcu-
lated from the strontium isotopic mass balance, applying a simple two-component mixing ap-
proach according to Eq.5.5 (Wickman and Jacks 1992). The subscripts runoff, weath, and atm indi-
cate the strontium isotope ratios of strontium of the input by runoff, weathering, and atmos-
pheric deposition; xweath and xatm are proportions of weathering and atmospheric deposition
inputs. It follows for the rate of weathering qweath
 87 Sr   87 Sr 
  −  
 86 Sr   86 Sr 
  runoff   atm
q weath = (5. 6)
 Sr 
87  Sr 
87
  −  
 86 Sr   86 Sr 
  weath   atm
It is assumed that strontium weathering rate QSr (kg ha-1 yr-1) is proportional to that of calcium
so that it can be referred to that of (QCa). Then
q weath
Q weath = Q atm ⋅
1 − q weath
where Qatm is the atmospheric deposition rate of calcium in (kg ha-1 yr-1).
For example, the 87Sr/86Sr ratios of precipitation, river water and soil from the catchment in
Svartberget, northern Sweden, are 0.7168, 0.7398, and 0.7402. Then, 98% of the strontium in
the runoff is due weathering. As the annual atmospheric deposition rate of Sr amounts to
0.76 (kg ha-1 yr-1) the corresponding rate for calcium is 38 (kg ha-1 yr-1).
Case study 3:
The effects of the interaction between infiltrating meteoric water into soils and plants on the
calcium-strontium system was studied by changes of the strontium isotopic composition at a
soil profile in forests of the Black Triangle in Czechoslovakia (Bendl 1992). Fig.5.31 illus-
trates how the 87Sr/86Sr ratio changes due to atmospheric acid deposition following the in-
crease in the calcium content and the decrease of pH. Continental precipitation contains more
radiogenic 87Sr (0.70999) than marine strontium (0.70906). The throughfall (0.71013) under
the spruce canopy dissolves a mixture of soil dust (increasing with depth from 0.71379 to
0.740425) and limestone (0.707859). The water infiltrating into the soil has a ratio of 0.71197
and that of the runoff in local small streams ranges from 0.72095 to 0.72160. The gradual in-
crease of the 87Sr/86Sr ratio from the lowest value in atmospheric water to the highest value in
the runoff indicates that a strontium isotopic equilibrium cannot be reached during the rela-
tively short residence time of the water in the soil.
Another case study about water-rock interaction at rock fractures in the Stripa mine granite in
Sweden is given in Sect.4.4.4.
94
5.2.2 GROUNDWATER DATING

The residence time of groundwater in an aquifer or the groundwater age is an important pa-
rameter in any palaeohydrologic and geohydraulic study. The chemical and isotopic composi-
tions of groundwater usually represent steady-state conditions which develop after a certain
time. Water-rock interactions (Chapter 4) occur during groundwater recharge within days/
weeks and during flow in the aquifer within years to even millions of years. Isotope hydro-
logical studies give at least an idea about approximate ages of the various groundwaters.
The radiogenic isotopes of hydrogen (3H – tritium; Sect.5.2.2.1 and 5.2.2.2) and carbon (14C
radiocarbon; Sect.5.2.2.3) and in special cases krypton (81Kr; Sect.5.2.2.7, 85Kr; Sect.5.2.2.8),
argon (39Ar; Sect.5.2.2.6) and chlorine (36Cl; Sect.5.2.2.5) with very different half-lives are
being used to evaluate relative or absolute groundwater ages (see Volume I).
Dating by radioactive decay: The physical process of radioactive decay is the basis of the age
determination of groundwater. Radioactive decay of a certain nuclide is completely independ-
ent of any environmental parameter such as pressure, temperature, pH or chemical bonds, and
only depends upon a characteristic degree of instability, expressed into a half-life. There are,
however, physical processes and geochemical reactions which secondarily change the specific
activity (= activity per L or per g) (Volume I; Chapters 3 and 5).
precipitation
lining throughfall
soil
profile
infiltration
50 cm
surface runoff
100 cm
.70 .71 .72 .73 .74

87
Sr/86Sr atomic ratio
Fig.5.31 Change of the 87Sr/86Sr ratio in a soil profile below a forest damaged by acidic deposition
in the Black Triangle of Europe, Czech Republic. The calcium content is increased and
the pH decreased. The change reflects the different 87Sr/86Sr ratios for continental precipi-
tation (= 0.70999) and marine sources (0.70906) (after Bendl 1992).
95
Chapter 5
Complications:
Hydrochemical reactions: The initial activity Ainit of a radioactive isotope present in the
groundwater at the time of recharge may not be 100 % as defined for the atmosphere (e.g. 14C,
39
Ar) (cf. Volume I, Chapter 8: for 14C defined as the relative activity 14a in % or pMC). Hy-
drochemical processes as the dissolution of fossil limestone without 14C lower the 14C activity
apart from radioactive decay. As a result 14C ages calculated conventionally with Ainit = 100%
are apparently too large. The actual initial 14C activity Ainit of the groundwater must be used in
Eq.2.2 (see Volume I).
Underground production: Mainly neutrons produced by the decay of uranium and thorium
and the daughter products create nuclear reactions with chemical elements of the rock matrix.
Radioactive nuclides as 39Ar, 36Cl and other may be formed (Florkowski et al. 1988). If this
underground production of environmental isotopes is not taken into account, apparently too
small groundwater ages would result.
Water-Rock interaction (Chapter 4): Exchange between the dissolved constituents of the
groundwater and the rock matrix, congruent and incongruent precipitation and dissolution
may have lowered the activity of the isotope used for dating and results in apparently too
large ages (Wigley et al. 1978).
Anthropogenic tracing of the hydrosphere: The hydrosphere has become polluted with an-
thropogenic radiocarbon, tritium, 36Cl and others isotopes by nuclear weapon tests during the
1950s and early 1960s and later by the release of environmental isotopes as 85Kr by the nu-
clear energy industry, and the use of isotopes in industrial applications. The occurrence of
these "artificial" isotopes in nature can be used to estimate mean residence times (Vol-
ume VI) or absolute ages of groundwater (Sect.5.2.2.3).
The presuppositions of any age determination is that the dated samples belong to groundwater
resources that behave as closed systems. In freshwater systems, this presupposition is seri-
ously prevented by geohydraulic mixing. The seepage of surface water into a phreatic aquifer
and the leakage between adjacent aquifers results in mixing of different old groundwaters. In
such cases the isotope data have to be interpreted by conceptional or lump-parameter models
(Chapter 3; Volume VI).
5.2.2.1 TRITIUM
The radioactive hydrogen isotope, tritium, has a half-life of 12.43 years. The tritium activity is
given in tritium units [TU]. One TU corresponds to one 3H atom to 1018 hydrogen atoms or
1.185 Bq/L (Volume I).
96
3
H acts as a conservative tracer as it is a constituent of the water molecule itself. Only in
highly saline groundwater with high uranium, thorium, and lithium contents, underground
production via boron results in 3H activity levels of up to 0.5 TU (Florkowski et al. 1988). A
slight retardation of the 3H movement has been observed at clay by anion exclusion (Sect.4.1).
Occurrence
The natural cosmogenic level of 3H in precipitation is a few TU. Since the fifties the level in
precipitation rose up to about 2000 TU due to nuclear weapons testing primarily on the North-
ern Hemisphere until 1963/1964. After the atom bomb moratorium it dropped exponentially
to about 10 TU in the northern hemisphere at present (Fig.2.1). On the southern hemisphere
the time course of the 3H levels was similar though on a lower level and retarded by about 2
years. Seasonal 3H fluctuations are less important for groundwater dating. One reason may be
that summer rainfall hardly contributes to groundwater recharge.
In order to record this change of 3H in precipitation IAEA established a global network of
about 125 stations to collect precipitation for isotope analysis. The measured isotopic abun-
dances have regularly been published in the IAEA Technical Reports Series since 1969
(IAEA 1969 – 1994). For more recent data contact http://www.iaea/org/worldatom. This data
bank provides sufficiently reliable input curves for extrapolation to nearly any site on the
globe. Samples which behaved as closed systems during the past century as cold ice, deep
groundwater, and deep ocean water may reflect this record.
There is a pronounced continental effect. Lower 3H values are found in coastal areas than in-
land.
On the conditions for sampling and the detection techniques the reader should consult Vol-
ume I. The sample size ranges between 2000 and 15 mL. The detection limit is 0.1 TU apply-
ing electrolytic enrichment of 3H.
Applications
Dating by 3H determines the residence time of shallow groundwater and of spring water in
fissured and fractured rocks less than about 150 years. The classical 3H method (Libby 1953)
was based on the environmental cosmogenic 3H activity in rain water. It had a very limited
applicability due to the drastic increase of the 3H level by up to four orders of magnitude, be-
tween the early fifties and 1963/64 as a result of nuclear weapons tests (Fig.2.1). This input of
3
H to the hydrosphere can, however, be used to estimate mean residence times applying
lumped-parameter models (exponential model, dispersion model, linear model; Sect.3.1.2;
Volume VI). In most cases the 3H activity of shallow groundwater and spring water is inter-
preted by the exponential model (Sect.3.1.2; Fig.3.5; Volume VI). It is assumed that spring
water consists of water of different aged components whose proportions decrease exponen-
tially with increasing age. The MRT may be between years and decades, implying short turn-
over times of the groundwater. Time-series of data provide the most precise and reliable re-
97
Chapter 5
sults and allow to test whether or not a used model was able to describe the system (Zuber
1986; Malozewski 1994). An alternative is applying the analysis of several isotopes as 85Kr
(Sect.5.2.2.8) (Grabczak et al. 1982; Zuber 1986). Appropriate models for routine evaluation
of 3H data are commercially available (e.g. MULTIS; Richter et al. 1993). Single 3H values
mostly yield ambiguous mean residence times, to be discarded because of geohydraulic re-
flections.
Other applications of 3H is studying lake dynamics, and the estimation of groundwater re-
charge rates in humid, arid and semi-arid regions. In regions with low precipitation samples
from dug wells offer a unique possibility to estimate upper limits of the groundwater recharge.
If the water table has a thickness d the measured 3H value of the water and the recharge rate
qrec is given by
3
H spl ⋅ d ⋅ n tot
q req = now
3 − λ ( now − t )
∑ H in ( t ) ⋅ e
1955
The 3H-interface method is an example of estimating groundwater recharge areas that are
heavily urbanised and have a high density of wells (Fig.5.32; Andres and Egger 1985; Deak et
al. 1995, Bertleff et al. 1993).
Penzing
m a.s.l.
600 m a.s.l.
550 Augsburg 550
500 Meitingen 500
450 Donau 450
400 400
350 tritium interface 350
300 300
250 filter well 250
200 0 5 10 km 200
Fig.5.32 Application of the 3H interface method to estimate the groundwater recharge in heavily
populated areas in southern Germany (after Egger and Andres 1985).
Geohydraulic information on the mixture of groundwater from different sources and of dif-
ferent age – an old 3H–free groundwater with a young groundwater containing 3H – is a rou-
tine application. It is related to the current hydrological problem of estimating the pollution
potential of groundwater resources pumped for the drinking water supply. It has been found
98
that elevated nitrate concentrations make 3H analyses useless because of the much lower mean
life of nitrate.
Case studies
The shape of the input function of 3H since 1963/1964 as shown in Fig.2.1 is preserved in the
fast moving groundwater in the alluvial deposits of the Danube River, Hungary, for over 30
years. The flow is radially away from the river over a horizontal distance of 12 to 15 km and
at a vertical depth of about 140 m. Due to radioactive decay and the preferential infiltration of
winter precipitation with relatively low 3H, the peak activity in the groundwater should be 200
to 300 TU. The measured values of 80 to 90 TU are due to hydrodynamic dispersion
(Fig.5.33).
Dunakiliti
Danube Mosonmagyaróvár Lébény
0 27 30 37 11
depth (m)
56
28 63 30 24
29 28 3749 43 25 18 30
57 58
bomb 49
50 25 24 peak 54 6
27
75 64 24 4
47 75 <1
272 <1
100 24 28
56
150
ve y
gra sand
Quaternary
l
e
200 9
fin
Pliocene
0 5 10 15 20 25 30 35 40
distance from Danube river (km)
Fig.5.33 Spatial 3H distribution in a depth profile at the Danube River, Hungary. The bomb peak
of 3H (grey area) travelled with about 500 m yr-1 from W to E and approached a depth of
50 – 100 m at 1993 (after Deak et al. 1995).
3
5.2.2.2 H/3He AND 3He METHODS
3
H decays with a half-life of 12.43 yr into the daughter isotope 3He. By measuring both the
mother and daughter activity actual water ages can be calculated, provided the samples were
unmixed and collected from an aquifer with a piston-flow like groundwater movement (Chap-
ter 3). The input function of 3H need not be known.
The activity of 3H is given by (Volume I):
3
H spl = 3 H init e − λ⋅t (5. 7)
99
Chapter 5
The growth of 3He in a sample is given by

3
He spl = 3 H init (1 − e − λ⋅t ) (5. 8)
Combining Eq.5.7 and 5.8 the unknown and variable initial 3H activity 3Hinit is eliminated and
the absolute age is obtained by
3
He spl = 3 H spl (e − λ⋅t − 1)
The 3He concentration has to be corrected for admixed 3He from the Earth's crust and from
the atmosphere.
Until now the high cost of the mass spectrometer analysis prevented a wide application. An
methodical problem of this method is diffusive gas loss, either due to natural processes or dur-
ing sample treatment and storage (Volume I; Schlosser et al. 1989; Ekwurzel et al. 1994).
The required high–precision measurement of 3H is obtained by the so-called 3H-ingrowth
technique (Volume I). The 3H activity is determined through measuring the stable 3He pro-
duced by the 3H decay. Water samples (typically ca. 45 ml) are thoroughly degassed and then
stored for at least a half year in a tightly sealed aluminosilicate container under vacuum. The
3
H value C(3H) is calculated from the concentration c(3He) of 3He produced during the stor-
age time t by Eq.5.7. The detection limit for 3H of this method is > 0.005 TU (Volume I).
Application
Schlosser et al. (1989) used this method to absolutely date shallow groundwater in an alluvial
aquifer in Germany. The precision of the dating was ± 10%, the loss of 3He by diffusion was
estimated to ≈ 20%. This is small enough to consider 3He as conservative tracer. The method
is found to be a very valuable complementary tool for the dating by CFC and SF6.
Owing to its sensitivity, the 3H/3He method is used for absolute groundwater dating up to
about 40 yr (Schlosser et al. 1989). The application may increase in the future as the applica-
tion of the conventional 3H method is temporarily limited (Carmi and Gat 1992) due to the
largely declined 3H activity in precipitation.
5.2.2.3 RADIOCARBON
Radiocarbon (14C) is the radioactive isotope of carbon with a half-life of 5730 years. It occurs
in atmospheric CO2, living biosphere and the hydrosphere after its production by cosmic ra-
diation. Underground production is negligible. The 14C activity is often given as an activity
ratio relative to a standard activity, about equal to the activity of recent or modern carbon.
Therefore, the 14C content of carbon containing materials is often given in percent modern
carbon (pMC): 100 % or 100 pMC (or 100 % Modern Carbon) corresponds by definition to
the 14C activity of carbon originating from (grown in) 1950 AD (Volume I).
100
Fallout 14C (in carbon dioxide) from the nuclear tests (Fig.2.1) offers the possibility – analo-
gous to 3H– to date young groundwater with mean residence times of up to 150 years of the
long-term components of karst spring-water and shallow groundwater applying suitable inter-
pretation models (Volume VI).
14
C is measured radiometrically using samples with an equivalent of 25 mg to 5 g carbon (cor-
responding to about 5 to 100 L of groundwater) and mass spectrometrically (AMS accelerator
mass spectrometry) with less than < 1 mg carbon (details in Volume I).
Occurrence
14
C may not behave as a conservative tracer in groundwater as it is a constituent of the dis-
solved inorganic carbon (DIC) compounds undergoing hydrochemical reactions with the rock
matrix of the host aquifer (Sect.4.4; Volume I; Clark and Fritz 1997).
14
C also occurs in the dissolved organic carbon compounds (DOC). The dissolved organic
carbon (DOC) in groundwater consists of organic liquids, hydrocarbons, methane and humic
components. It is produced by microbial activity from humic matter in the top soil, peat layers
and lignite. The youngest dissolved constituents in groundwater are fulvic acids (FA) which
are most promising for groundwater dating (Geyer et al. 1993; Wassenaar et al. 1991). Humic
acids (HA) are less suitable.
The concentration of FA in groundwater is as low as 1 mg/L carbon. As the fulvic acids are
composed of variable-age organic carbon of pedogenic and geogenic origin with an age range
of many hundreds to thousands of years. Ao is usually lower than 100 pMC. Geyer et al.
(1993) found a range of 34 – 100 pMC but most frequently between 75 and 100 pMC. The
initial 14C activity can only empirically be estimated. The expectation that 14C dating of DOC
may overcome the hydrochemically involved problems of 14C dating of DIC has not been ful-
filled though sometimes the contribution of old sedimentary organic carbon can be estimated
(Aravena and Wassenaar 1993). 14C dating of DOC is, however, a useful supplement to 14C
dating of DIC (Volume I).
Processes and Reactions

Dating of groundwater, initially considered as the main purpose of isotope hydrology, applies
the 14C method developed by Libby (1946) for organic samples with ages up to some 50 000
years. According to Libby's model, the 14C produced by cosmic rays is oxidised to CO2 in the
atmosphere and is mixed into the CO2 cycle. Through the assimilation by plants and their con-
sumption by animals and man, 14C enters the biocycle and thus the various earth reservoirs of
14
C (atmosphere, biosphere and hydrosphere), for each of which a different specific initial
specific acitvities Ainit applies (reservoir effect). Within the time span of the 14C dating
method the production rate and therefore also the global 14C reservoir, is taken as approxi-
mately constant. Cosmogenic production of 14C is balanced by radioactive decay. As soon as
an organism dies the assimilation of 14C ceases and the specific 14C activity (14C value) de-
101
Chapter 5
creases with a half-life of 5730 years. In order to determine the age by Eq.2.2 it is therefore
necessary to measure the specific 14C activity of a reference material Ainit of known age (stan-
dard) and of the sample Aspl to be dated.
Münnich (1957, 1968) recognised that groundwater can be dated based on the carbonate/bi-
carbonate chemistry. 14C is present in groundwater in the form of CO2, mainly as HCO3−. CO2
in soil air (up to 3 vol.%), which is produced by the respiration of roots and the decomposition
of organic material that has recently died (14C activity = 100 pMC, δ13C = −25‰) is dissolved
by infiltrating rainwater and dissolves marine and fossil carbonate in the topsoil (assumed to
be 0 pMC, δ13C = 0‰) as carbonic acid forming bicarbonate (Eq.4.1). There is a large differ-
ence between open and closed systems (Volume I; Clark and Fritz 1997).
After hydrochemical equilibrium between the CO2 and carbonate has been reached Ainit in
newly regenerated groundwater is in the range of 55 to 65 pMC, corresponding to a reservoir
correction of −4500 to −3500 yr. Consequently, Ainit increases with increasing DIC.
There are various models to estimate Ainit by applying the concentrations of bicarbonate and
CO2 or the isotopic composition of carbon including isotopic fractionation and mixing
(Sect.4.4.1; Volume I; Mook 1980; Clark and Fritz 1997). Most common is the estimation of
the initial 14C activity (Cinit) by means of the Gonfiantini model (Salem et al. 1980; Eq.5.5). It
relates the δ13C of the DIC in groundwater (δ13CDIC = 0 ± 0.3‰) to mixing of carbon from
calcite (δ13Ccalc = 0 ± 2‰) with carbon from soil CO2 (δ13CCO2 = -22 ± 1.5‰) and isotopic
fractionation factor ε between dissolved bicarbonate and gaseous CO2 is a function of tem-
perature and pH and amounts to 8 to 9‰. The model yields the initial activity of 14C for
closed carbonate-CO2 systems, and the calculated model age t according to Eq.5.9.
Experience with these models shows that using the same hydrochemical and isotope hydro-
logical information they produce corrections varying by up to many thousands of years (Geyh
1992). The best results are obtained with the program NETPATH, provided chemical and iso-
topic data are available from samples taken from wells along the same flowpath of the
groundwater. This presupposition cannot easily be fulfilled. A mayor problem of all model-
ling remains that the isotopic compositions of the chemical components – limestone and CO2
are rarely accurately known, while isotopic equilibrium is usually not attained (Geyh 1992).
In any case, the time scales of the different models for most fresh groundwater resources are
linearly related to each other (Fig.5.34). Therefore, the numerous possible secondary changes
in 14C values of fresh groundwater, due to water-rock interactions in the saturated zone and
unrelated to radioactive decay (Chapter 4), appear to play a minor role. The 14C values of DIC
thus represent reliable time differences producing reliable flow rates in solute transport mod-
elling.
One problem of the estimate of Ainit by hydrochemical or isotopic models is that a thorough
error analysis, adopting the ranges of initial 14C activity and δ13C of the hydrochemically in-
volved components, considerably lowers the precision of groundwater dating. This becomes
102
the more pronounced the more components are used in the model. In the case of the relative
simple Gonfiantini model (Eq.5.5) the precision rises from ± 100 yr to ± 2700 yr. Fortunately,
the results of many case studies show that the 14C groundwater dates scatter less than ± 500 yr
(Geyh 1992). The reason is that the range of the initial δ13C values of the participating hydro-
chemical constituents from restricted recharge areas are smaller than the global ranges though
not accurately known.
A possibility to overcome the problems in selecting the appropriate correction model and de-
termining representative regional parameters are empirical approaches to estimate Ainit and to
calibrate the 14C ages of DIC. Frequently the fixed correction value of 85 pMC (Vogel & Eh-
halt 1963) is applied. Geyh (1972) evaluated a differentiated array of Ainit for different geo-
logical settings of the recharge area (Table 5.2).
40
true water age (kyr)
maximum reservoir
correction
30
20
10
glacial
period
0
0 10 20 30 40
conventional C age of DIC (kyr)
14
Fig.5.34 Example of an interrelationship between true water ages and conventional 14C ages of
DIC from central USA. It shows that secondary 14C changes during groundwater flow
cannot play a dominant role as the slope of the best-fit line is near unity. Moreover, the
interruption of the groundwater recharge during the last pleniglacial period is well do-
comented by the gap (grey area) of the 14C dates. The reservoir correction amounts
maximum to 5000 yr (data from Phillips et al. 1989).
A very effective way is to plot the 14C ages of DIC along the flow path and to extrapolate
them towards the recharge area where the actual water age is assumed to be zero (Vogel 1970;
Fig.5.35).
103
Chapter 5
A very reliable approach is to plot the 3H value (alternatively 85Kr) versus the 14C activity
(Fig.5.36; Verhagen et al. 1991). The initial 14C activity is found where the curve hits the de-
tection limit of 3H. This approach is based on the assumption that a groundwater which does
not contain bomb 3H may also not contain bomb 14C (Fig.2.1).
Table 5.2 Empirically estimated initial 14C values Ainit and corresponding reservoir corrections for
different geological settings (Geyh 1972).
geology of the catchment Ainit reservoir correction

(pMC) (yr)
crystalline 90 to 100 −1000 to 0
loess covered 85 −1300
uncovered karst, dunes 55 to 65 −5000 to –3500
Palaeohydrological, palaeoclimatological and prehistoric information (Geyh 1992; Clark et al.

1996) may always be used to check the reliability of the estimated initial 14C activity or to
check its accuracy. An example is given by Clark et al. (1996) who applied supplementary
correction models for carbonate dissolution and sulphate reduction (Clark & Fritz 1997) until
the 14C(DIC) dates fit with the palaeohydrological situation (Fig.5.37).
30
conventional 14C age (kyr)
20
tracer velocity = 0.66 (m yr-1)
10
reservoir correction = -1300 (yr)

0
0 5 10 15 20
distance from outcrop (km)
Fig.5.35 Increase of 14C water ages of DIC over the distance from the recharge area used to esti-
mate the initial 14C activity of 85 pMC or the corresponding reservoir correction of –1300
yr (after Vogel 1970).
104
There are several hydrochemical reactions of water-rock interaction (Sect.4.4.1) and processes
which may change the 14C value after the groundwater recharge, resulting in apparently too
large water ages. Concurrent dissolution and precipitation of carbonate is one process (Wigley
et al. 1978), matrix diffusion and isotopic exchange within the aquifer another, but more im-
portant the oxidation of fossil organic matter by sulphate reduction and subsequent dissolution
of additional carbonate as well as the admixture of magmatic and crust CO2 (Sect.4.4.1). All
these processes lower the 14C activity, accompanied with an increase of the DIC concentra-
tion, CT. As shown in Sect.5.2.2.3 the resulting dissolution of the 14C activity cannot be cor-
rected by means of the changes of the δ13C values. A solution is the so-called Oeschger cor-
rection applied instead of Eq.2.2 for the age determination:
5730 A ⋅C
t= ⋅ ln init Tinit (5. 9)
ln 2 A spl ⋅ C Tspl
H va lu e (T U )
25
20
3
15
10
in itia l 14
C a ctiv ity
5
d e te ctio n lim it
0
60 80 100 120
14 C a ctiv ity (p M C )
14
Fig.5.36 C-3H plot to estimate the initial 14C activity of groundwater in the northern Kalahari (af-
ter Verhagen et al. 1974). Samples at or below the 3H detection limit should not contain
bomb 14C.
In summary the hydrochemical reactions before and after groundwater recharge as well as
several physical processes may change the 14C activity as well as DIC concentration, and in-
fluence the 14C time scale of the groundwater. This is shown in Fig.5.38.
105
Chapter 5
35
water age (kyr)
without correction
30
25
20 carbonate dissolution
15
sulphate reduction
10 pluvial period
0
63 62 66 55 56 57 58 64
site
Fig.5.37 Application of different hydrochemical correction models to estimate the initial 14C value
of DIC of groundwater in the Ad Rhuma aquifer, Oman. The validity of the results is
proved by the agreement with the palaeohydrological situation (after Clark et al. 1996).
secondary chemical conventional

model water age
reactions with the rocks 14C age of DIC
of the aquifer
on
ducti
14 C pro
r age
w ate
e
tru
correction bias =
reservoir correction actual water age
corrected 14C water age
Fig.5.38 Changes of the 14C time scale of DIC as result of radioactive decay (conventional ages),
hydrochemical reactions due to water-rock interactions and 14C production after ground-
water recharge.
106
Applications
The broad application of the 14C dating method to hydrological problems and the interpreta-
tion of the results is largely covered by the proceedings of the international conferences on
hydrology organised by the IAEA and reviewed by a number of publications mentioned in the
section on Recommended Literature. Palaeohydrogeological and quantitative geohydraulic
aspects have been treated in Verhagen et al. (1991). In spite of the above mentioned limita-
tions of the method, 14C age determinations on DIC in groundwater are in demand in various
ways. This field covers the age determination for palaeohydrological and palaeoclimatological
studies (Geyh 1994), the determination of flow rates and flow direction of groundwaters
(Fig.5.35), the search for arid or pluvial periods in present semi-arid and arid regions
(Fig.3.7), the estimation of recharge rates in phreatic deep aquifers (Verhagen et al. 1991), the
determination of regional geohydraulic parameters as porosity and hydraulic conductivity
(Geyh et al. 1984), and a check on and improvement of hydrological conceptions (Verhagen
et al. 1991).
5.2.2.4 SILICON-32
32
Si is the radioactive isotope of silicon with a half life of about 140 yr. It is cosmogenically
produced and shows high variations during the season (Morgenstern et al. 1996). Biochemical
processes result in an uncontrolled uptake of silicon by plants in the unsaturated zone and se-
riously accelerate the decrease of the 32Si activity with time, apart from radioactive decay.
Moreover, mixing with natural resources in the subsoil complicate the evaluation of the 32Si
activity. The geochemical and biochemical processes in the soil, modifying the 32Si activity
are not yet well known. They are responsible that 32Si does not behave as a conservative tracer
in groundwater. Thus, dating of groundwater in a theoretical range between 100 and 1500 yr
has not (yet) been successful (Volume I).
5.2.2.5 CHLORINE-36
36
Cl is the radioactive isotope of chlorine and has a half-life of 300 000 years. Its specific ac-
tivity is given in disintegrations per minute and litre water (dpm L−1) or as the atomic ratio be-
tween 36Cl and Cl. The initial 36Cl/Cl ranges from 5 to 30 × 10−15 for young groundwater
(Volume I).
If 36Cl is measured by AMS, 1 to 2 mg AgCl are analysed. This can be obtained from a few li-
tres of water (Bentley et al. 1986).
Occurrence and processes

36
Cl is produced cosmogenically, by natural underground production and by nuclear weapon
tests. The subsurface production by radionuclide-derived neutron fluxes on 35Cl depend heav-
107
Chapter 5
ily of the variable geological settings (e.g. Andrews and Fontes 1992). As radioactive decay
and underground production on the one hand, and dilution by dissolution of salt or salt en-
richment by evaporation on the other interfere, the interpretation of 36Cl data in terms of
groundwater ages remains ambiguous (Mazor 1992). If uranium-rich or chlorine-bearing min-
erals are present, apparently too low 36Cl groundwater ages may be obtained (Bentley et al.
1986).
The relative 36Cl abundance in groundwater is not changed by evaporation of the water, min-
eral interactions or secondary mineral formation, but it is influenced by dissolving of chloride.
Therefore, the total chloride concentration has to be always determined. The plot of 36Cl/Cl
versus the chloride concentration yields information on groundwater mixing, evaporation, re-
mobilisation of chloride, and radioactive decay and subsurface production of 36Cl (Florkowski
et al. 1988). The complex situation of the interpretation of chlorine isotope data is shown in
Fig.5.39.
Applications
36
Cl is applied to groundwater with transit times of >40 000 yr up to 3 000 000 yr (Fabryka-
Martin et al. 1987). 36Cl is also a bomb tracer and was used for dating young groundwater in
the unsaturated zone and in unconfined aquifers recharged during the last four decades. How-
ever, AMS analyses are expensive compared to 3H and 14C measurements.
production
reaction evaporation
chloride
concentration
salt leaching
decay
Fig.5.39 Physical processes which change the chlorine-36 activity in groundwater and complicate
the interpretation of the isotope data (after Mazor 1992).
108
Case study 1: Great Artesian Basin, Australia

36
Cl dating is limited to fresh groundwater resources in large basins as the Great Australian
Basin. The results confirmed the geohydraulically estimated water ages of up to 1 Myr
(Fig.5.40). The initial 36Cl/Clinit ratio was estimated to be around 100 to 120×10−5 (Bentley et
al. 1986; Herczeg et al. 1999). There is, however, a large difference to the estimated 81Kr wa-
ter ages which has not yet been explained (Sect.5.2.2.7; Lehmann et al. 1999).
1.4
water age (Myr)
1.2
1.0
e
ag
ic
am
0.8 yn
od
dr
hy
0.6
0.4
0.2
= less than 0.1 Myr
0
0 100 200 300 400 500 600 700 800 900 1000
flow distance from outcrop (km)
Fig.5.40 Concordant 36Cl ages and geohydraulically estimated groundwater ages along the south-
ern flow line in the Great Artesian Basin in Australia (after Bentley et al. 1986).
Case study 2: Milk River Aquifer, Canada

The problematics of hydrogeological 36Cl studies was recognised by 36Cl dating attempts in
the Milk River aquifer in Alberta, Canada, in which the chloride concentrations cover a range
of two orders of magnitude (Phillips et al. 1986). It is the general reason why the application
of the 36Cl method is still very limited.
Case study 3: Mixing studies
There is a potential to apply 36Cl analyses to differentiate between mixing components, to set-
up a chloride balance for geothermal fluids in hydrothermal systems (Chapter 6), for old
groundwater systems with extensive water-rock interaction as well as with a high input of en-
dogenous CO2 (Phillips et al. 1984a, Balderer 1993; Balderer and Synal 1995; Yechieli et al.
1996).
109
Chapter 5
Case study 4: Young groundwater

36
Cl produced by the nuclear bomb tests has also been used to determine the vertical velocity
of soil water. Reasonable flow rates of 2.5 mm⋅yr−1 were found in arid regions (Bentley et al.
1982; Elmore et al. 1982, Phillips et al. 1984b; Clark and Fritz 1997). This application may
have been overlived, as most of such young groundwater has already discharged.
5.2.2.6 ARGON-39
39
Ar is the radioactive isotope of argon and has a half life of 269 yr. Its activity is given in
pMAr (equivalent to the definition for 14C: % Modern Argon) referring to the 39Ar activity in
atmospheric argon which is by definition 100 pMAr. 39Ar is cosmogenically produced.
Groundwater ages are calculated by Eq.2.2 analogous to 14C if the groundwater system be-
haved as closed system in the age range of several decades to about 1000 yr (Loosli 1992).
Hydrochemical water-rock interaction of noble gas can be excluded. The occurrence of un-
derground production, however, may considerably increase the 39Ar activity (Florkowski et al.
1988).
The extraction of samples of about 15 m3 of water in the field is complicated and the radio-
metric measurement is time-consuming with 5 to 30 days counting time (Volume I).
Occurrence and processes

In granitic and other rocks having a high uranium concentration the production of 39Ar by
neutron reaction with 39K [39K(n, p)39Ar] (Florkowski et al. 1988) explains the too small 39Ar
ages (Loosli 1992). In leaky aquifer systems 39Ar-saturated pore water from the aquitards may
falsify 39Ar dates of groundwater (Geyh et al. 1984). An indication of underground produced
39
Ar is obtained from the measurement of 37Ar (T1/2 = 35 d). In old groundwater the contribu-
tion of 40Ar produced by the decay of 40K must be taken into account.
Applications
Case study 1: Concordant 14C and 39Ar water ages

Forster et al. (1992) presented concordant 39Ar, 14C, 3H, 39Ar, and 85Kr ages of groundwater
for the range of 120 to 800 yr. In two sandstone aquifers in Germany underground production
could be excluded. In all cases maximum 85Kr and 3H ages were obtained, whereas 14C re-
sulted in minimum ages.
Case study 2: Discrepancy between 39Ar and 14C(DIC) ages

39
Ar water ages deviated by as much as one order of magnitude from the 14C ages of DIC in
groundwater from a leaky, confined sandstone aquifer in southern Germany. Underground
production of 39Ar in the sandstone aquifer was excluded. In spite of this, a high specific 39Ar
110
activity was found for groundwater of more than several 1000 yr of age. This was explained
by contributions of groundwater seeped from the shallow aquifer, becoming saturated in 39Ar
during the passage of the aquitard. The high thorium content causes a high underground pro-
duction (Geyh et al. 1984). This process may partly be responsible for other deviating 14C and
39
Ar water ages (Loosli 1992; Andrews et al. 1984).
5.2.2.7 KRYPTON-81
81
Kr is the long-lived radioactive isotope of the noble gas krypton and has a half-life of
230,000 yr. It is cosmogenically produced and considered to be a conservative tracer. Most
likely underground production is negligible. The concentration is given in dpm L−1 81Kr (Ro-
zanski and Florkowski 1979). The atmospheric 81Kr/Kr ratio is about 5 × 10-13 and independ-
ent from climatic conditions in the past.
Krypton is degassed from 15 m3 of groundwater and obtained by fractionated vacuum tech-
niques. The measurement is done by AMS. Contamination with modern atmospheric krypton
during sampling must be avoided (Volume I; Collon et al. 1999).
Occurrence
81
Kr enters the groundwater during the recharge by dissolution of atmospheric gases.
Application
81
Kr has the potential for dating old and saline groundwater with isolation ages of 50 ka to
1 Ma (Andrews et al. 1989; Collon et al. 1999). First datings of fresh groundwater was carried
out in the Great Artesian Basin, Australia (Collon et al. 1999). The results were compared
with 36Cl dates (Sect.5.2.2.5; Lehmann et al. 1999). The agreement is reasonable within the
age range of 1 000 000 yr though in both methods methodical problems may exists.
5.2.2.8 KRYPTON-85
85
Kr is the short-lived radioactive isotope of the noble gas krypton with a half-life of 10.76 yr.
The Kr specific activity is given in dpm L−1 of 85Kr. The detection limit is about
85
100 dpm L−1 of Kr, while the present level is around 5500 (Fig.2.1). As a chemically inert gas,
krypton offers nearly ideal possibilities for studying hydrodynamic movement and mixing of
groundwater into which it has diffused (Salvamoser 1986).
For the analysis 85Kr is extracted from about 100 L of groundwater within a vacuum chamber
and measured in a small proportional counter over a week (Volume I; Salvamoser 1986).
111
Chapter 5
Occurrence
The specific activity of 85Kr in the atmosphere has been monotonously increasing world-wide
since the beginning of the 1950s (Fig.2.1; Weiss et al. 1983). The primary source of 85Kr is
the nuclear reprocessing industry.
Applications
The 85Kr method allows to estimate mean residence times in the range of 10 to 50 years by
means of lump-parameter models. The results are more precise and less ambiguous than those
obtained by the 3H method (Salvamoser 1986) (Fig.5.41). Presupposition is the analysis of
unmixed samples. The limiting factor of this dating method is that the input function is not
precisely known (Forster et al. 1992), but analysing this isotope serves as a valuable supple-
ment to other tracer studies with CFC, SF6, 3H, 3He/3H.
10 1.0
Kr activity (Bq/ml)
H value (TU)
1985
3 H 0.8
A
3
85
10
0.6
0.4
5
0.2
85
Kr B
0 0
0 5 10 15 20 25 30 35 40 45 50
mean residence time (yr)
Fig.5.41 Theoretical relationship between the mean residence times (MRT) of 3H and 85Kr calcu-
lated with the exponential groundwater model for 1985 (Fig.3.5) and southern Germany.
The 3H value A yield two MRT values of 6 and 32 yr, the 85Kr value B yields an even
more precise MRT of 33 yr (after Salvamoser 1986).
Case studies are given by Forster et al. (1992); the potentials of the method are discussed by
Ekwurzel et al. (1994).
112
5.2.2.9 IODINE-129
129
I is radioactive and has a half-life of 15.7 Ma. It is cosmogenically formed in the upper at-
mosphere and anthropogenically by nuclear weapons tests (Paul et al. 1987). In addition, 129I
is present in gaseous emissions from nuclear reactors and reprocessing plants. Its concentra-
tion is usually given as atomic ratio to the stable 127I.
Samples are extracted from a few litres of water and measured by AMS (Volume I).
Applications
Hydrogeological applications are being proposed for the age range of 3 to 80 Myr (e.g.
Fabryka-Martin et al. 1987), 129I is applied for dating and tracing slow-moving groundwater
but also for the detection of young groundwater. As for the other environmental isotopes,
mixing of groundwater from different sources can be monitored (Fabryka-Martin et al. 1987).
The nuclear 129I bomb pulse was also detected (Paul et al. 1987).
In groundwater, the 129I/127I atomic ratio is mainly controlled by the rate of its recharge, the
leaching from the aquifer rock and of the amount of in-situ uranium fission. Except for under-
ground production, the 129I/127I ratio is quite constant.
Most probably due to the expensive analytical technique case studies are not known.
5.2.2.10 URANIUM/HELIUM AND K/Ar METHODS
238 235 232
The parent nuclides of the natural U, U, and Th decay series and many of the subse-
quent daughter nuclides (Volume I) are α emitters, i.e. producers of 4He. For example, during
the decay of 238U to 206Pb 8 helium atoms are produced, seven are produced by the decay of
235
U to 207Pb and 6 by the decay of 232Th to 208Pb. Hence, the helium content increases in a
closed system (e.g. in a confined aquifer) as a function of the uranium concentration and age.
Provided loss and gain of helium does not occur, the water age t can be calculated from the
production rates of 4He by the 235U, 238U and 232Th. If radioactive equilibrium in a rock has
been established, 1.19×10−13 cm3 STP He/µg U and 2.88×10−14 cm3 STP He/µg Th are pro-
duced annually (Volume I).
The helium content of groundwater is determined using 100 L samples. After degassing and
separation of the noble gases, helium is isolated by fractional distillation. The argon concen-
tration is used to correct for disturbing concentration of atmospheric helium.
Applications
The U/He method is recommended to determine groundwater ages between several thousand
years up to 400 Ma (Andrews et al. 1982). The growth of 4He can be used to estimate resi-
113
Chapter 5
dence times of up to 100 000 yr by comparing the Ne/He ratio of the groundwater to that of
atmospherically equilibrated recharge water (e.g. Bottomley et al. 1990) .
For groundwater dating, the uranium and thorium concentrations are roughly estimated via
their α activities, because the error due to loss of helium predominates. This is sometimes cor-
rected for by measurement of the 20Ne or 40Ar isotopes.
Case studies in England and Austria

The results showed a linear increase of the helium concentration with 14C groundwater age
However, this increase was larger than the expected excess by helium ingrowth from uranium
and thorium decay. This is obviously due to migration of helium from adjacent strata. The
3
He/4He ratio would have yielded information on the proportion of crustal helium, that is of-
ten degassed from fracture zones in active tectonic regions (Andrews 1985, Torgersen and
Clarke 1987).
An analogous dating method is based on the ingrowth of 40Ar by the decay of the frequently
occurring 40K (T1/2 = 1.28 Gyr) in rocks (Geyh and Schleicher 1990).
Case study: Great Artesian Basin, Australia

In the Great Artesian Basin the 4He concentration increases due to in-situ production, resulting
in a water age of up to 50 kyr . For ages above 100 kyr, an additional helium flux equivalent
to the entire crustal production has been taken into account (Torgersen and Clarke 1985;
Torgersen and Ivey 1985).
5.2.2.11 RADIUM/RADON DATING METHOD
222
Rn, the daughter of 226Ra, is a radioactive noble gas with a half-life of 3.6 days. Radium is
easily soluble in water and is gained by dissolution from rock and alpha recoil of 230Th. The
enrichment of 226Ra in groundwater approaches radioactive equilibrium after about 8000 yr
(Volume I) (Andrews et al. 1989), and theoretically allows dating up to 5000 yr (Hillaire-
Marcel et al. 1997).
Sampling for Rn is straightforward, and relatively simple counting devices can measure the
activities. Because of its short half-life, Rn must be analysed within a few days after sampling
to obtain the maximum measurement precision (Volume I).
Applications
The presence of the short-lived radon in groundwater always means that the source radium is
not too distant. A fast turn-over time of the groundwater in the aquifer system can be as-
sumed. Rn concentration approaches radioactive equilibrium in the aquifer after a few weeks.
Radon degasses completely after its discharge to the surface. This allows the detection of dis-
114
charge zones of groundwaters into rivers and lakes (e.g. Corbett et al. 1997). Also pumping
tests profit from radon measurements.
The radon method can also be applied in areas of karstic flow and in fractured rocks. If the Rn
concentration in groundwater is known and the Rn flux from the rock surface can be esti-
mated for a particular flow system, the mean fracture width in the system can be estimated
(Andrews 1991).
Case Studies: Artificial recharge

Hoehn et al. (1992) obtained residence times of up to 15 days for artificially recharged river
water in the aquifer used for the drinking water supply of the town Dortmund, Germany. Also
the proportion of admixed lake water and pipe leakage could be estimated.
In hydrothermal systems the [226Ra/222Rn] activity ratio has been shown to be a sensitive in-
dicator of low-temperature interactions of hydrothermal solutions with crustal rocks along the
Galapagos Rift. Information was gained about the mixing and flow history of these hydro-
thermal solutions (Dymond et al. 1983).
234
5.2.2.12 U/238U DATING METHOD
234
U is produced by radioactive decay (T1/2 = 247,000 yr) of 238U, the most abundant uranium
isotope.
Uranium is extracted from 2 – 10 L of groundwater either by precipitation with Fe(OH)3 or
aluminium phosphate or by adsorption on a strongly basic anion exchange resin (Gascoyne
1981). The activities of the uranium isotopes are determined alpha-spectrometrically or mass-
spectrometrically (Volume I).
Processes
In solid lattices 234U is bound less tightly than 238U. In the UVI+ state it is more easily dis-
solved (Petit et al. 1985). As a result there is a wide range of 234U/238U activity ratios between
0.5 and 40 in sediments and rocks and consequently also in groundwater with uranium con-
centrations between 0.1 and 25 ppb.
There are three zones of differing uranium chemistry. In the oxidising zone near the catch-
ment area, uranium occurs in the chemically stable, highly soluble +6 oxidation state. Here,
uranium acts as a conservative tracer and becomes enriched like 234U. This is due to α recoil
ejection of 234Th (from the disintegration of 238U: Volume I) at the rock-water interface and
the preferential leaching of 234U due to lattice radiation damage. Leaching of uranium from
the rocks of the aquifer results in a nearly linear increase in uranium concentration and in an
increase of the 234U/238U activity ratio (Rogojin et al. 1998).
115
Chapter 5
In the transition zone (downstream from the oxidising zone), both this ratio and the uranium
concentration pass through a maximum (Fig.5.42). Further downstream, in the reducing zone,
the 234U/238U activity ratio decreases slowly and more or less linearly as a function of the resi-
dence time, while the uranium concentration remains relatively constant at a very low level
(Pearson et al. 1983).
u ra n iu m c o n c e n tra tio n
equilibrium
between
dissolution input/putput precipitation
groundwater flow
ratio
U activity
U
234
238
selective
dissolution of 234U recoil decay of 234U excess
Oxydation Intermediate Reduction

Zone Zone Zone
Fig.5.42 Illustration of the changes of the uranium concentration and 234U/238U activity ratio in the
oxidising, transition, and reducing zones of an aquifer (after Osmond et al. 1983; Pearson
et al. 1983; Fröhlich and Gellermann 1986). The rise in the oxidation zone seems to be
suitable for water age determination (Fig.6.43; Rogojin et al. 1998).
Andrews et al. (1982) developed a model for closed systems to calculate the evolution of the
234
U/238U activity ratio and the uranium concentration of the water as function of the density,
the water-rock surface and the leachable uranium concentration of the rock. The width of the
fractures is the most sensitive parameter. The inhomogeneity of the corresponding distribution
does not allow absolute age determinations but yield valuable information on changes in the
flow regime.
Applications
The first attempt to date groundwater with the 234U/238U activity ratio was concentrated on
the oxygen-free part of aquifers. They were all not successful mainly due to complicated and
not yet fully understood chemical reactions of uranium with the aquifer rocks (Andrews et al.
1982). However, the 234U/238U activity ratio allows to study hydrodynamic mixing processes
116
from rock joints and flow regimes (Osmond et al. 1983). Additionally, it yields valuable in-
formation on the hydrogeological history of the aquifer. Values around one confirm that the
aquifer was not tectonically disturbed since many hundred thousands of years. Higher values
indicate relative young rock surfaces that are formed after earthquakes or tectonic movement
(Wakshal and Yaron 1974).
Groundwater datings of samples from the oxidising zone in a limestone and a sandstone aqui-
fer in Israel were successful. A reasonable agreement was found between 14C water ages and
those of the 234U excess (Rogojin et al. 1998) (Fig.5.43).
75
C activity (pMC)
70
65
14
60
55
50
45
40
0.4 0.6 0.8 1.0 1.2 1.4 1.6
Uexcess activity (dpm/L)
234
Fig.5.43 Exponential fit between the specific 14C activity of groundwater DIC from the Judea
Group aquifer, Israel, and the corresponding specific 234U-excess activity (after Rogojin
et al. 1998).
117
Chapter 5
118
6 APPLICATIONS TO HIGH-TEMPERATURE
SYSTEMS
In natural systems (gas-water-rock assemblages) variations in the isotopic composition occur

as a result of natural and anthropogenic processes. In geothermal systems mainly the isotopic
ratios of the four elements – hydrogen, oxygen, carbon and sulphur – are of interest (Vol-
ume I). These elements are important constituents of geothermal fluids and rocks.
Techniques based on natural variations of the isotopic compositions are now common tools in
the geochemical survey during the stages of exploration and exploitation of a geothermal re-
source. Two opposite properties of isotopes are used:
1) the change in the isotopic composition due to temperature-dependent, fast, incomplete or
uni-directional processes associated with water-rock interactions, steam separation, dilu-
tion and mixing, and
2) the constancy of the isotopic composition, largely unaffected by physical and chemical
processes during the movement of the water from the source area to the sampling point.
Isotopic tracing is used to unravel hydrological problems. Essential to the interpretation of the
change in the stable isotopic composition is our knowledge of the magnitude and temperature
dependence of the isotopic fractionation factors α between the common minerals and fluids
(gases and water).
Because of the high exchange rate between the liquid and vapour phases (Giggenbach 1971),
the isotopic composition can usually be assumed to be close to equilibrium and, therefore,
strongly governed by the isotopic equilibrium constant α. The determined isotope delta values
(Eq.2.1) δliqu and δvap for oxygen and hydrogen of the liquid and vapour phases are related to
α through
δ liq − δ vap ≈ ε lv = (α lv − 1) ⋅ 10 3 ‰ ≈ ln α lv (×10 3 ‰) (6.1)
The corresponding isotopic fractionation factors are compiled in Table 6.1. The thermody-
namic fractionation factors ε for both 2H and 18O for temperatures >100°C and < 100°C are
given by Truesdell et al. (1977) and Majoube (1971), respectively.
The fractionation factors α are obtained in three ways: (i) semi-empirical calculations using
spectroscopic data or methods of statistical mechanics, (ii) laboratory calibration studies, and
(iii) measurements of natural samples whose formation conditions are well-known or highly
constrained.
119
Chapter 6
Table 6.1 Temperature dependence of equilibrium isotope fractionation (ε values in ‰) between

liquid water and vapour (liq-vap). for 18O and 2H. The enthalpies of liquid water, H1iq, and
steam, Hvap, are given in (J/g). The vapour fractions xvap are given for fluid mixtures at
temperatures of first boiling at 300° and 260°C as a function of temperature: data >100°C
(Truesdell et al. 1977) and < 100°C (Majoube 1971).
Temp. ε(18Oliq-vap) ε(2Hliq-vap) H1iq Hvap xvap

0
C ‰ ‰ J/g J/g 300oC 260oC
0 11.68 112.3 0 2499 0.538 0.454

20 9.81 85.1 84 2538 0.513 0.428
40 8.22 64.5 168 2574 0.489 0.402
60 6.95 48.6 251 2610 0.463 0.374
80 6.03 36.8 355 2644 0.437 0.346
100 5.25 28.2 419 2676 0.410 0.317
120 4.53 21.5 504 2706 0.382 0.286
140 3.91 16.3 589 2734 0.352 0.254
160 3.37 11.7 676 2758 0.321 0.220
180 2.90 7.4 763 2778 0.288 0.184
200 2.48 3.5 853 2793 0.253 0.145
220 2.10 0.1 944 2802 0.215 0.102
240 1.77 -2.2 1037 2804 0.174 0.055
260 1.46 -3.6 1134 2797 0.126 0.000
280 1.19 -4.0 1236 2780 0.070 -
300 0.94 -3.4 1344 2749 0.000 -
320 0.70 -2.2 1462 2700 - -
340 0.45 -1.3 1594 2622 - -
360 0.19 -0.5 1761 2481 - -
Isotopic analyses of water from springs and wells yield information on the origin and the evo-
lution of geothermal fluids such as underground mixing between waters of different origin, on
effects of water-rock interaction (Chapter 4), on the isotopic geothermometry (Sect.6.1.2), and
on steam separation processes (Sect.6.2.2). Studies of the stable isotopic compositions of geo-
thermal gases may offer particular advantages with respect to studies of aqueous fluids, as the
gases and their stable isotopes will be less affected by near surface conditions. From the hy-
drochemical and isotopic composition of geothermal fluids information is gained on their ori-
gin, the recharge area and the flow patterns, on the temperature in the depth, the molar frac-
tion of vapour and vapour saturation. The cooling mechanism undergone by the fluid during
its ascent to the surface, including heat conduction, mixing with shallow groundwater and
120
High-Temperature Systems
steam loss, may be quantitatively evaluated. Last but not least the effects of re-injection and
the evolution of geothermal fields can be studied.
Criteria for the sampling strategy, information on sampling techniques and arising problems
are discussed by Paces (1991).
6.1 NATURAL PROCESSES

Local meteoric water from different geothermal areas has usually different isotopic composi-
tion. The mean annual isotopic δ values of precipitation are, in fact, largely related to the local
mean annual air temperature – the lower the temperature, the lower the content of heavy iso-
topes, corresponding to more negative δ18O and δ2H values in colder regions. This is also re-
flected in the altitude effect (Sect.5.2.1.1). The rainfall at a higher altitude is isotopically
lighter than in plains (Volume II). Last but not least, the continental effect may play a role if
the distance between the studied areas is large.
The origin of the groundwaters in high-temperature geothermal systems can be distinguished
by their geochemical and isotopic compositions. The following major water types are found in
geothermal systems worldwide:
• andesitic water – recycled sea water which has been subducted in regions with andesitic
volcanism or convergent plate volcanism (Giggenbach 1992). The δ18O and δ2H values
are about +10 ± 2 and +20 ± 10 ‰, respectively, while the chloride concentration is simi-
lar to that of the sea water,
• juvenile water – water coming from the Earth's mantle or core that has never been part of
the hydrospheric cycle. Because of mantle-crust interactions and subduction processes,
juvenile water has never been knowingly recognised,
• magmatic water – water that equilibrated with magma, regardless of its initial origin;
only the separated aqueous phase is magmatic water but not the water physically dis-
solved in the magma,
• meteoric water – originated from precipitation and of any age (rain, snow, ice, river wa-
ter, lake water, groundwater),
• ocean water or sea water – water in the open oceans which may enter the geothermal sys-
tems.
In most geothermal fields the isotopic composition of the water is relatively constant and
equals to that of the local meteoric water of the area. The δ18O often shows a characteristic
enrichment of the heavy isotope ("oxygen-isotope shift") with respect to the isotopic compo-
sition of the local meteoric water. Oxygen-isotope shift is the significant property of any geo-
thermal water in high-temperature systems. There are two physical processes which might
have produced such isotopic pattern:
121
Chapter 6
80°C
‰ separated vapor
δ2 H
L
120°C
MW
-30
-35
-40
220°C
-45
250°C
-50 residual liquid after

20%
vapor separation
40%
-55
-8 -7 -6 -5 -4 ‰
δ18O
Fig.6.1 Scheme of the shift in δ18O and δ2H values between the residual water and the vapour af-
ter separation.
1) liquid-vapour isotopic exchange at 220°C (Fig.6.1). At this temperature the two phases
at equilibrium have the same hydrogen isotopic composition while there is still
appreciable oxygen isotope fractionation. The heavy oxygen isotope becomes enriched in
the liquid phase. This phenomenon is only observed if the temperature of any water did
exceed 220°C in the area.
2) Oxygen-isotope shift due to isotopic exchange with minerals forming the rock matrix
through which the water has moved. Meteoric water that infiltrated to depth and formed a
geothermal reservoir is in isotopic disequilibrium with the rock: oxygen-isotope exchange
with the surrounding rocks results in an enrichment of the heavy isotopes with respect to
the initial water, controlled by the temperature of the geothermal reservoir. The fast con-
tinuous removal of heavy isotopes leads to a steady depletion in 18O of the rock (Clayton
and Steiner 1975; Fig.6.2). The δ18O value of a groundwater in isotopic equilibrium with
quartz or albite at 300°C is ≈ +3‰ and ≈ +4.5‰, respectively. A quantitative approach to
estimate the oxygen-isotopic shift in water was made by Taylor (1977).
Not all geothermal systems are exclusively fed by meteoric water. In some systems deep
fossil marine (connate) water may be present (e.g. Salton Sea, California). Systems near
the coast may be fed by both meteoric water and seawater (e.g. Svartsengi, Iceland).
Other geothermal fields may be fed by already evaporated waters. In these cases the phe-
nomenon of the oxygen-isotope shift is still visible on a horizontal alignment but the in-
tercept with the MWL will be less negative than that found for meteoric water.
122
Example:
The slope of the lines in the δ18O/δ2H plot is controlled by the temperature of steam separa-
tion (Fig.6.1): the black dot and the open circles represent the initial water and the residual
liquid after loss of 20% and 40% as steam, respectively. Dashed lines represent the isotopic
composition of the separated vapour.
6.1.1 WATER-ROCK INTERACTION AT HIGH TEMPERATURE
The thermodynamic equilibrium fractionation factor α for mineral-water 18O exchange reac-
tions increases with increasing strength of the oxygen bonds within a specific mineral. Matsu-
hisa et al. (1979) determined values of α as a function of temperature for the major "geother-
mal" minerals quartz, calcite and two feldspars (Giggenbach 1991). The highest fractionation
shows oxygen tightly bound in quartz; the fractionation factor for feldspars is considerably
smaller.
Fig.6.2 shows the isotopic compositions of oxygen and hydrogen for surface water and deep
thermal water and those of the corresponding altered and unaltered rocks from geothermal
systems. The δ2H values of the rocks equal that of the corresponding thermal water and do not
reflect those of any hydrous minerals actually present. Lines parallel to the meteoric water
line belong to fractions of andesitic vapour possibly contributing to the formation of the ther-
mal water. Fig.6.2 allows to compare the actually observed isotopic fractionation between
thermal water and the coexisting altered rock and that expected for isotopic equilibrium with
the major minerals at the measured temperature of the deep groundwater.
The rate of oxygen-isotopic exchange between water and rock decreases rapidly with declin-
ing temperature. The presence of an 18O shift in water is, therefore, usually taken as evidence
for a present or former high temperature (> 250°C) within the geothermal system. However,
the magnitude of any oxygen-isotope shift depends, beside on temperature, on the degree of
isotopic exchange and the proportions and δ18O values of the exchanging water and rock.
Case studies:
In Ngawha, New Zealand, the isotopic compositions of both altered and unaltered rock are
visually indistinguishable, pointing to a very low degree of water-rock exchange (Blattner
1985). The least diluted water has a δ18O value of around +6‰, which is about 5‰ lower than
that of the rock. The 5‰ difference in δ18O corresponds to an isotopic exchange temperature
of >350°C or 300°C if equilibrium with quartz or albite is assumed, respectively. The tem-
peratures encountered in a deep drillhole (2255 m) were 320°C. The large oxygen-isotope
shift of the water suggests that the relative proportions of water and rock involved in isotopic
exchange were small. The water has almost completely isotopically equilibrated with the pre-
dominant sedimentary rocks at the temperature measured over the deep parts of this essen-
tially stagnant system (Giggenbach and Lyon 1977).
123
Chapter 6
-15 -10 -5 0 +5 +10
local groundwater
δ2H
‰
0 most "shifted" thermal water seawater
unaltered rock
altered rock "andesitic"
Ngawha water
Tongonan
-50 igneous sedimentary

rocks
L Sagon Sea "basaltic"

MW water
shales sandstone
-100 t°C quartz calci albite
te
300° ap
art
Wairakei
hit
Ohaaki
Cerro Preto
Ngawha
400° deep e
Tongon
Sagon
temperature
500°
0.2 0.4 0.6 0.8 1.0
-15 -10 -5 -10 -5 0 εMW ‰

δ18O
Fig.6.2 Isotopic compositions of oxygen and hydrogen of surface water and deep thermal waters
and those of the altered and unaltered rocks from geothermal systems. The δ2H values of
the rocks correspond to those of the corresponding thermal waters and do not represent
those of any hydrous minerals actually present. Lines parallel to the meteoric water line
represent fractions of andesitic vapour possibly contributing to the formation of the ther-
mal water (after Giggenbach and Lyon 1977).
The reverse is observed at Wairakei. The δ18O shift is only 1.2‰ (Stewart 1978) which is in-
terpreted as an indication of large amounts of local meteoric water having passed through the
system (Clayton and Steiner 1975; Blattner 1985). The altered rocks are isotopically consid-
erably lighter (+2.5 to +5‰) than fresh rock (+7 to +9‰; Clayton and Steiner 1975). The
prevailing temperature within the Wairakei system is 260°C, corresponding to the observed
δ18O shift of about 8.5‰ for an isotopic equilibrium with the dominant mineral quartz.
Based on the likely component dominating the water-rock interaction process, the examples
of Fig.6.2 may be split into two groups:
1) essentially stagnant, rock-dominated systems with large δ18O shift, indicating adjustment
of the isotopic composition of water to those of the unaltered, generally sedimentary rock
(Ngawha, New Zealand; Salton Sea),
2) dynamic, fluid-dominated systems with comparatively small δ18O shift of the water. The
isotopic composition of the altered, generally igneous rocks reflect isotopic equilibrium
with the ascending groundwater.
124
The δ18O values of altered rocks, encountered at comparatively shallow levels in drillholes,
are thus likely the product of an interaction with waters already isotopically modified with a
δ18O shift. The dominant water-rock isotopic exchange, reflected by the isotopic composition
of the ascending groundwater, may already have occurred well below the drilled depth, possi-
bly within the zones of primary neutralisation of initially magmatic fluids or other deep, high
temperature zones of major water-rock equilibration (Giggenbach 1988).
This example is representative for many geothermal systems. The major processes responsible
for the δ18O shift in the water occurred well below the presently accessible depth. The actu-
ally observed wide range of the δ18O shift may, in many cases, simply reflect varying degrees
of dilution of a highly shifted end-member component by local meteoric groundwater.
6.1.2 ISOTOPIC GEOTHERMOMETRY

The gas component of geothermal fluids always contains carbon dioxide, methane, hydrogen
and, of course, water vapour . As the relative distribution of isotopes between the compo-
nents of the geochemical system is solely a function of temperature, any pair of these com-
pounds may in principle act as an isotopic geothermometer. In order to apply this, the equilib-
rium fractionation factor α of the isotopic exchange reactions must be known. The decipher-
ing of the thermal history of a geothermal system by any isotopic geothermometer depends
critically on whether or not isotopic equilibrium has been approached between the considered
species. The following requirements must be fulfilled:
1) in the temperature range of interest, the regular temperature gradient of the isotopic frac-
tionation factor α must be large enough to be easily measurable; mixing with the same
chemical species of different origin is to be excluded,
2) the isotopic equilibrium achieved in the geothermal reservoir is not altered at the sam-
pling point, the rate of isotopic exchange is slow enough to prevent isotopic re-
equilibration between the time of sampling and the time of analysis.
The following isotopic geothermometers are well developed:
12
CO2 + 13CH4 ↔ 13CO2 + 12CH4
C1H32H + 1H2O ↔ 1H2HO + C1H4

1
H2H + C1H4 ↔ 1H2 + C1H32H
1
H2D + 1H2O ↔ 1H2 + 1H2HO
C16O2 + H218O ↔ C16O18O + H216O

In systems where the concentration of gas species is too low for an isotopic temperature de-
termination, sulphate water/sulphate-sulphide isotopic exchange can be used for geothermom-
etry:
125
Chapter 6
S16O42- + H218O ↔ S16O318O2- + H216O

32
SO42- + H234S ↔ 34SO42- + H232S
If the temperature of the fluid remains constant sufficiently long to establish isotopic equilib-
rium, all geothermometers should give the same isotopic temperature. However, a change of
the fluid temperature towards the point of discharge will result in different isotopic tempera-
tures as indicated by the different geothermometers.
Example:
The kinetics of the reaction CO2–H2O is, for instance, very fast. Thus, the continuous isotopic
re-equilibration does not permit to determine the maximum temperature of the system. The
slowest reaction rate is for the CO2–CH4 geothermometer.
The best geothermometers are those for which the temperature coefficient of the fractionation
factor is large. Quartz and magnetite are a proper choice. Quartz is the most 18O rich, isotopi-
cally stable mineral and magnetite is the most 18O deficient mineral (Becker and Clayton
1976). On the other hand, quartz and feldspar are not suitable because the δ18O temperature
gradient is small and particularly feldspar is susceptible to isotopic exchange with post-
formational fluids.
There is a generalised temperature relation for all geothermometers for the component pair I
and II (T in Kelvin):
RI 10 3 B 10 6 C
ln α I− II = ln =A+ + 2 ‰ (6.2)
R II T T
In Table 6.2 the coefficients A, B and C of Eq.6.2 are given for the most common geother-
mometers.
Table 6.2. Coefficients of the most common geothermometers according to Eq.6.2.
temperature phase A B C
range (°C)
quartz–magnetite δ18O >500 empirical 4.8
CO2 –CH4 δ13C 100 – 400 theoretical -9.560 15.25 2.432
vapour -217.4 396.8 11.76

H2 O – H2 δ2H 100 – 400 theoretical
liquid -294.0 396.8 25.196
vapour -8.87 7.849 2.941
CO2 – H2O δ18O 100 – 400 theoretical
liquid 1961 18.29 7.626
Lloyd 1968 -5.6 0 3.251
SO42+– H2O δ18O 0 – 300 quartz Mizutani and -4.1 0 2.880
Rafter 1969
126
The isotope equilibrium fractionation factor of the carbon dioxide - methane isotopic geo-
thermometer at different temperatures (Fig.6.3) has been calculated from spectroscopic data
by Richet et al. (1977). Lyon and Hulston (1984) found that the temperature T in °C may be
estimated with a precision of about 2°C for a temperature range of 150 to 500 °C by:
15.79
T = −173 +
δ C CO 2 − δ13 C CH 4 + 9 ‰
13
where the δ values are small numbers (in ‰; 9‰ ≡ 0.009). This geothermal method has since
been applied to most of the major geothermal fields in the world (e.g. Lyon and Hulston 1984;
Nuti et al. 1985).
temperature (°C)
100 150 200 250 300 350
40
1000 x lnα
35
30
CO 2(gas)-CH 4(gas)
25
CO 2 (gas)-H 2O(vap)
20
CO 2(gas)-H 2 O(liq)
15
Fig.6.3 Isotopic equilibrium factor 100 × ln α of the CO2 – CH4 and CO2 – H2O geothermome-
ters as function of the temperature calculated by Richet et al. (1977).
As the 13C equilibration reaction is by several orders of magnitude slower than that of the sil-
ica geothermometer (Truesdell and Hulston 1980), the 13C temperature may probably reflect
earlier periods of the gas history than the present conditions of the exploited reservoir (Lyon
and Hulston 1984). The experimentally determined reaction half-lives of the CO2−CH4 geo-
thermometer are 3, 75, 3000 and 10×106 years at temperatures of 600°C, 500°C, 400°C and
300°C. Due to the slow rates, the temperature as determined by this geothermometer refers to
a depth of a cooling magma body well below the actual productive horizon.
127
Chapter 6
tem perature (°C

380
360
340
320
300
acidic water
280
260
rm
t he
is o
240
T(SiO 2)°C
T(CO 2 - CH 4 )°C
220
210 220 230 240 250 260 270 280 290 300
T(H 2 O-H 2 )°C
Fig.6.4 Isotope temperatures computed from the CO2-CH4 pair and the silica content (quartz) ver-
sus that of the H2O−H2 pair for the Palinpinon field, Philippines.
Case studies
Gunter and Musgrave (1971) applied the CO2–CH4 geothermometer to a vapour system in the
Yellowstone Park at Broadlands, Panichi et al. (1979) to the geothermal field of Larderello,
Italy, and Nuti et al. (1985) to the Phlegraean Fields. The temperatures obtained were usually
higher than observed probably due to conditions of equilibration temperatures at deep hori-
zons below the productive zone.
The water-hydrogen geothermometer based on theoretical data by Richet et al. (1977) is well
calibrated experimentally and theoretically and yields the best agreement between estimates
and observed underground temperatures in geothermal exploration. This may be due to the
relatively high exchange rate between water and hydrogen with less than one year to reach
90% equilibrium (Hulston 1973).
Case study: Palinpinon field, Philippines

Fig.6.4 shows the good correlation between the temperatures computed from the pairs
H2O-H2 and CO2-CH4 pairs for the Palinpinon field, Philippines, though the temperature
computed from the pair CO2-CH4 is by more than 70°C higher. The temperatures computed
128
from the silica content and the H2O-H2 pair agree well.
For the vapour-dominated field of Larderello the carbon dioxide-water geothermometer (Ri-
chet et al. 1977) yielded a temperature comparable to the one observed for the wellhead. This
is due to high reaction rate of the isotopic exchange.
The use of the sulphate-water geothermometer for water-dominated geothermal fields is well
proven. Two equations by Lloyd (1968) and Mizutani and Rafter (1969) are valid for the tem-
perature range of 0 to 300°C. The results differ by about 10°C. The corresponding isotopic-
exchange reaction rate is inversely proportional to the pH. Under neutral conditions the time
required to reach 90% isotopic equilibrium is 500 and 2 years at 100°C and 300°C, respec-
tively. Residence times of water in most geothermal reservoirs are larger.
The draw-back of this geothermometer is that mixing with sulphate-bearing, shallow ground-
water oxidation of H2S by atmospheric O2 and evaporation may modify the isotopic composi-
tion of the dissolved sulphate. In these cases the isotopic signature does no longer reflect that
of the deep geothermal sulphate.
‰
δ18O(SO4)
+20
100°C
+15
150°C
+10
seawater
200°C
+5
300°C
0
-10 -8 -6 -4 -2 0 ‰
δ O(H 2 O)
18
Fig.6.5 Oxygen isotope geothermometer based on the SO4–H2O pair (Mizutani and Rafter, 1969).
Open circles represent samples of geothermal water from the Zhangzhou geothermal
field, China (from Pang and Wang , 1995).
Case study: Zhangzhou field, China

The Zhangzhou geothermal field is located in a Quaternary fault basin with a Mesozoic gran-
ite basement. The deeply circulating thermal water has a temperature of 114°C at the well-
head and 122 °C at a depth of 90 m. The water is highly saline: 12g/L of total dissolved solids
129
Chapter 6
and 6g/L of Cl–. SO4 is mainly of marine origin. Fig.6.5 shows the geothermometry results
based on the δ18O values of the SO4–H2O pair. The estimated reservoir temperature (140–
150°C) (Mizutani and Rafter 1969) is in good agreement with that obtained by geochemical
modeling (Pang and Reed 1998).
6.1.3 TRACING THE ORIGIN AND HISTORY OF FLUIDS

Apart from geothermometry, the isotopic composition of stable isotopes in geothermal fluids
and their constituents may sometimes be used to trace their origin and history.
The 13C value of the carbon dioxide discharged from geothermal and volcanic systems, usu-
ally in the range of -8‰ to -3‰ can be distinguished from that of CO2 from organic sedi-
ments (<–20‰) or marine limestone (0 ± 1‰). The δ13C value of geothermal methane usually
ranges between -25 ‰ and -35‰, well above that of organically produced natural gas (–100
to –40‰). According to Galimov (1973) the carbon isotopic composition of methane depends
on the stage of coalification of organic matter. Methane with δ13C values less negative than
-35‰ would derive from carbonaceous matter of the late stage of catagenesis.
The δ34S values of H2S and SO4 of the geothermal discharge also contain information on their
origin. Sulphur of the primordial mantle, usually originated from basalts, has a δ34S ≈ 0‰
close to that of meteoritic sulphur (Rye and Ohmoto 1974). Sulphur from the crust has δ34S
values ranging from +2 to +6‰; the lower values correspond to andesitic sources and the
higher to rhyoliths (Giggenbach 1977). In Icelandic geothermal systems, where sulphur origi-
nates partly from seawater, higher δ34S values were found (Sakai et al. 1980).
6.1.4 MIXING WITH GEOTHERMAL FLUIDS

Deviations of the isotopic composition of geothermal waters from that the local meteoric wa-
ter usually results from mixing of waters of different origin. Admixture of highly saline for-
mation water or of connate water is frequently detected in lower temperature mineral springs,
but may also play an important role in high temperature systems situated in sedimentary
rocks. Another component may be isotopically ill-defined metamorphic water produced by
dewatering of sediments (White et al. 1973).
Case study:
For the vapour-dominated fields of Larderello, Italy, and The Geysers a schematic model was
designed of the main processes generating the observed isotopic compositions of the steam
and water (Fig.6.6). It may be also applicable to other geothermal fields.
Magmatic water is the most common source for geothermal systems with close volcanic-
magmatic associations. Because of the very small fractionation factor governing isotope ex-
change at magmatic temperatures, the δ18O value of any magmatic water is likely to be near
that of the parent magma (+5 to +10‰). The δ2H values of basaltic water associated with
130
magmatic activity along divergent plate margins are between –60‰ and –90‰ (Allard 1983).
Andesitic water typical for volcanic discharges along convergent plate boundaries has δ2H
values in the range of –10 to –30‰ (Sakai and Matsubaya 1977; Taran et al. 1988). The oxy-
gen shift is often only due to simple mixing of local groundwater with 18O enriched "mag-
matic" water (Fig.6.7; Giggenbach 1989).
Local Recharge of
Deep Sediments Local Magmatic (and Meteoric Water
and Metamorphic) Fluids
Connate Water Reaction, Heating
and δ18O Shift
Hydraulic Fracturing
of Shallow Rocks
Me l t i n g FRACTURED GEOTHERMAL
Me t a mo r p h i s m RESERVOIR
and D e w a t e r i n g
Ascent
Shallow Magmatic Intru
Mi x i n g
sio
n
ling and Crystallizati
o on
Co
Water-Rock Interaction
PRI MARY MAGMA LOCALLY CONTAMINATED and Mineralization
MA GMA
Local Magmatic (and
Metamorphic) Fluids
PHASE 1 PHASE 2 PHASE 3
Fig.6.6 Schematic model of the main proposed processes generating the observed isotopic com-
position of the steam at Larderello and The Geysers geothermal systems.
In volcanic, topographically highly variable mountainous areas, geothermal and meteoric wa-
ters may originate from different altitudes, and therefore may have different isotopic composi-
tions. A δ18O-chloride mixing-line may allow to recognise fresh groundwater as one end
member locally recharged at the highest parts of the associated volcanic structures and geo-
thermal water as the second end member derived from precipitation onto the surrounding low
altitude areas (Fig.6.7).
Assuming that the oxygen-isotope shift of a geothermal system along convergent plate
boundaries is due to admixture of andesitic water, its fraction xand can be estimated. The δand
value as assumed to be known (Xi; e.g. δ2H ≈ -20‰ and δ18O ≈ +10‰) and the δmet (Y) and
δtherm (XII) values for the meteoric water and the geothermal discharge, respectively, are
measured. The two-component mixing model yields xand (Eq.3.4).
131
Chapter 6
δ2H
Mediterranean
geothermic well discharge
0 magmatic water
fumarolic condensate
-10 local meteoric water
CONVERGENT
-20 MARGIN
degassed
bo
i natu magmatic water
-30 P
n
-40 gona
Ton
-50 ino
n
linp residual
Pa
-60 magmatic
water
-70
L
MW
-80 ba
l
C um
o
-90 vad
Ne
-100
-110
-14 -12 -10 -8 -6 -4 -2 0 +2 +4 +6 +8 +10 ‰

δ18O
Fig.6.7 The oxygen-isotope shift of the steam of high temperature fumaroles is often only the re-
sult of single two-component mixing shown for various areas.
TONGONAN
line
‰
geothermal well
ter
-30
3.7
discharge
wa
+1
ric
teo
O
xδ 18
-34
me
=8
al
2.6
loc
O-3
δ 2H
18
2xδ
-38 local
meteoric δ2 H = 1.2
water
-42
-46
-8 -7 -6 -5 -4 -3 -2 -1 0 ‰
δ OSMOW
18
Fig.6.8 Isotopic compositions of the steam of wells from Tongonan geothermal field, Philippines
(after Alvis-Isidro et al. 1993).
Case study:
The slope of the δ2H/δ18O line is so low that is explained by mixing rather than by evapora-
tion because of the high temperature (250 – 300°C) of the water pumped from the wells.
132
According to Eq.3.4, the fraction xand in the least diluted waters from El Ruiz, Amatitlan,
Wairakai, Philippines, and Ohaaki, Japan, is equal to 5 to 12%, to about +20% for Zunil and
Miravalles, and to about +40% for Tongonan, Philippines.
Further downstream entries all parameters varied quite regularly: the δ18O value shifts to-
wards less negative values, the gas/steam ratios decreased strongly and the computed
temperature increased. The molal steam fraction dropped to nearly zero, corresponding with a
liquid saturation of almost 100%. The presence of liquid water in the matrix rock with a tem-
perature of up to 250°C is interpreted as condensate layer. According to the isotopic composi-
tion of the steam from the gas cap and that of the condensate layer, steam separation occurs at
about 200°C. Below this layer fluids of different characteristics belong to a typical two-phase
reservoir: (i) a gas/steam ratio of more than 3 times the value observed for the condensate
layer, (ii) an increased steam molal fraction indicating liquid saturation as result of mixing be-
tween condensate and the two-phase layers. The isotopic composition corresponds to that of
the local meteoric water.
‰
δ2HSMOW
0
SHOWASHINZAN
-10 fumarolic condensate
-20 convergent margin

L
magmatic waters
MW
-30
ing
mix
-40
ng
ixi
local m
-50
meteoric
water
-60 δ18O shift
-10 -8 -6 -4 -2 0 +2 +4 +6 +8 +10 ‰
δ18OSMOW
Fig.6.9 Isotopic composition of the high-temperature fumarolic steam ("Convergent margin

magmatic waters ") from Showashinzan volcano, Japan.
Case study: Showashinzan volcano, Japan

The isotopic composition of the high-temperature fumarolic steam from Showashinzan vol-
133
Chapter 6
cano is consistent with a δ18O shift due to water-rock interaction and an admixture of local
convergent margin andesitic water (Fig.6.9). A similar situation exists in the vapour-
dominated fields of Larderello, Italy, and The Geysers.
Fig.6.10 shows a schematic cross section of the Volcano Island, Sicily, with fluid types and
mixing from the hydrothermal system. Fig.6.11 shows the isotopic compositions of oxygen
and hydrogen of water samples from shallow wells and of the condensate of high temperature
fumaroles (up to 500°C) located at the rim of the crater for different years of observation. The
changing temperature is explained by dilution of the magmatic vapour supported by the tem-
poral shift of the δ18O values. The two-component mixing concept of a parent geothermal wa-
ter and locally recharged freshwater is supported by the linear relationship between tritium
values and chloride concentration well as the δ18O and δ2H values (Fig.6.12).
fumaroles
t
t=1 =90°
40
°
groundwater groundwater
steam
seawater steam-heated heating
n waters bo
ilin geothermal mixing
sitio g
po reservoir
l de
ra
ne
mi water-rock interaction magmatic
ca. 5 km
and neutralization vapour
HCl magmatic
water
sediments
an
and connate wat d
ents r er
sedim te
te wa
conna MA GMA
heat flow of the earth
Fig.6.10 Schematic cross section (not to scale) showing fluid types, processes and regions of fluid
mixing in the volcanic hydrothermal system of Vulcano Island.
6.2 ANTHROPOGENIC PROCESSES
6.2.1 STEAM LOSS

Boiling and steam loss are the most important cooling processes in geothermal systems with
large surface discharge. The amount of heat loss by a phase shift is greater than that by con-
134
duction which is often hindered by mineral deposition in the upflow paths of the descending
cold groundwater. In low temperature environments two physical processes are mainly re-
sponsible for isotopic fractionation:
1) subsurface evaporation and
2) evaporation on the surface.
Subsurface evaporation has been discussed by Giggenbach (1971) and Truesdell et al. (1977).
In natural systems the convective rise of hot water to the surface produces steam as pressure
decreases. Adiabatic steam production in its turn determines a decrease in temperature. The
resulting isotopic compositions of the steam and water phases depend greatly on the mode of
the phase separation. "Single-step steam separation" shows the largest isotopic effect. During
fluid ascent steam coexists with the liquid phase . The two are separated at the surface in the
well at the separator. This conception is also valid for hot springs and fumaroles. "Continuous
steam separation" requires a continuous steam removal immediately after its formation
(Henley et al. 1984). The isotopic fractionation effect is minimal.
‰ connate water
δ2H
SHALLOW WELLS
contaminated magma
+15 groundwater
well w2 seawater
steam-heated water
+5 magmatic vapour
FUMAROLES
1978 -- 1988 geothermal
1989 - 1990 parent
-5 88 1985 deep magmatic
19
contribution
ing 985 1979
L
mix
MW
1
-15
er 9 typical
wat 197 "andesitic
al
rm water"
e
-25 th
-35 deep "primary

magmatic water"
cold
groundwater
-45
-8 -6 -4 -2 0 +2 +4 +6 +8 +10 +12 ‰
δ18O
Fig.6.11 Isotopic compositions of the water from shallow wells (triangles for the condensate of the
Gran Catere fumaroles). Three mixing lines are shown for different years of observation
of "primary magmatic water" and andesitic water (Giggenbach 1992). The isotopic com-
position of the condensate of the Gran Cratere fumaroles for the period 1978 – 1990 re-
flects changes in the discharge temperature due to dilution of magmatic vapour (Taylor
1974).
135
Chapter 6
5000 5000
geothermal geothermal
Cl (mg/kg)
(a) geothermal
water (b) water (c)
water
4000 1988 4000
3000 3000
2000 2000
1000 1000
140° 140°
evaporation evaporation
0 0
-40 -30 -30 -20 ‰ -10 -6 -4 -2 0 +2 ‰ 30 20 10 0
δ2H δ18O H value(TU)
3
Fig.6.12 Cl– concentration versus δ2H, δ18O and 3H values in well water of the Volcano Island, Sic-
ily. The grey open circles representing the isotopic compositions of the parent geothermal
water have been obtained by linear extrapolation to zero TU.
Both separation modes can be considered as extreme situations. Many examples of intermedi-
ate natural processes have been discussed for Yellowstone (Truesdell et al. 1977) and El Tatio
(Giggenbach 1978) though single-step steam separation was predominant. Intermediate ef-
fects are also called "multi-stage steam separation" (Henley et al. 1984).
The isotopic composition of the separated steam (δvap) and the water (δliqu) for the single-step
process may be evaluated by the isotope balance equation (Eq.3.3) with the proportions xvap
and xliq:
δ vap ⋅ x vap + δ liq ⋅ x liq = δ vap ⋅ x vap + δ liq (1 − x vap ) = δ init
(6.3)
with x vap + x liq = 1
where δinit represents the initial isotopic composition of the single liquid phase fluid before
separation of the steam fraction xvap. At the initial stage (before evaporation) xvap can also be
computed by the corresponding enthalpy (H) balance of the fluid and for the separation tem-
perature of the water and steam.
H init − H liq
x vap = (6.4)
H vap − H liq
Combining Eq.6.1 with Eq.6.3 allows to calculate the isotopic compositions δliq and δvap of
136
the liquid and vapour phases for different fractions xvap of steam after its separation (see also
Eq. 6.7).
Example:
Underground liquid-vapour separation in liquid dominated systems effectively is a single-step
process (Giggenbach and Stewart 1982) as isotopic equilibration between water and steam is
rapidly established (Giggenbach 1971). The slope s of the relationship between δ18O and δ2H
can be approximated by
(α 2 H − 1) ⋅ (δ 2 H + 1)
s= (6.5)
(α18 O − 1) ⋅ (δ18 O + 1)
We assume an infiltration of meteoric water into the underground. The initial δ18O and δ2H
values are –6.5‰ and –42‰, respectively. The calculated δ18O and δ2H values after steam
separation at different temperatures are compiled in Tab.6.3. An example is given. In the
δ18O/δ2H plot the delta values of the residual liquid and separated vapour after loss of a frac-
tion of steam at 80°C lie on a line with a slope 5.8. The δ18O value of the residual liquid will
be -5.3‰ and -4.1‰ in the case of 20% or 40% of separated vapour, respectively.
Table 6.3 Change of the δ18O and δ2H values by water/steam separation as function of the tempera-
ture and the percentage of the separated steam fraction.
temp residual liquid slope separated steam fraction

o
C δ18O δ2H 20% 40% 20% 40%
‰ ‰ δ18O δ2H
80 6.03 36.8 5.8 -5.3 -4.1 -34.8 -27.6
120 4.54 21.7 4.6 -5.6 -4.7 -37.7 -33.4
220 2.10 0.1 0.0 -6.1 -5.7 -42.0 -42.0
260 1.46 -3.6 -2.4 -6.2 -5.9 -42.7 -43.5
Column 1 contains the separation temperature of the steam, columns 2 and 3 list the δ18O and
δ2H values of the residual liquid, respectively. Column 4 compiles the slope and the columns
5 and 6 as well as 7 and 8 contain the δ18O and δ2H values for separated steam fractions of
20% and 40%, respectively.
At 220°C and above the fractionation factor of hydrogen isotopes shows an "inversion" while
the isotopic fractionation of oxygen further decreases.
137
Chapter 6
Truesdell et al. (1977) and Henley et al. (1984) developed an approach for the more complex
situation of a continuous steam separation to compute the isotopic enrichment of residual liq-
uid water with respect to initial water. The isotopic composition of the residual liquid water
differs for the single step and continuous steam separation modes if the initial and final tem-
peratures differs by more than 150°C.
While the subsurface evaporation is governed by the equilibrium constant α, evaporation

from surface water is controlled by kinetic fractionation (Volume I). The isotopic composi-
tions of rapidly flowing thermal water as usual in thermal springs are not greatly affected by
evaporation. During the initial exploration phase, steam-heated pools may be present of which
isotopic composition is indirectly related to those of the deep supply water. Steam-heated wa-
ter is also common in the superficial zone of geothermal systems where boiling occurs in the
reservoir as indicated by high sulphate to chloride ratios and low pH. This water originates
from the condensation of rising steam from the underlying reservoir into deep groundwater.
This steam- heated water may boil and lose mass. A steady-state model allows to calculate the
isotopic composition.
A pool with initially cold shallow groundwater is heated by geothermal steam. The isotopic
composition of this groundwater (δinit) and that of the water leaving the pool (δdis) allow to
calculate the delta value of the steam (δvap) entering the pool for heating:
δ vap = δ init + (δ dis − δ init ) ⋅ x vap + (1 − β) (6.6)
where xvap is the fraction of vapour entering the pool (considered equal to that leaving the
pool) and β is the overall fractionation factor given by
n
 D H2 0 
β = α liq − vap ⋅  

 D isot 
where α is the equilibrium fractionation factor between liquid water and steam, D /Disot the ra-
tio between the diffusion coefficients in air of H2O and 1H2HO or H218O, respectively. n is an
exponent related to the Rayleigh distillation. For a temperature below 100°C α = 1.024 and
= 1.028 for O and H, respectively (Merlivat 1970). The exponent n ranges from 0 (equilib-
rium) to 0.578 for kinetic fractionation (Stewart 1975). More complex models considering
Rayleigh distillation and even more complicated processes are discussed by Giggenbach and
Stewart (1982).
6.2.2 UNDERGROUND LIQUID-VAPOUR SEPARATION PROCESSES

During the temperature rise to values in excess of 100°C the vapour pressure will at a certain
stage exceed the hydrostatic pressure, and the geothermal water will start to boil. The associ-
ated vapour separation process is accompanied by isotopic fractionation. The heavy isotopes,
2
H and 18O, become enriched in the liquid phase and the separated vapour phase becomes iso-
138
topically depleted. For deuterium this holds true for each temperature below 220°C. At higher
temperature 2H remains preferentially in the vapour phase.
Apart from the temperature, the isotopic compositions of the separated liquid depend on the
fraction xvap of the formed vapour. and can be calculated for single mode separation of vapour
at a given temperature, continuous vapour separation, a separation process which is described
by the Rayleigh fractionation or isothermal batch evaporation (Giggenbach and Stewart
1982). The latter process is active for sudden decompression or in vapour-dominated systems
with small fraction of liquid suspended in pores (D'Amore and Truesdell 1979).
Case Studies: Wairakei Geothermal Field, Philippines

Fig.6.13 illustrates the theoretically expected and actually observed effects of vapour separa-
tion in natural water and steam discharged from the Wairakai geothermal field (Giggenbach
and Stewart 1982).
‰
δ18 O
-30
steam-heated groundwater
primary steam from 100°
diluted deep water 760° GVP
ion
-40 730° dilut
140°
secondary steam from 180°
steam-heated groundwater 260° 220°
primary water
local groundwater after single-step
-50 original deep water steam loss
180°
primary steam from

° 140°
-60 140 undiluted deep water
° 100°
100
-70 L WAIRAKEI
MW
-11 -10 -9 -8 -7 -6 -5 -4 ‰
δ2H
Fig.6.13 The isotopic compositions of steam and water formed from an initial 260°C warm deep
groundwater at various temperatures after dilution with local groundwater from the
Waraikai geothermal field, Philippines. Single-step vapour separation is assumed. Open
circles are data points for fumarolic steam samples (Giggenbach and Stewart 1982).
The isotopic compositions of the residual water after removal of steam at 220°, 180°, 140°
and 100° from a deep water with an initial temperature of 260°C are shown by the curved line
marked "primary water" after single–step steam loss. The effect of dilution by surface water is
indicated by lines connecting the separated water to the local groundwater. The isotopic com-
139
Chapter 6
position of the dominant natural chloride-water discharge from the Wairakei field, Geyser
Valley Pool, GVP, prior to exploitation, plots on the steam-loss line at a temperature of about
135°C. For such a surface discharge, a separation temperature of about 100°C would be ex-
pected. Preservation of the deeper separation composition is likely to be due to some conduc-
tive cooling, reducing the amount of steam produced from the boiling pool.
The lower δ values for fumaroles point to secondary processes as e.g. steam separation from
pre-diluted water. In this case, the separation temperature is likely lower, though the isotopic
composition of the water before steam separation is shifted to lower δ values (connecting "di-
lution" line between the deep primary water and local groundwater). The line "primary steam
from diluted deep water" represents the isotopic composition of the steam formed from a pre-
diluted water. Most of the data points fall within the area representing steam from undiluted to
diluted primary water. The few samples with even stronger isotopic depletion represent sec-
ondary steam separated from steam-heated bicarbonate water frequently formed at the mar-
gins of geothermal fields (Hedenquist 1990).
Fig.6.14 shows the effect of steam loss at 280 - 290°C from a primary deep geothermal water
in the Cl-/δ18O diagram for some wells of the Berlin geothermal field, El Salvador. Mixing
with fresh shallow groundwater is obvious.
The above examples demonstrate the wide range of isotopic compositions of natural geother
mal surface discharge. It may come from a single source of deep groundwater and caused by
underground steam-vapour separation and dilution. The wide range provides the basis for
apowerful tool to reconstruct deep hydrological processes active within a geothermal system
during the early stage of exploration when only surface water can be sampled and analysed.
δ18O
‰
-1
deep geothermal water
-2
-3
steam loss
-4 at 200 - 290 °C
e
li n
ng
-5
ix i
m
-6
-7
-8
0 1000 3000 5000 7000
chloride (mg/L)
Fig.6.14 The relationship between chloride concentration and δ18O value of the geothermal fluid
from the Waraikai geothermal field, Philippines, may be interpreted as mixing between
shallow groundwater and deep andesitic groundwater.
140
Geothermal groundwater of high temperature cools as it rises to the surface by conduction,

mixing and boiling. Each of these processes is separately traced by the isotopic (and chemi-
cal) composition. The process of boiling can be easily monitored by a change in the isotopic
composition.
Conductive heat loss. During ascent of liquid water with conductive heat loss the hydrogen
composition is not changed as there is no other hydrogen containing material . The oxygen
isotopic composition may slowly change due to water-rock interaction with oxygen bound in
the rocks (e.g. carbonate, sulphate) at a temperature well below 220°C. Conductive cooling is
assumed to be important for springs with discharge rates of less than 1 L/sec.
Mixing with cold water. Admixture of cold groundwater can be identified by an isotopic
composition falling along the meteoric water line. It is very common in hot spring systems be-
fore or after boiling. The source may be locally recharged groundwater of large depth and
from far away (up to 100 km).
Boiling and steam loss are the most important cooling processes in high temperature geo-
thermal systems with large surface discharge. The loss of heat is greater than by conduction,
and because mineral deposition seal supflow paths from invading cold groundwater.
For the calculation of the effect of single stage separation at spring water at a temperature of
100°C we assume a temperature of the reservoir water of 260°C and δ18O and δ2H values of
-5‰ and -40‰, respectively. From Table 6.1 follows 1000×ln α100°C equals 5.24 and 27.8
for oxygen and hydrogen isotopes, respectively.
The enthalpy and isotopic balances are given analogous to Eq.3.3 by:
* * *
H 1260°C = x vap ⋅ H 1100°C + (1 − x vap ) H 1100°C
δ1260°C = x vap ⋅ δ1100°C + (1 − x vap ) δ1100°C
Using the figures in Table 6.3 we calculate the steam fraction xvap at the surface by combining
the isotope balance equations with the equations derived earlier and obtain
δ1iq (100°C) = δ1iq (260°C) + x vap ln α (×1000‰) (6.7)
From the value of xvap and lnα we obtain δ18Oliq(100°C) and δ2Hl iq(100°C) of -3.33‰ (≡
−0.00333) and -31.3‰ (≡ −0.0313), respectively.
6.2.3 ISOTOPE TECHNIQUES IN RE-INJECTION STUDIES

The chemical composition of the waste water produced in large quantities from geothermo-
electric power-plants is such (high concentrations of ammonia, boric acid and sulphides) that
it cannot be discharged into the runoff of rivers. The problem of getting rid of these polluting
effluents has been solved by re-injecting the waste water back to the underground at some
suitable sites of the geothermal field. This procedure may also be useful for an artificial re-
141
Chapter 6
charge of the field. It partly compensates the natural fall of the reservoir pressure caused by
the negative hydrological balance between exploited groundwater and the often limited natu-
ral recharge.
In order to avoid eventually irreversible negative effects of re-injection in the field, some ex-
periments must be made prior launching the full-scale re-injection. Apart from radioactive
isotopes the stable isotopes of oxygen and hydrogen are suitable to trace quantitatively the
underground pathways of the re-injected waste water within the geothermal field (Nuti et al.
1981).
The turbine steam is partly condensed in cooling towers but a considerable part is lost to the
atmosphere. During this process the residual water is enriched in the heavy isotopes 2H and
18
O. As the isotopic composition of the injected water differs from that of the local groundwa-
ter the system can be systematically monitored throughout the re-injection test.
The isotopic compositions of the undisturbed groundwater are variable with time due to a
variable contribution of the steam sources (condensate layer, two-phase layer) and areal fluid
redistribution. In previously non-exploited areas, the isotopic effect of re-injection are over-
lapped by the natural temporal evolution of the δ18O value towards more negative values, and
of the gas/steam ratio (= steam saturation G/S) towards higher values (Box et al. 1987).
‰
δ2H
-35
-40
A'
-45
-50
A
+
‰
+ A''
δ18O
B'
-3
-4
-5
B
-6 +
+ B''
C
800
G/S
600 C'
400
200
1979 1980 1981 1982 1983 1984 1985 1986 1987
Fig.6.15 Temporal and re-injection induced variations of the δ18O and δ2H values as well as the
G/V ratio. Lines A, B and C (open circles) represent the variation in wells not affected by
re-injection. Lines A', B' and C' (full circles) represent the variation in wells affected by
re-injection. Lines A'' and B'' represent the variation induced by cooling.
142
The isotopic compositions of the other component of the admixed injected waste water is also
variable (mass loss in the cooling tower and isotopic fractionation due to partial re--
evaporation of re-injected water). Under such a complex situation it is likely to obtain data
which do not fit simple straight mixing lines (Fig.6.15).
2
H is the parameter least affected by fractionation (fractionation factor α is close to 1 at boil-
ing temperatures near 220°C), by any kind of water-rock interaction, or by areal fluid dis-
placement. As a consequence, δ2H values allow to evaluate the relative contribution of the
original vapour and injection-derived steam. They also trace the flow paths of steam produced
by injected water and the relative contribution to production of this steam (Nuti et al. 1981).
D'Amore et al. (1988) studied the following phenomena in a reservoir:
1) mixing of original steam with re-injected steam, and the isotopic fractionation during
steam production from re-injected water,
2) effects of fluid redistribution (displacement), where areal gradients of the isotopic com-
position and gas/steam ratio exist, and
3) cooling of the rock matrix.
All these processes have to be taken into account when the proportion of the injected water is
estimated for the surrounding wells. Depending on the number of measurements available
δ18O/δ2H and gas/steam/δ2H diagrams may permit a quantitative calculation of the contribu-
tion of steam from the different sources and an assessment of eventual cooling effects in the
reservoir matrix.
Case Studies: Larderello geothermal field, Italy

The temporal variation of the isotopic compositions and the gas/steam ratio in the Larderello
geothermal field during three experiments of re-injection is shown in Fig.6.16. These experi-
ments yielded mixing lines for the δ2H and δ18O values of the initial water and those of the
steam separated from the re-injected condensate (Fig.6.17).
6.2.4 VARIABILITY OF THE ISOTOPIC COMPOSITION IN GEOTHERMAL

FLUID
In any geothermal field the isotopic composition of the discharged water and/or steam varies
locally. Rain water infiltrated through permeable rocks, spring water and groundwater
pumped from wells are usually of meteoric origin. Along the underground flow in a geother-
mal field the δ18O value of the groundwater may increase due to progressive isotopic ex-
change with increasing distance from the recharge area. Differences in the chemical and iso-
topic compositions at different localities in the Larderello geothermal field are interpreted in
such a way for the lateral steam flow from central boiling zones (upflow points) toward the
edges of the system before the start of exploitation.
143
Chapter 6
Fig.6.18 shows a scheme of the lateral steam movement and condensation in vapour domi-
nated systems. During this lateral flow partial condensation occurs as well as conductive heat
loss through the surface. Gases are concentrated in the residual steam, while volatile salts are
slowly removed into the condensate (H3BO3, HCl). This process is modelled as a Rayleigh
‰
δ2H
-10
W1
-20 W2
-30
-40
10
G/S (%we ig ht)
5 W1
W2
0
/h)
200
flow rate (m
3
100
0 I II III
1979 1980 1981 1982
Fig.6.16 Temporal variation of the δ2H and δ18O values as well as of the gas/steam ratio monitored
in two wells W1 and W2 of the central area during and after re-injection tests. Undis-
turbed pre-reinjection values and low-rate of injected water are shown. I, II and III refer
to the three re-injection periods.
condensation obeying the equation
1
 rvap  k −1
c vap = c init ⋅  
 (6.7)
 rinit 
144
where cvap/cinit is the ratio of the concentration of a steam component to its original concentra-
tion at any point, and rvap/rinit the ratio of the corresponding fractions r of condensed steam. k
is the distribution coefficient of the component between steam and water (cvap/cinit).
‰
δ2H +20
Period III f res
T(°C) +240 .8 .6 .4
+220
RC
0 +200
7
3
6
-20 5 2
2 4
1
-40 W1 8
-4 -2 0 +2 +4 +6 +8 ‰
‰ δ O
18
+20 Period I
δ22Η fres
T(°C) +240 .8 .6 .4
+220
0 RC
+200
3 4
-20 6 5
2
1 7
-40 W1
8
-4 -2 0 +2 +4 +6 +8 ‰
δ 18 O
Fig.6.17 Variation of the δ18O and δ2H values of the fluid pumped from well Wl during three suc-
ceeding test periods shown in Fig.6.16 for well RC (central area). The different isotopic
compositions of the monitored waters are reported together with the theoretical isotopic
pattern of the steam produced by re-injected water, assuming continuous steam separation
at depth:
δvap = δinit + {(1—fres)α − t –1}.
Since the actual evaporation temperature and the fraction of residual water are unknown,
calculations were made for three different temperatures and fractions fres of residual liquid
water after boiling. Progressive numbers indicate the chronological sampling order during
the test (open symbols) and after the test (solid symbols).
145
Chapter 6
For δ18O the equation of condensation can be expressed as:
 r  αliq − vap −1 
=   − 1 × 1000‰
vap
δ vap − δ liq
 rliq  
 
Fig.6.19 shows the calculated results (Eq.6.7) for k = 0.05 to 1000. The magnitude of the
variation at Larderello geothermal field, Italy, (-3‰ in δ18O, 5 and 3 times in CO2 and NH3
concentrations) suggests that the productive field is limited by excessive liquid water and
non-condensable gas after 80% of the original steam flow has condensed. At The Geysers, a
7‰ decrease in δ18O and a 17 times increase in CO2 are expected at 95% condensation.
Fig.6.20 shows the observed concentration profiles of different species in steam along a line
through the northern Larderello Field, far from recharge areas. It reflects the disturbance due
to the well discharge.
heat loss by conduction heat loss by conduction
caprock
vapour
dominated
reservoir
brine
steam
main heat source
liquid water
Fig.6.18 Lateral steam movement and condensation in vapour-dominated geothermal systems.
Another common process in geothermal spring systems is mixing of the ascending geothermal
water with varying proportions of local groundwater. The former will be enriched in heavy
isotopes because of the δ18O-shift and/or steam loss as described before. An additional proc-
ess resulting in isotopic changes is artificially caused by re-injection of waste water from geo-
thermal power plants (Sect.6.2.3).
A variation of the isotopic composition of the steam with time is observed in exploited geo-
thermal fields mainly due to re-injection. It may be, however, also be caused by the mode of
fluid production. As in geothermal fields strong spatial variation of the isotopic composition
is observed, the widening of the area affected by steam production has the same effect.
146
The δ18O/Cl relationship of the waters in the Palinpinon field, Philippines (Fig.6.21) after sev-
eral years of exploitation reflects mixing processes due to re-injection of water, admixture of
meteoric water and acidic-SO42+ water.
k = 1000-50
6
Co/C
4 10
5
2
1.5
1 k = 1.0
0.75
0.5
0.25
0.05 0.1
0
0 1
steam fraction condensed
Fig.6.19 Results obtained from the Rayleigh condensation equation for k=0.05 to 1000 for the
Larderello Geothermal Field.
‰
0
δ18O
extrapolation to
magmatic water
-2 mixing with B C
acid-sulphate + + + + + +
water +
+ + + +
+ + + +
-4
steam separation
at 220°C
-6
upflowing parent meteoric water
geothermal fluid x injection water at two sites
mixing with
-8 meteoric water exploitation well at two sites
A + mixing with injection water
-10
0 2000 4000 6000 8000 10 000 12 000
Clres (mg/kg)
Fig.6.20 Measured and calculated vertical distributions of the δ18O value, the gas/steam ratio, the
temperature T and the proportion xvap.
147
Chapter 6
During drilling in exploited and previously non-exploited parts of The Geysers geothermal
field, the steam chemistry was monitored in six new wells at different depths down to 2000 m.
Samples were taken from steam entries at non-connected fractured zones. A vertical zonation
of the chemical and isotopic compositions in the reservoir fluids were found (Fig.6.22).
In the short interval of the first steam entry, both δ18O and δ2H values were more negative
than in the surrounding productive wells. The gas/steam ratio and the temperature were meas-
ured at the well head. The molal steam fraction was computed from the chemical gas analyses
(D'Amore and Truesdell 1985). The gas/steam ratio was at least one order of magnitude
higher than that of the fluids normally delivered by productive wells. The calculated tempera-
ture was < 200°C, while the molal steam fraction was close to 100%, indicating an extremely
low liquid saturation. The reactive gases are in chemical equilibrium at relatively low tem-
perature. This observation has been interpreted as a local upper gas cap.
gas/steam Cl
NH3 δ18O
H3BO4 mmol/L ‰
6 -2
δ18O
5 -3
4 -4
3 -5
0 1 km
1
well 80
north-west east
Fig.6.21 Chloride/δ18O relationship of geothermal water reflecting admixture of ascending parent

water (near B), dilution and steam separation prior to exploitation of The Geysers geo-
thermal field. The origin of the parent water is mixed meteoric (indicated by detectable
3
H) and magmatic waters (trend line AB: δ18O=8.16×10-4Cl–7.9). During exploitation
mixing between geothermal fluids, injected water (trend line BC: δ18O = 3×10-4 Cl – 5.8),
and acidic SO4 fluids occurs.
Further down steam entries all parameters varied quite regularly: the δ18O value shifts towards
less negative values, the gas/steam ratios decreased strongly and the computed temperature
increased. The molal steam fraction dropped to nearly zero, corresponding with a liquid satu-
ration of almost 100%. The presence of liquid water in the matrix rock with a temperature of
up to 250°C is interpreted as condensate layer. According to the isotopic composition of the
148
steam from the gas cap and that of the condensate layer, steam separation occurs at about
200°C. Below this layer fluids of different characteristics belong to a typical two-phase reser-
voir: (i) a gas/steam ratio of more than three times the value observed for the condensate
layer, (ii) an increased steam molal fraction indicating liquid saturation as result of mixing be-
tween condensate and the two-phase layers. The isotopic composition corresponds to that of
the local meteoric water.
δ18O G/S (x103) temperature (°C) η (%)

measured measured modelled modelled
-8 -7 -6 -5 -4 ‰ 0.1 1 10 100 200 220 240 0.1 1 10 100
1000
depth (m)
1250
gas cap
1500
1750
condensate layer
2000
2250 two-phase layer
2500
Fig.6.22 Measured and calculated vertical distributions of the δ18O value, the gas/steam ratio, the
temperature T and the relative molar steam fraction η for the The Geysers geothermal
field.
D'Amore and Truesdell (1979) hypothesised different fluid sources at different depths which
may contribute in different and time-dependent proportions to the total production. Usually
the gas cap is exhausted after a short time. As the contribution from the condensate layer de-
creases in new wells in previously exploited areas, the two-phase reservoir gradually becomes
the most important productive level. The temporal variation of the isotopic compositions in
steam of wells located in the south-eastern area of The Geysers geothermal field is interpreted
as a result of a changing contribution of fluid from admixed different sources.
149
Chapter 6
150
7 PLANNING AND PERFORMANCE OF
MULTIPLE ISOTOPE STUDIES
In Fig.3.1 (Chapter 3) the most simple geohydraulic conditions are shown, described by the
piston-flow model and the exponential model. In nature the conditions are generally more
complicated. Young water may be admixed to very old water. Leakage between aquifers may
result in mixtures of differently old groundwaters. In such cases measured and modelled
isotope data often deviate from each other. To overcome this problem trial and error
procedures are applied using different model conceptions (e.g. by applying the MULTI
program; Richter et al. 1993). A final agreement between these two values does not mean that
the model is a good reflection of natural conditions (Oereskes et al. 1994; Maloszewski and
Zuber 1993, 1998).
There are may attempts to express a close agreement between modelled and measured isotope
data as a good approximation of the actual situation. An example is the long-term record of
the stable isotopic composition of the Fijeh spring in the Antilebanon mountains (Kattan
1996b). Even a slight disagreement shows that a model cannot be applied and a completely
deviating geohydraulic constellation may exist. In this case the approximate estimate of a
mean residence time is hydrogeologically misleading. The proposed explanation of the
deviation between the model and the observed isotopic composition is then unsatisfactory
(Fig.7.1).
In order to understand the hydrogeological system two or even more independent isotope
determinations are required, combined with hydrochemical analyses. The fact is that the
applicability of the model is not proven by an apparent agreement between the model result
and the data obtained. As the above mentioned example demonstrates that a long-term
monitoring of one isotope instead of multiple isotope analyses may give evidence for such
disagreement. On the other hand, it still may not allow to understand the actual geohydraulic
situation of the system. Hence serious case studies in isotope hydrogeology usually consist of
a wide spectrum of techniques (e.g. 3H, 14C, 36Cl, 85Kr; Bath et al. 1979; Andrews et al. 1984;
Phillips et al. 1989; Verhagen et al. 1991), in order to describe a realistic geohydraulic situ-
ation with more than one groundwater component. The occurrence of groundwaters of
different age in the same hydraulic system requires independent information on different time
scales. That is why multiple-isotope analyses are usually essential. An example is the
determination of the mean residence time (MRT) of young groundwater by means of the
exponential model or any other lump-parameter model (Sect.3.1.2; Volume VI). Using
complementary 14C and 3H analyses of the same water samples, two unknowns exists – the
151
Chapter 7
mean residence time (MRT) and the initial 14C activity Cinit. Time-series of these isotope data
yield more accurate and reliable estimates. Moreover, it is recommended to analyse samples
of as many as possible sites of the same catchment, in order to check which interpretation mo-
del yields the best fit to the data.
100
H value (TU)
80
10 years
20 years
50
3
30 years
40
40 years
30 50 years
20
10
1970 1975 1980 1985 1990
Fig.7.1 Temporal trend of the 3H value of groundwater discharged from the Fijeh spring in the
Antilebonaon mountains. The discrepancy between modelled (lines) and the measured
δ values (open circles) shows (Kattan et al. 1996b) that the exponential model cannot be
applied to estimate a mean residence time which would be geohydraulically misleading.
Any multiple isotope hydrological study can only develop its full potential if there is a lack of
hydrogeological information or the hydrogeological questions are very specific. When
planning such an applied hydrological study the first question is if there are sufficient funds
and time .
In case of a scientific study as many as possible isotopic and hydrochemical analyses are to be
carried out and The time of sampling should be extended over at least one hydrological cycle
of 12 months. The goal is usually to understand the whole system without answering specific
hydrological questions. One of the best examples is the most comprehensive multi-isotope
study which was conducted in the marly sandstones of southern England (Andrews et al.
1984). The aim was to assess the value of individual environmental isotopes for establishing
hydrogeological data. The results confirmed that 3H and 14C activity measurements along with
the determinations of the stable isotopic composition of carbon, hydrogen and oxygen provide
practically all information of hydrogeological interest to be expected from environmental
isotope methods, provided hydrochemical analyses are implemented.
152
Multiple Isotope Studies
The applied isotope hydrological studies usually suffer from the shortness of the period
available for sampling and often also from restricted financial resources (Verhagen et al.
1991). On the other hand, the hydrogeologically interesting questions are often well-defined.
The limitations require a thorough planning including all information on the site to be studied:
The size of the region and the distance of the sampling sites defines the required age
resolution and possible influence of the continental effect on δ18O (Sect.5.2.1.1).
The morphology determines whether or not the altitude effect on δ18O (Sect.5.2.1.1) may play
a role, allowing a rough estimate of the tracer velocity of groundwater in relation to the
required age resolution.
The sampling sites may be drilled or dug wells. The pumping rate and the totally abstracted
amount of groundwater may be important to estimate if groundwater mining has occurred that
may have modified the 14C ages of groundwater DIC (Sect.5.1.2.3). In the case of springs the
fluctuation of the spring discharge during one hydrological cycle may allow to decide whether
or not a spot sampling is sufficient or sampling and analysis is required in short distances (e.g.
month or weeks).
The hydrogeological situation of the study region (unconsolidated sediments, fractured rocks,
phreatic or confined aquifers, leaky aquifer systems) allow to resolve what age range of the
groundwater has to be expected, how many groundwater components with what estimated age
have to be expected in order to decide how many and which isotopes should be analysed.
The geohydraulic conditions are reflected by the piezometric surface of the groundwater in
different aquifers and allows reliable estimates of the tracer velocity and expected flow
directions. Based on this the minimum and maximum distance of the sampling sites can be
determined.
The palaeohydrologic situation of the study is important to set up the spatial distribution of
the sampling sites, this in order to get an impression whether or not steady-state or non-
steady-state geohydraulic conditions have to be taken into account in the interpretation of the
isotope date (Verhagen et al. 1991).
The hydrochemistry of the groundwater resources is important in order to recognise if
hydrochemical analyses are indispensable for a hydrochemical correction of the isotope
compositions (14C, 13C) (Volume I; Clark and Fritz 1997), in order to correct and to calibrate
the time scale of groundwater.
Based on this information and on the hydrogeological questions an optimum sampling and
analytical program is to be established. The main aims are determining:
1) the age of the groundwater where the determination of relative water ages is sufficient
for checking or calibrating the geohydraulic model results. Tracer velocities, groundwater
recharge rates, regional aquifer parameters (hydraulic conductivity, total porosity),
mixing proportions, or contributions to the groundwater budget can be obtained with
153
Chapter 7
conventional 14C ages of the groundwater DIC. Palaeoclimatic information to be used for
numerical model calibration requires absolute ages. This requires the estimating the
initial 14C activity and thoroughly making hydrochemical analyses in order to exclude or
to correct secondary changes of the isotopic composition. This is also necessary if the
pollution potential of an aquifer has to be substantiated.
2) the origin of the groundwater, possibly allowing to make mixing balance studies, to
localise the recharge areas or to determine and distinguish between the participating
groundwater components.
Comparing the estimated costs of sampling and analysis, and possibly of data interpretation,
an optimal multiple-isotope programme can be set up. The quality finally determines the
hydrogeological value of the isotope hydrological contribution.
154
REFERENCES
87
Aberg, G.G., Jacks, G. and Hamilton, P.J., 1989. Weathering rates and Sr/86Sr ratios: An
isotopic approach. Jour. Hydrology, 109: 65-78.
Adar, E.M., Gev, I., Berliner, P. and Issar, A.S. 1995. The effect of forestation on a shallow
groundwater reservoir in an arid sand dune terrain. J. Arid Studies, 55: 259-262.
Adar, E.M., 1996. Quantitative evaluation on flow systems groundwater recharge and trans-
missivities using environmental tracers. Manual on Mathematical Models in Isotope Hyd-
rogeology. IAEA-TECDOC-910, IAEA Vienna: 113-154.
Allard P. , 1983. The origin of hydrogen, carbon, sulphur, nitrogen and rare gases in volcanic
exhalations: evidence from isotope geochemistry. In: H. Tazieff and J.C. (Editors),
Forecasting Volcanic Events, Elsevier, Amsterdam, New York: 337-386.
Allison, G.B., 1982. The relationship between 18O and deuterium in water and sand columns
undergoing evaporation. J. Hydrol., 55: 163-169.
Allison, G.B., Barnes, J.B., Hughes, M.W. and Leaney, F.W.J., 1983a. The distribution of
deuterium and 18O in dry soils, 2. Experimental. J. Hydrol., 64: 377-397.
Allison, G.B., Barnes, J.B., Hughes, M.W. and Leaney, F.W.J., 1983b. The effect of climate
and vegetation on oxygen-18 and deuterium profiles in soils. In: Isotope Hydrology 1983,
IAEA Vienna: 105- 123.
Allison, G.B., Colin-Kaczala, C., Filly, A. and Fontes, J.Ch. , 1987. Measurement of isotopic
equilibrium between water, water vapour and soil CO2 in arid zone soils. J. Hydrol., 95:
131-141.
Alvis-Isidro, R.R., Solana, R.R., D'Amore, F., Nuti, S. and Gonfiantini, R., (1993). Hydrology
of the greater Tongonan Geothermal System, Philippines, as deduced from geochemical
and isotopic data. Geothermics, 22: 435-449.
Andres, G. and Egger, R., 1985. A new tritium interface method for determining the recharge
rate of deep groundwater in the Bavarian Mollasse basin. J. Hydrol., 82: 27-38.
Andrews, J.N., 1985. The isotopic composition of radiogenic helium and its use to study
groundwater movement in confined aquifers. Chem. Geology, 49: 339-351.
Andrews, J.N., 1991. Noble gases and radioelements in groundwaters. In: R.A. Downing and
W.B. Wilkinson (Editors), Applied Groundwater Hydrology: A British Perspective.
Chapter 15, Clarendon Press, Oxford: 243-265.
155
References
Andrews, J.N., 1992. Mechanisms for noble gas dissolution by groundwaters. In: Isotopes of
Noble Gases as Tracers in Environmental Studies, IAEA Vienna: 87-110.
Andrews, J.N. and Fontes, J.C., 1992. Importance of the in situ production of 36Cl, 36Ar and
14
C in hydrology and hydrogeochemistry. In: Isotope Techniques in Water Resources
Development, IAEA Vienna: 245-269.
Andrews, J.N., Giles, I.S., Kay, R.L.F., Lee ,D.J., Osmond, J.K., Cowart, J.B., Fritz, P.,
Barker, J.F. and Gale, J., 1982. Radioelements, radiogenic helium and age relationships
of groundwaters from the granites at Stripa, Sweden. Geochim. Cosmochim. Acta, 46:
1533-1543.
Andrews, J.N., Balderer, W., Bath, A.H., Clausen, H.B., Evans, G.V., Florkowski, T.,
Goldbrunner, J.E., Ivanovich, M., Loosli, H. and Zojer, H., 1984. Environmental isotope
studies in two aquifer systems: A comparison of groundwater dating methods. In: Isotope
Hydrology 1983, IAEA Vienna: 535-576.
Andrews, J.N., Hussain, N. and Youngman, M.J., 1989. Atmospheric and radiogenic gases in
groundwaters from the Stripa Granite. Geochim. Cosmochim. Acta, 53: 1831-1841.
Aranyossy, J.F., Filly, A., Tandia, A.A., Ousmane, B., Louvat, D. and Fontes, J.C., 1991.
Estimation du flux dévaporation sous couvert sableux en climat hyper aride (erg de
Bilma, Niger. In: Isotope Techniques in Water Resources Development, IAEA Vienna:
309-324.
Aravena, R., Evans, M. L. and Cherry, J. A., 1996. Stable isotopes of oxygen and nitrogen in
source identification of nitrate from septic systems. Ground Water, 31: 180-186.
Aravena, R. and Wassernaar, L.I. , 1993. Dissolved organic carbon and methane in a regional
confined aquifer: Evidence for associated subsurface sources. Appl. Geochem., 8: 483-
493.
Balderer W. , 1993. Conclusions on the possible variations of chemical and isotopic
composition of groundwater systems in response to changed hydrodynamic conditions.
In: Isotopic and geochemical precursors of earthquakes and volcanic eruptions. IAEA-
TECDOC-726, IAEA Vienna: 87-107.
Balderer W. and Synal A. , 1995. Characterization of the groundwater circulation of
tectonically active areas in western Turkey by the 36Cl method. In: Isotopes in Water
Resources Management Vol. 2, IAEA Vienna: 164-167.
Barnes, C.J. and Allison, G.B., 1983. The distribution of deuterium and oxygen-18 in dry
soils: 1. Theory. J. Hydrol., 60: 141-156.
Barnes, C.J. and Allison, G.B., 1984. The distribution of deuterium and oxygen-18 in dry
soils: 3. Theory for non-isothermal water movement. J. Hydrol., 74: 119-135.
156
References
Barnes, C.J. and Allison, G.B., 1988. Tracing of water movement in the unsaturated zone
using stable isotopes of hydrogen and oxygen. J. Hydrol., 100, 1-3: 143-176.
Barnes, C.J. and Walker, G.B., 1989. The distribution of deuterium and oxygen-18 during
unsteady evaporation. J. Hydrol., 112: 55-67.
Barth, S., 1993. Boron isotope variations in nature: a synthesis. Geol. Rundsch., 82: 1177-
1188.
Bates, R.L. and Jackson, J.A. (Editors), 1980. Glossary of Geology (2nd edition), American
Geological Institute, Falls Church, Virginia: 751 pp.
Bath, A. H., Edmunds, W.M. and Andrews, J. N., 1979. Palaeoclimatic trends deduced from
the hydrogeochemistry of a Triassic sandstone aquifer, United Kingdom. In: Isotope
Hydrology 1978, Vol. II, IAEA Vienna: 545-567.
Becker R.H. and Clayton R.N., 1976. Oxygen isotope study of a Precambrian banded iron
formation. Hamersley Range, Western Australia. Geochim. Cosmochim. Acta, 40: 1153-
1165.
Beekman, H.E., Gieske, A. and Selaolo, E.T., 1996. GRES – groundwater recharge studies in
Botswana (1987 – 1996). Botswana J. Earth Sci., III: 1-17.
Behrens, H., Moser, H., Oerter, H., Rauert, W., Stichler, W., Ambach, W. and Kirchlechner,
P., 1979. Models for the runoff of a glaciated catchment area using measurements of
environmental isotope contents. In: Isotope Hydrology 1978, Vol. II, IAEA Vienna: 829-
845.
Bendl, J., 1992. A study of 87Sr/86Sr ratios in the exogene zone of the Krusne Hory Mts. (W.
Bohemia). Casopis pro mineralogii a geologii, 37: 339-347.
Bentley, H.W., Phillips, F.M., Davis, S.N., Gifford, S., Elmore, D., Tubbs, L., and Gove,
H.E., 1982. The thermonuclear 36Cl pulse in natural water. Nature, 300: 737-740.
Bentley, H. W., Phillips, F. M. and Davis, S. N., 1986. Chlorine-36 in the terrestrial
environment. In: P. Fritz and J. C. Fontes (Editors), Handbook of Environmental Isotope
Geochemistry Vol. IIB, The Terrestrial Environment, Elsevier, Amsterdam New York:
427-480.
Bertleff, B., Stichler, W., Stober, I. and Strayle, G., 1985. Geohydraulische und isotopen-
hydrologische Untersuchungen im Mündungsbereich zwischen Donau und Iller. Abh.
geol. Landesamt Baden-Württemberg, 11: 7-44.
Bertleff, B., Watzel, R., Eichinger, L., Heidinger, M., Dchneider, K., Loosli, H.H. and
Stichler, W., 1993. The use of isotope based modelling techniques for groundwater
management in a Quaternary aquifer system. In: Isotope Techniques in the Study of
Environmental Change, IAEA Vienna: 437-452.
157
References
Black, J.H., Kipp Jr. and K.L., 1983. Movement of tracers through dual porosity media -
Experiments and modelling in the Cretaceous Chalk, England. J. Hydrol., 62: 287-312.
Blattner P., 1985. Isotope shift data and the natural evolution of geothermal systems. Chem.
Geol., 49: 187-203.
Böttcher J, Strebel, O., Voerkelius, S. and Schmidt, H.L., 1990. Using isotope fractionation of
nitrate nitrogen and nitrate oxygen for evaluation of nitrate in a sandy aquifer. J. Hydrol.,
114: 413-424.
Bottomley, D. J., Gascoyne, M. and Kamineni, D. C., 1990. The geochemistry, age and origin
of groundwater in a mafic pluton, East Bull Lake, Ontario, Canada. Geochim.
Cosmochim. Acta, 54: 993-1008.
Box W.T., D'Amore F. and Nuti S., 1987. Chemical and isotopic composition of fluids
sampled during drilling at The Geysers (CA, USA). In: Proc. Int. Symp. on Development
and Exploitation of Geothermal Resources, CFE-CEE, Cuernavaca, Mexico: 172-177.
Burdon, D.J. , 1977. Flow of fossil groundwater. Quaterly J. Eng. Geol., 10: 97-124.
Busenberg, E. and Plummer, L. N., 1992. The use of chlorofluorocarbons (CCl3F and CCl2F2)
as hydrologic tracers and age-dating tools: the alluvium and terrace system of central
Oklahoma. Water Res. Res., 28: 2257-2283.
Butler, M. J. and Verhagen, B. T., 1997. Environmental isotopic tracing of water in the urban
environment of Pretoria, South Africa. In: P. J. Chilton I(Editor), Groundwater in the
Urban Environment Vol. 1, Problems, Processes and Management, Balkema, Rotterdam:
101-106.
Buzek, F., Kadlecová, R. and Zák, K., 1998. Nitrate pollution of a karstic groundwater
system. In: Isotope Techniques in the Study of Environmental Change, IAEA Vienna:
453-464.
Calf, G.E. and Habermehl, M.A. , 1984. Isotope hydrology and hydrochemistry of the Great
Artesian Basin, Australia. In: Isotope Hydrology 1983, IAEA Vienna: 397-414.
Carmi, I. and Gat, J.R., 1992. Estimating the turnover time of groundwater reservoirs by the
helium-3/tritium method in the era of declining atmospheric tritium levels: Opportunities
and limitations in the time bracket 1990-2000. Israel J. Earth Sci., 43: 249-253.
Chiba, H. and Sakai H., 1985. Oxygen isotope exchange rate between dissolved sulfate and
water at hydrothermal temperatures. Geochim. Cosmochim. Acta, 49: 993-1000.
Clark, I.D., Bajjali, W.T. and Phipps, G. Ch., 1996. Constraining 14C ages in sulphate
reducing groundwaters: two case studies from arid regions. In: Isotope in Water
Resources Management, IAEA Vienna: 43-56.
Clark, I. D. and Fritz, P., 1997. Environmental Isotopes in Hydrogeology, Lewis Publishers,
New York, 328 pp.
158
References
Clark, L., 1988. The Field Guide to Water Wells and Boreholes, Open University Press,
Milton Keynes and Halsted Press, John Wiley and Sons, New York, Toronto, 155 pp.
Claypool, G.E., Holser, W.T., Kaplan, I.R., Sakai, H. and Zak, I., 1980. The age curves of
sulfur and oxygen isotopes in marine sulfate and their mutual interpretation. Chem.
Geology, 28: 199-260.
Clayton, R.N. and Steiner, A.S., 1975. Oxygen isotope studies of the geothermal system at
Wairakei, New Zealand. Geochim. Cosmochim. Acta, 39: 1179-1186.
Collon, P.A.E., Kutschera, W., Lehmann, B.E., Loosli, H.H., Purtschert, R., Love, A.,
Sampson, L., Davids, B., Fauerbach, M., Harkewicz, R., Morrissey, D., Sherrill, B.,
Steiner, M., Pardo, R. and Paul, M., 1999. Development of Accelerator Mass
Spectrometry (AMS) for the detection of 81Kr and its first application to groundwater
dating. In: Int. Symp. on Isotope Techniques in Water Resources Development and
Management, IAEA Vienna, SM-361-18.
Cook, P.G. and Solomon, D.K., 1997. Recent advances in dating young groundwater:
chlorofluorocarbons, 3H/3He and 85Kr. J. Hydrol., 191: 245-265.
Corbett, D.R., Burnett, W.,C., Cable, P.H. and Clark, S.B., 1997. Radon tracing of
groundwater input into Par Pond, Savannah River Site. J. Hydrol., 203: 209-227.
D'Amore F. and Truesdell A.H. (1979). Models for steam chemistry at Larderello and The
Geysers. In: Proc. Fifth Stanford Geothermal Reservoir Engineering Workshop: 283-297.
D'Amore, F. and Truesdell, A.H., 1985. Calculation of geothermal reservoir temperatures and
steam fraction from gas compositions. Geotherm. Res. Coun. Trans., 9: 305-310.
D'Amore, F., Nuti, S. and Fancelli, R., 1988: Geochemistry and reinjection of waste waters in
vapor dominated fields. In: Proc. Int. Symp. on Geothermal Energy, Kumamoto and
Beppu, Japan: 244-248.
Dansgaard, W., 1964. Stable isotopes in precipitation. Tellus, 16: 436-468.
Darling, W.G., Gizaw, B. and Arusei, M.K., 1996. Lake-groundwater relationships and fluid-
rock interaction in the East African Rift Valley: an isotopic study. J. African Earth Sci.,
22: 423-431.
Datta, P.S., Goel, P.S., Rama, F.A. and Sangal, S.P., 1973. Groundwater recharge in western
Uttar Pradesh. Proc. Ind. Acad. Sci., Vol. LXXVIII (1A): 1-12.
Davidson, G.R. and Bassett, R.L., 1993. Application of boron isotopes for identifying
contaminants such as fly ash leachate in groundwater. Environ. Sci. Techn., 27: 172-176.
Davis, S.N. and DeWiest, R.M., 1966. Hydrogeology, J. Wiley, New York, London, Sydney,
463 pp.
159
References
Deák, J., Stute, M., Rudolph, J. and Sonntag, C., 1987. Determination of the flow regime of
Quaternary and Pleistocene layers in the Great Hungarian Plain (Hungary) by D, 18O, 14C
and noble gas measurements. In: Isotope Techniques in Water Resources Development,
IAEA, Vienna: 335-350.
Deák, J., Deseö, E., Böhlke, J.K. and Révész, R., 1995. Isotope hydrology studies in the
Szigetköz region, northwest Hungary. In: Isotopes in Water Resources Management Vol.
I, IAEA Vienna: 419-432.
Degueldre, C., Pfeiffer, H.R., Alexander, W., Wehrli, B. and Breutsch, R., 1996. Colloid
properties in granitic groundwater systems. I: Sampling and characterisation. Appl.
Geochem., 11: 677-695.
Dincer, T., Al-Mugrin, W. and Zimmermann, V., 1974. Study of the infiltration and recharge
through the sand dunes in arid zones with special reference to the stable isotopes and
thermo-nuclear tritium. J. Hydrol., 23: 79-109.
Drever, J.I., 1997. The Geochemistry of Natural Waters (3rd Edition), Prentice Hall, N.J.,
436 pp.
Dreybroth, W., 1988. Processes in Karst Systems, Springer, Heidelberg, 288 pp.
Dürbaum, H.J., 1969. Der Durchlässigkeitsbeiwert von Lockergesteinen und seine
Bestimmung. In: A. Bentz and H.J. Martini (Editors), Lehrbuch der angewandten
Geologie Vol. 2 (2), Ferdinand-Enke Verlag, Stuttgart: 1474-1513.
Dymond, J., Cobler, R., Gordon, L., Biscaye, P. and Mathieu, G., 1983. 226Ra and 226Rn
contents of Galapagos Rift hydrothermal waters - the importance of low-temperature
interactions with crustal rocks. Earth Planet. Sci. Letters, 64: 417-429.
Eastoe, C.J. and Guilbert, J.M. , 1992. Stable chlorine isotopes in hydrothermal processes.
Geochim. Cosmchim. Acta, 56: 4247-4255.
Edmunds, W.M., Cook, J.M., Darling, W.G., Kinniburgh, D.G., Miles, D.L., Bath, A.H.,
Morgan-Jones, M. and Andrews, J.N., 1987. Baseline geochemical conditions in the
Chalk aquifer, Berkshire, UK: a basis for groundwater quality management. Appl.
Geochem., 2: 251-274.
Eggenkamp, H.G.M. and Coleman, M.L., 1998. Heterogeneity of formation waters within and
between oil fields by halogen isotopes. In: G.B. Arehart and J.R. Hulston (Editors),
Water-Rock Interaction, Balkema, Rotterdam: 309-312.
Eggenkamp, H.G.M., 1994. The geochemistry of Chlorine isotopes. Geologica Ultraiectina,
Mededelingen van de Faculteit Aardwetenschappen, Rijksunversiteit Utrecht: 116 pp.
Ekwurzel, B., Schlosser, P., Smethie, Jr., W.M., Plummer, L.N., Busenberg, E., Michel, R.L.,
Weppernig, R. and Stute, M., 1994. Dating of shallow groundwater: comparison of the
transient tracers 3He/3H, chlorofluorocarbons, and 85Kr. Water Res. Res., 30: 1693-1708.
160
References
Elmore, D., Tubbs, L.E., Newman, D., Ma, X.Z., Finkel, R., Nishiizumi, K., Beer,
J.,Oeschger, H. and Andree, M., 1982. 36Cl bomb pulse measured in a shallow ice core
from Dye 3, Greenland. Nature, 300: 735-737.
129 36
Fabryka-Martin, J., Davis, S.N. and Elmore, D., 1987. Application of I and Cl in
hydrology. Nucl. Instr. Meth. Phys. Res. B, 29: 361-371.
Florkowski, T., Morawska, L. and Rozanski, K., 1988. Natural production of radionuclides in
geological formations. Nucl. Geophys, 2: 1-14.
Fontes, J.C., 1992. Chemical and isotopic constraints on 14C dating of groundwater. In:
Taylor, R.E., Long, A. and Kra, R.S., (Editors). Radiocarbon after Four Decades. An
Interdisciplinary Perspective, Springer, New York: 242-275.
Fontes, J.-C., Yousfi, M. and Allison, G.B., 1986. Estimation of the long term, diffuse
groundwater discharge in the Northern Sahara using stable isotope profiles in soil water.
J. Hydrol., 86: 315-327.
Forster, M., Loosli, H. and Weise, S., 1992. 39Ar, 85Kr, 3He and 3H isotope dating of
groundwater in the Bocholt and Segeberger Forest Aquifer Systems. In: G. Matthess et al.
(Editors), Progress in Hydrogeochemistry, Springer, Berlin: 467-475.
Foster, S.S.D. and Smith-Carrington, A., 1980. The interpretation of tritium in the chalk
unsaturated zone. J. Hydrol., 46: 343-364.
Frape, S.K., Bryant, G., Blomquist, R. and Ruskeeniemi, T., 1995. Evidence from stable
chlorine isotopes for multiple sources of chlorine in groundwaters from crystalline shield
environments. In: Isotopes in Water Resources Management Vol. I, IAEA Vienna: 19-30.
Frape, S.K., Bryant, G., Durance, P., Ropchan, J.C., Doupe, J., Blomquist, R., Nissinen, P.,
Kaija, J., 1998. The source of stable chlorine isotopic signatures in groundwaters from
crystalline shiled rocks. In: G.B. Arehart and J.R. Hulston (Editors) Water-Rock
Interaction, Balkema, Rotterdam: 223-226.
Freyer, H.D. , 1978. Seasonal trends of NH4+ and NO3- nitrogen isotopic composition in rain
collected at Jülich, Germany. Tellus, 30: 83-92.
Fritz, P., Cherry J.A., Weyer R.V. and Sklash M.G., 1976. Runoff analyses using
environmental isotopes and major ions. In: Interpretation of Environmental Isotope and
Hydrochemical Data in Groundwater Hydrology, IAEA Vienna: 111-130.
Fritz, B., Clauer, N. and Sam, M., 1987. Strontium isotopic data and geochemical calculations
as indicators of the origin of saline waters in crystalline rocks. In: P. Fritz and S.R. Frape
(Editors) Saline Water and Gases in Crystalline Rocks, Special Paper 33, Geol. Assoc. of
Canada: 121-126.
Fritz, P., Frape, S.K., Drimmie, R.J., Appleyard, E.C. and Hattori K., 1994. Sulfate in brines
in the crystalline rocks of the Canadian Shield. Geochim. Cosmochim. Acta, 58: 57-65.
161
References
Fröhlich, K. and Gellermann, R., 1986. On the potential use of uranium isotopes for
groundwater dating. Isot. Geosci. Sect., 65: 67-77.
Galimov, E.M., 1973. Carbon Isotopes in Petroleum Geology, Nedra, Moscow.
Gascoyne, M., 1981. A simple method of uranium extraction from carbonate groundwater and
its application to 234U/238U disequilibrium studies. J. Geochem. Explor., 14: 199-207.
Gat, J.R. and Carmi, I., 1970. Evolution of the isotopic composition of atmospheric waters in
the Mediterranean Sea area. J. Geophys. Res., 75: 3039-3048.
Gat, J. and Gonfiantini, R. (Editors), 1981. Stable Isotope Hydrology. Deuterium and
Oxygen-18 in the Water Cycle, Technical Reports Series No 210, IAEA Vienna: 337 pp.
Geyer, S., Wolf, M., Wassenaar, L.I., Fritz, P., Buckau, G. and Kim, J.I., 1993. Isotope
investigations an fractions of dissolved organic carbon from 14C dating. In: Isotope
Techniques in the Study of Past and Current Environmental Changes in the Hydrosphere
and Atmosphere, IAEA Vienna: 359-380.
Geyh, M.A., 1972. Basic studies in hydrology and 14C and 3H measurements. In: Proc. XXIV
Int. Geol. Congr., 11: 227-234; Montreal.
Geyh, M.A., 1992. The 14C time-scale of groundwater. Correction and linearity. In: Isotope
Techniques in Water Resources Development 1991, IAEA Vienna: 167-177.
Geyh, M.A., 1994. The paleohydrology of the eastern Mediterranean. In: O. Bar-Yosef and
R.S. Kra (Editors) Late Quaternary Chronology and Paleoclimates of the Eastern
Mediterranean, Radiocarbon, Tuscon.: 131-145.
Geyh, M.A. and Backhaus, G., 1979. Hydrodynamic aspects of carbon-14 groundwater
dating. In: Isotope Hydrology 1978 Vol. II, IAEA Vienna: 631-643.
Geyh, M.A. and Kantor, W., 1998. Zusammenspiel zwischen Isotopenhydrologie und
numerischer Strömungsmodellierung am Beispiel der Dübener Heide. In: Proc. 4. GBL-
Kolloquium, 26.- 28. November 1997, Ergebnisse und Empfehlungen, Hannover, GBL-
Heft, 5: 111-121.
Geyh, M.A. and Künzl, R., 1981. Methane in groundwater and its effect on 14C groundwater
dating. J. Hydrol., 52: 355-358.
Geyh, M.A. and Michel, G., 1981. Isotopen- und hydrochemische Betrachtungen über die
Süßwasser/Salzwasser-Zone am Nordostrand des Münsterländer Beckens. Z. dtsch. geol.
Ges., 132: 597-611.
Geyh, M.A. and Michel, G., 1982. Isotopical differentiation of groundwater of different
hydrogeologic origin. J. Hydrol., 59: 161-171.
Geyh, M.A. and Schleicher, H. , 1990. Absolute Age Determination. Physical and Chemical
Dating Methods and Their Application, Springer, Berlin Heidelberg New York, 503 pp.
162
References
Geyh, M.A., Backhaus, G., Andres, G., Rudolph, R. and Rath, H.K. , 1984. Isotope study on
the Keuper sandstone aquifer with a leaky cover layer. In: Isotope Hydrology 1983,
IAEA Vienna: 499-513.
Geyh, M.A., Bender, H., Rajab, R. and Wagner, W., 1995. Application of 14C-groundwater
dating to non-steady systems. In: Adar, E.M. and Leibundgut, Ch. (Editors) Application
of Tracers in Arid Zone Hydrology, IAHS Press, Wallingford, Oxfordshire, IAHS Publ.
No. 232: 225-234.
Giggenbach, W.F., 1971. Isotopic composition of waters of the Broadlands geothermal field
(New Zealand). N.Z. J. Sci., 14: 959-970.
Giggenbach, W.F., 1977. The isotopic composition of sulphur in sedimentary rocks bordering
the Taupo Volcanic Zone. Geochemistry 1977. N.Z. DSM Bull., 218: 57-64.
Giggenbach, W.F., 1978. The isotopic composition of waters from the El Tatio geothermal
field, Northern Chile. Geochim. Cosmochim. Acta, 42: 979-988.
Giggenbach, W.F., 1988. Geothermal solute equilibria. Derivation of Na-K-Mg-Ca
geoindicators. Geochim. Cosmochim. Acta, 52: 2749-2765.
Giggenbach, W.F., 1989. The chemical and isotopic position of Ohaaki field within the Taupo
Volcanic Zone. Proc. Eleventh N.Z. Geothermal Workshop, Aukland: 81-88.
Giggenbach, W., 1991. Isotopic composition of geothermal water and steam discharges. In: F.
D'Amore (Editor), Application of Geochemistry in Geothermal Reservoir, UNITAR--
UNDP: 119-144.
Giggenbach, W., 1992. Isotopic shifts in water from geothermal and volcanic systems along
convergent plate boundaries and their origin. Earth Planet. Sci. Letters, 113: 495-510.
Giggenbach, W.F. and Lyon G.L., 1977. The chemical and isotopic composition of water and
gas discharges from the Ngawha geothermal field, Northland. (Dept. Sci. Ind. Res.,
Chem. Div.) Geotherm. Circ. CD 30/555/7-WFG: 37 pp.
Giggenbach, W.F. and Stewart M.K., 1982. Processes controlling the isotopic composition of
steam and water discharges from steam vents and steam-heated pools in geothermal area.
Geothermics, 11: 71-80.
Gislason, S.R. and Eugster, H.P., 1987. Meteoric water-basalt interactions. II: A field study in
N.E. Iceland. Geochim. Cosmochim. Acta, 51: 2841-2855.
Grabczak, J., Zuber, A., Maloszewski, P., Rozanski ,K., Weiss, W. and Sliwka, I., 1982. New
mathematical models for the interpretation of environmental tracers in groundwaters and
the combined use of tritium, C-14, Kr-85, He-3, and freon-11 for groundwater studies.
Beiträge zur Geologie der Schweiz – Hydrologie, 28 II: 395-406.
Grindrod, P., 1993. The impact of colloids on the migration and dispersal of radionuclides
within fractured rock. J. Contaminant Hydrol., 13: 167-181.
163
References
Gunter, B.D. and Musgrave, B.C., 1971. New evidence on the origin of methane in
hydrothermal gases. Geochim. Cosmochim. Acta, 35: 113-118.
Heaton, T.H.E., 1984. Sources of the nitrate in phreatic groundwater in the western Kalahari.
J. Hydrol., 67: 249-259.
Heaton, T.H.E., 1986. Isotopic study of nitrogen pollution in the hydrosphere and atmosphere:
a review. Chem. Geology (Isot. Geosci. Sect.), 59: 87-102.
Hedenquist, J.W., 1990. The thermal and geochemical structure of the Broadlands-Ohaaki
geothermal system. Geothermics, 19:151-185.
Henley R.W., Truesdell, A.H. and Barton, P.B., 1984. Fluid-mineral equilibria in
hydrothermal systems. Soc. of Econ. Geol., Reviews in Economic Geology, 1: 267 pp.
Hem, J. , 1985. Study and interpretation of Chemical Characteristics of Natural Water
(3rd ed.), US Geol. Survey Water Supply, Paper, 2254: 263 pp.
Herczeg, A.L., Love, A.J., Sampson, L., Cresswell, R.G. and Fifield, L.K., 1999. Flow
velocities estimated from Cl-36 in the South-West Great Artesian basin, Australia.– Int.
Symp. on Isotope Techniques in Water Resources Development and Management, IAEA
Vienna: SM-361-34P.
Hillaire-Marcel, C. and Ghaleb, B., 1997. Thermal ionization mass spectrometry
measurements of 226Ra and U isotopes in soils, surface and groundwaters. Analytical
aspects and pore water–matrix interactions revisited. In: Isotope Techniques in the Study
of Past and Current Environmental Changes in the Hydrosphere and Atmosphere, IAEA
Vienna: 727-743.
Hoehn, E., Willme, U., Hollerung, R., Schulte-Ebert, U. and Gunten, H.R., 1992. Application
of the 222Rn technique for estimating the residence times of artificially recharged
groundwater. In: Isotope in Water Resources Development, IAEA Vienna: 712-714.
Holser, W.T., Magaritz, M. and Wright, J., 1986. Chemical and isotopic variations in the
world ocean during Phanerozoic time. In: O. Walliser (Editor), Lecture Notes in Earth
Sciences Vol. 8, Global Bio-Events, Springer, Heidelberg: 63-74.
Hübner, H., 1986. Chapter 9. Isotope effects of nitrogen in the soil and biosphere. In: P. Fritz
and J. Ch. Fontes (Editors), Handbook of Environmental Isotope Geochemistry Vol. II,
Elsevier, Amsterdam: 361-425.
Hübner, H., Kowski, P., Hermichen, W.-D., Richter, W. and Schütze, H., 1979. Regional and
temporal variations of deuterium in the precipitation and atmospheric moisture of Central
Europe. In: Isotope Hydrology 1978, IAEA, Vienna, Vol. 1: 289-305.
Hulston J.R., 1973. Estimation of underground temperature distribution in active
hydrothermal systems using stable isotope equilibria. In: Proc. 2nd Conf. Australian and
New Zealand Society for Mass Spectrometry, Melbourne.
164
References
IAEA (International Atomic Energy Agency), 1969, 1970, 1971, 1973, 1975, 1979, 1983,
1986, 1990, 1994. Environmental isotope data, Nos. 1 – 10: World Survey of Isotope
Concentration in Precipitation. Tech. Rep. Ser. Nos. 96, 117, 129, 147, 169, 192, 226,
264, 311, 371. IAEA, Vienna.
IAEA, 1983. Guidebook on Nuclear Techniques in Hydrology. Techn. Reports Series, 91:
456 pp.
IAEA, 1987. Studies on Sulfur Isotope Variations in Nature: Chemistry, Geology and Raw
Materials / Hydrology (Proc. Advisory Group Meeting), Vienna, 17 - 20 June, 1985: 124
pp..
International Glossary of Hydrology, 1998. UNESCO, WMO, WMO/OMM/BMO, Geneva,
No. 12: 343 pp.
Johnston, C.D., 1988. Water and Solute Movement in Deeply Weathered Lateritic Soil
Profiles Near Collie Western Australia. M. Sc. Thesis, Dept Soil Science and Plant
Nutrition, Univ. Western Australia.
Juraske, S., 1994. Diploma Thesis, University of Regensburg, Germany.
Kattan, Z., 1996a. Chemical and environmental isotope study of precipitation in Syria.-
Isotope Field Applications for Groundwater Studies in the Middle East. In: IAEA-
TECDOC-890, IAEA Vienna: 185-202.
Kattan, Z., 1996b. Environmental isotope study of the major karst springs in Damaskus lime-
stone aquifer systems: case of the Fijeh and Barada springs. In: Isotope Field
Applications for Groundwater Studies in the Middle East, IAEA-TECDOC-890: 127-
150.
Krause, H. R., 1987. Relationships between the sulphur and oxygen isotope composition of
dissolved sulphate. In: Studies on Sulfur Isotope Variations in Nature. Panel Proc. Series,
IAEA Vienna: 31-47.
Krouse, H. R., 1980. Sulphur isotopes in our environment. In: P. Fritz and J.C. Fontes
(Editors), Handbook of Environmental Isotope Geochemistry Vol. I, The Terrestrial
Environment, Elsevier, Amsterdam: 435-471.
Lehmann, B.E., Loosli, H.H., Rauber, D., Thonnard, N. and Willis, R.D. , 1991. 81Kr and 85Kr
in groundwater, Milk River aquifer, Alberta, Canada. Applied Geochemistry, 6: 419-423.
Lehmann, B.E., Purtschert, R., Loosli, H.H., Love, A., Sampson, L., Collon, P.A.E.,
Kutschera, W., Beyerle, U., Aechbach-Hertig, W. and Kipfer, R., 1999. 81Kr, 36Cl and
4
He dating in the Great Artesian basin, Australia. In: Isotope Techniques in Water
Resources Development and Management, IAEA Vienna: SM-361-93P.
Libby, W.F., 1946. Atmospheric helium three and radiocarbon from cosmic radiation. Phys.
Rev., 69: 671-672.
165
References
Libby, W.F., 1953. The potential usefulness of natural tritium. Proc. Nat. Acad. Sci., 39: 245-
247.
Lloyd, R.M. , 1968. Oxygen isotope behaviour in the sulfate-water system. J. Geophys. Res.,
73: 6099-6110.
Loosli, H.H. , 1992. Applications of 37Ar, 39Ar and 85Kr in hydrology, oceanography and
atmospheric studies. In: Isotopes of Noble Gases as Tracers in Environmental Studies,
IAEA Vienna: 73-85.
Lyon, G.L. and Hulston, J.R., 1984. Carbon and hydrogen isotopic compositions of New
Zealand geothermal gases. Geochim. Cosmochim. Acta, 48: 116-1171.
Majoube, M., 1971. Fractionnement en oxygene-18 et en deuterium entre láu et sa vapeur. J.
Chim. Phys., 68: 1423-1436.
Maloszewski, P. and Zuber, A., 1993. Principles and practice of calibration and validation of
mathematical models for the interpretation of environmental tracer in aquifers. Advances
in Water Res., 16: 173-190.
Maloszewski, P. and Zuber, A., 1996. Lumped parameter models for the interpretation of
environmental tracer data. In: Manual on Mathematical Models in Isotope Hydrology,
IAEA Vienna: 9-58.
Maloszewski, P. and Zuber, A., 1998. Discussion: A general lumped parameter model for the
interpretation of tracer data and transit time calculation in hydrologic systems (Journal of
Hydrology 179 (1996) 1–21). Comments. J. Hydrol., 204: 297-300.
Mariotti, A. , 1984. Utilisation des variations naturelles d’abondance isotopique en 15N pour
tracer l’origine des pollutions des aquiferes par les nitrates. In: Isotope Hydrology 1983,
Mariotti, A., Landreau, A. and Simon, B., 1988. 15N isotope biogeochemistry and natural
denitrification process in groundwater: Application to the chalk aquifer of northern
France. Geochim. Cosmochim. Acta, 52: 1869-1878.
Matsuhisa, Y., Goldsmith, J.R. and Clayton, R.N., 1979. Oxygen isotope fractionation in the
system quartz-albite-anorthite-water. Geochim. Cosmochim. Acta, 43: 1131-1140.
Mazor, E., 1991. Applied Chemical and Isotopic Groundwater Hydrology, John Wiley, New
York: 274 pp.
Mazor, E. , 1992. Reinterpretation of Cl-36 data: physical processes, hydraulic
interconnections, and age estimates in groundwater systems. Appl. Geochem., 7: 351-
360.
McNutt, R.H. , 1987. Sr87/Sr86 as indicators for water-rock interactions: applications to brines
found in Precambrian age rocks from Canada.- In: P. Fritz and S.K. Frape (Editors),
166
References
Saline Water and Gases in Crystalline Rocks, Geol. Assoc. of Canada, Special Paper 33:
81-88.
Merlivat L., 1970. L'etude quantitative de bilans de lacs a l'aide des concentrations en
deuterium et oxygene-18 dans l'eau. In: Isotope Hydrology, IAEA Vienna: 89-107.
Merlivat, L. , 1978. Molecular diffusivities of H216O, HDO and H218O in gases. J. Chem.
Phys., 69: 2864-2871.
Merlivat L. and Jouzel J., 1979. Global climatic interpretation of the deuterium-oxygen 18
relationship for precipitation. J. Geophys. Res., 84: 5029-5033.
Michel, G. and Struckmeier, W., 1985. The Cretaceous Basin of Münster – a regional
groundwater system in response to multiple impacts (water supply, spas, deep mining).
Mem. 18th IAH Congr., Cambridge: 150-159.
Mizutani Y. and Rafter T.A. , 1969. Oxygen isotopic composition of sulphates, Part 3: -
Oxygen isotopic fractionation in the bisulphate ion-water system. N.Z.J. Sci., 12: 54.
Mook, W.G., 1970. Stable carbon and oxygen isotopes of natural waters in the Netherlands.
In: Isotope Hydrology 1970, IAEA Vienna: 163-190.
Mook, W. G., 1980. Carbon-14 in hydrogeological studies. In: P. Fritz and J. Ch. Fontes
(Editors), Handbook of Environmental Isotope Geochemistry Vol. I, Elsevier,
Amsterdam: 49-74.
Mook, W.G., Groeneveld, D.J., Brouwn, A.E. and Van Ganswijk, A.J., 1974. Analysis of a
run-off hydrograph by means of natural 18O. In: Isotope Techniques in Ground-Water
Hydrology, IAEA Vienna: 145-153.
Morgenstern, U., Taylor, C.B., Parrat, Y., Gäggeler, H.W. and Eichler, B., 1996. 32Si in
precipitation: evaluation of temporal and spatial variation and as dating tool for glacial
ice. Earth Planet. Sci. Letters, 144: 289-296.
Moser, H. and Rauert, W. (Editors), 1980. Isotopenmethoden in der Hydrologie, Borntraeger,
Berlin Stuttgart, 400 pp.
14
Münnich, K.O., 1957. Messung des C-Gehaltes von hartem Grundwasser. Naturwiss., 34:
32-33.
Münnich, K.O., 1968. Isotopen-Datierung von Grundwasser. Naturwiss., 55: 158-163.
Münnich, K.O., 1983. Moisture movement in the unsaturated zone. In: Guidebook on Nuclear
Techniques in Hydrology. Techn. Reports Series No. 91, IAEA Vienna: 109-118.
Nuti S., Calore C. and Noto P., 1981. Use of environmental isotopes as natural tracers in a
reinjection experiment at Larderello. In: Proc. 7th Stanford Geothermal Reservoir
Engineering Workshop: 85-89.
167
References
Nuti S., Caprai A. and Noto P., 1985. Hypothesis on the origin of steam and on the deep
temperatures of the fluids of Pozzuoli Solfatara (Campania, Italy). In: Proc. 9th
Geothermal Energy Annual Meeting, Geothermal Resources Council Transactions.
Oreskes, N., Shrader-Frechette, K. and Belitz, K., 1994. Verification, validation, and
confirmation of numerical models in the earth sciences. Science, 263: 641-646.
O'Neil, J.R., 1987. Preservation of H, C, and O isotopic ratios in the low temperature
environment. In: T.K. Kyser (Editor), Stable Isotope Geochemistry of Low Temperature
Processes. Mineral. Soc. Canada Short Course, 13: 85-128.
Osmond, J.K., Cowart, J.B. and Ivanovich, M., 1983. Uranium isotopic disequilibrium in
ground water as an indicator of anomalies. Int. J. Appl. Radiat. Isot., 34: 283-308.
Ousmane, B., Fontes, J.-C., Aranyossy, J.-F. and Joseph, A., 1983. Hydrologie isotopique et
hydrochemie des aquiferes discontinus de la bande sahelienne et de LÁír (Niger). In:
Isotope Hydrology 1983, IAEA Vienna: 367-395.
Paces, T., 1987. Hydrochemical evolution of saline wasters from crystalline rocks of the
Bohemian Massif (Czechoslovakia).- In: P. Fritz and S.K. Frape (Editors), Saline Water
and Gases in Crystalline Rocks, Geol. Assoc. of Canada, Special Paper, 33: 145-156.
Paces T. (Editor) 1991. Fluid Sampling for Geothermal Prospecting, UNITAR/UNDP Centre
on Small Energy Resources, Rome: 93 pp.
Pang Zhonghe and Reed, M.H., 1998. Theoretical chemical geothermometry on geothermal
waters: Problems and methods. Geochim. Cosmochim. Acta, 62: 1083-1091.
Pang Zhonghe and Wang Jiyang, 1995. Application of isotope and geochemical techniques to
geothermal exploration - the Zhangzhou Case. In: Proc. 1995 World Geothermal
Congress, International Geothermal Association, Vol. 2: 1037-1042.
Panichi, C., Nuti, S. and Noto P., 1979. Remarks on the use of isotopic geothermometers in
the Larderello geothermal field. In: Isotope Hydrology Vol. II, IAEA Vienna: 613-630.
Paul, M., Fink, D., Hollos, G., Kaufman, A., Kutschera, W. and Magaritz, M., 1987. Measu-
rement of 129I concentrations in the environment after the Chernobyl reactor accident.
Nucl. Instr. Meth. Phys. Rev. B, 29: 341-345.
Pauwels, H., Fouillac, C., Goff, F. and Vuataz, F.-D., 1997. The isotopic and chemical
composition of CO2-rich thermal waters in the Mont-Dore region (Massif-Central,
France). Appl. Geochemistry, 12: 411-427.
Pearson, Jr. F.J. and Rightmire, C.T., 1980. Sulfur and oxygen isotopes in aqueous sulfur
compounds. In: P. Fritz and J.Ch. Fontes (Editors), Handbook of Environmental Isotope
Geochemistry, Elsevier, Amsterdam: 227-258.
168
References
Pearson, Jr., F.J., Noronha, C.J. and Andrews, R.W., 1983. Mathematical modeling of the
distribution of natural 14-C, 234-U, and 238-U in a regional groundwater system.
Radiocarbon, 25: 291-300.
Petit, J.-C., Langevin, Y. and Dran, J.-C., 1985. 234U/238U disequilibrium in nature. theoretical
reassessment of the various proposed models. Bull. Mineral., 108: 745-753.
Phillips, F.M., Goff, .F, Vuataz, .F, Bentley, H.W., Elmore, D. and Gove, H.E., 1984a. 36Cl as
a tracer in geothermal systems: example from Valles Caldera, New Mexico: Geophys.
Res. Letters, 11 (12): 1227-1230.
Phillips, F.M., Trotman, K.N., Bentley, H.W., Davis, S.N. and Elmore, D., 1984b. Chlorine-
36 from atmospheric nuclear weapons testing as a hydrologic tracer in the zone of
aeration in arid climates. In: Proc. RIZA Symp, Munnich: 47-56.
Phillips, M., Bentley, H.W., Davis, S.N., Elmore, D. and Swanick, G.B., 1986. Chlorine-36
dating of very old groundwater 2. Milk River aquifer, Alberta, Canada. Water. Resourc.
Res., 22 (13): 2003-2016.
Phillips, F.M., Tansey, M.K. and Peeters, L.A., 1989. An isotopic investigation of
groundwater in the central San Juan Basin, New Mexica: carbon 14 dating as a basis from
numwerical flow modeling. Water Res. Res., 25: 2259-2273.
Plöthner, D. and Geyh, M.A., 1991. δ18O values as tracer of artificial groundwater recharge
downstream of a reservoir. Memoires XXII (Part 2), IAH, Lausanne: 533-539.
Plummer, L.N., Prestemon, E.C. and Parkhurst, D.L., 1994. An interactive code (NETPATH)
for modeling Net Geochemical Reactions along a Flow Path. Version 2.0. Water-
Resources Investigation Report, 94-4169, U.S. Geol. Survey, Reston: 227 pp.
Richet, P., Bottinga, Y. and Javoy, M., 1977. A review of hydrogen, carbon, nitrogen,
oxygen, sulfur and chlorine stable isotope fractionation among gaseous molecules. Ann.
Reg. Earth Planet. Sci.: 65-110.
Richter, J., Szymczak, P., Abraham, T. and Jordan, H., 1993. Use of combinations of lumped
parameter models to interpret groundwater isotopic data. J. Contaminant Hydrol., 14: 1-
13.
Rogojin, V., Carmi, I. and Kronfeld, J., 1998. 14C and 234U-excess dating of groundwater in
the Haifa Bay region, Israel.. Radiocarbon, 40 (2): 945-951.
Rozanski, K., 1985. Deuterium and Oxygen-18 in European groundwaters - links to
atmospheric circulation in the past. Chem. Geology (Isot. Geosci. Sect.), 52: 349-363.
Rozanski, K. and Florkowski, T., 1979. Krypton-85 dating of groundwater. In: Isotope
Hydrology 1978 Vol.II, IAEA Vienna: 949-959.
Rye R.O. and Ohmoto H., 1974. Sulphur and carbon isotopes in ore genesis. Econ. Geology,
69: 910.
169
References
Sakai H. and Matsubaya O., 1977. Stable isotope studies of Japanese geothermal systems.
Geothermics, 5: 97-124.
Sakai, H., Gunnlaugsson, E., Tòmasson, J. and Rouse, J.E., 1980. Sulphur isotope systematics
in Icelandic geothermal systems and influence of seawater circulation at Reykianes.
Geochim. Cosmochim. Acta, 44: 1223-1231.
Salem, O., Visser, J.M., Deay, M. and Gonfiantini, R., 1980. Groundwater flow patterns in
the western Lybian Arab Jamahitiya evaluated from isotope data. In: Arid Zone
Hydrology: Investigations with Isotope Techniques, IAEA Vienna: 165-179.
Salvamoser, J., 1986. Quantitative separation of admixed young groundwater and surface
water with the 3H-85Kr method. In: Conjunctive Water Use, IAHS Publ. 156: 355-363.
Saxena, R.K. and Dressie, Z., 1984. Estimation of groundwater recharge and moisture
movement in sandy formations by tracing natural oxygen-18 and injected tritium profiles
in the unsaturated zone. In: Isotope Hydrology 1983, IAEA Vienna: 139-150.
Schaefer, R.W. and Usdowski, E., 1992. Application of stable carbon and sulfur isotope
models to the development of groundwater in a limestone-dolomite-anhydrite-gypsum
area. In: G. Matthess, G.F. Frimmel, P. Hirsch, H.D., Schulz, H.-E. and E. Usdowski
(Editors) Progress in Hydrogeochemistry, Springer, Berlin: 157-163.
Schlosser, P., Stute, M., Sonntag, C. and Münnich, K. O., 1989. Tritiogenic 3He in shallow
groundwater. Earth Planet. Sci. Letters, 94: 245-256.
Seiler, K.P. and Rodríguez, C.O., 1980. Geological and hydraulic boundary conditions for the
interpretation of isotope data. In: Proc. Interamerican Symp. on Isotope Hydrology,
Fondo Colombiano de Investigaciones Cientificas y Proyectos Especiales, Bogota: 43-59.
Smejkal V., 1978. Isotope geochemistry of the Cypris formation in the Cheb Basin, West
Bohemia. I. Sulphur isotopes in sulphates and pyrites. Vestnik Ustredniho ustava
geologickeho, 53: 3-18.
Smejkal, V. and Jetel, J., 1990: Isotopic and geochemical indications of a drainless sulfate
lake in the PermoCarboniferous of the Krkonose-piedmont basin. Vestnik Ustredniho
ustavu geologickeho, 65: 339-352.
Sonntag, C., Thoma, G., Münnich, K.O., Dincer, T. and Klitzsch E., 1980a. Environmental
isotopes in North African groundwaters and the Dahna sand-dune study, Saudi Arabia.
In: Arid-Zone Hydrology: Investigations with Isotope Techniques, IAEA Vienna: 77-84.
Sonntag, C., Thorweihe, U., Rudolf, J., Löhnert, E.P., Junghans, C., Münnich, K.O., Klitzsch,
E., El Shazly, E.M. and Swailem, F.M., 1980b. Paleoclimatic evidence in apparent 14C
ages of Saharian groundwaters. Radiocarbon, 22 (III): 871-878.
Sonntag, C., Christmann, D. and Münnich, K.O., 1985. Laboratory and field experiments on
infiltration and evaporation of soil water by means of deuterium and oxygen-18. In:
170
References
Stable and Radioactive Isotopes in the Study of the Unsaturated Zone, IAEA-TECDOC-
357, IAEA Vienna: 145-160.
Stagg, K.A., Kleinert, U., Tellam, J.H. and Lloyd, J.W, 1997. Colloidal populations in urban
and rural groundwaters, UK. In: P.J. Chilton (Editor), Groundwater in the Urban
Environment Vol. I, Problems, Processes and Management Balkema, Rotterdam: 187-
192.
Stewart, M.K., 1975. Stable isotope fractionation due to evaporation and isotopic exchange of
falling water drops: application to atmospheric processes and evaporation of lakes. J.
Geophys. Res., 80: 1133-1146.
Stewart, M.K., 1978. Stable isotopes in waters from the Wairakei geothermal system, New
Zealand. In: Stable Isotopes in the Earth Sciences, N.Z. DSIR Bull., 220: 113-119.
Stichler, W. and Herrmann, A., 1983. Application of environmental isotope techniques in
water balance studies of small basins. In: New Approaches in Water Balance
Computations, IAHS, Hamburg , IAHS-148: 93-112.
Stute, M. and Deak, M., 1989. Environmental isotopic study (14C, 13C, 18O, D, noble gases)
on deep groundwater circulation systems in Hungary with reference to paleoclimate.
Radiocarbon, 31 (3): 902-918.
Suckow, A. and Sonntag, C., 1993. The influence of salt on the noble gas geothermometer. In:
Isotopic Techniques in the Study of Past and Current Environmental Changes in the
Hydrosphere and the Atmosphere, IAEA Vienna: 307-318.
Sukhija, B.S. and Shah, C.R., 1976. Conformity of groundwater recharge rate by tritium
method and mathematical modelling. J. Hydrol., 30: 167-78.
Taran, Y.A., Pokrovsky B.G. and Esikov, A.D. , 1988. Deuterium and oxygen-18 in fumarolic
steam and amphiboles from some Kamchatka volcanoes. "Andesitic" waters. IAVCEI,
Commission on the Chemistry of Volcanic Gases, Newsletter, 1: 15-18.
Taylor H.P., 1974. The application of oxygen and hydrogen isotope studies to problems of
hydrothermal alteration and ore deposition. Econ. Geol., 69: 843-883.
Taylor, H.P. jr., 1977. Water/rock interaction and the origin of H20 in granitic batholits.
J. Geol. Soc. London, 133: 509-558.
Taylor, B.E., Wheeler, M.C. and Nordstrom, D.K., 1984. Isotopic composition of sulfate in
acid mine drainage as measure of bacterial oxidation. Nature, 308: 538-541.
Thoma, G., Esser, N., Sonntag, C., Weiss, W. and Rudolph, J., 1979. New technique of in-situ
soil-moisture sampling for environmental isotope analysis applied at Pilot sand dune near
Bordeaux - HETP modelling of bomb tritium propagation in the unsaturated and satura-
ted zones. Isotope Hydrology 1978, Vol. II, IAEA Vienna: 191-204.
171
References
Thorburn, P.J. and Walker, G.R., 1994. Variations in stream water uptake by Eucalyptus
camaldulensis with differing access to stream water. Oecologia, 100: 293-301.
Todd, D.K., 1959. Groundwater Hydrology, Wiley, New York: 336 pp.
Toran, L. and Harris, R.F., 1989. Interpretation of sulphur and oxygen isotopes in biological
and abiological sulfide oxidation. Geochim. Cosmochim. Acta, 53: 2341-2348.
Torgersen ,T. and Clarke, W.B., 1985. Helium accumulation in groundwater I: an evaluation
of sources and the continental flux of crustal 4He in the Great Artesian Basin, Australia.
Geochim. Cosmochim. Acta, 49: 1211-1218.
Torgersen, T. and Clarke, W.B., 1987. Helium accumulation in groundwater. III. Limits on
helium transfer across the mantle-crust boundary beneath Australia and the magnitude of
mantle degassing. Earth Planet. Sci. Letters, 84: 345-355.
Torgersen ,T. and Ivey, G.N., 1985. Helium accumulation in groundwater. II: A model for the
accumulation of the crystal 4He degassing flux. Geochim. Cosmochim. Acta, 49: 2445-
2452.
Tóth, J., 1963. A theoretical analysis of groundwater flow in small drainage basins. J.
Geophys. Res., 68: 4795-4812.
Truesdell A.H. and Hulston J.R., 1980. Isotopic evidence on environments of geothermal
systems. In: P. Fritz and J. Ch. Fontes (Editors), Handbook of Environmental isotope
Geochemistry Vol. I: 179-226.
Truesdell, A.H., Nathenson, M. and Rye, R.O., 1977. The effects of subsurface boiling and
dilution on the isotopic composition of Yellowstone thermal waters. J. Geophys. Res., 82:
3694-3704.
Van Warmerdam, E.M., Frape, S.K., Aravena, R., Drimmie, R.J., Flatt, H. and Cherry, J.A.,
1995. Stable chlorine and carbon isotope measurements of selected organic solvents.
Appl. Geochem., 10. 547-552.
Vengosh, A., Chivas, A.R., McCulloch, M.T., Starinsky, A. and Kolodny, Y., 1991. Borone-
isotope geochemistry of Australian salt lakes. Geochim. Cosmochim. Acta, 55: 2591-
2606.
Vengosh, A., Heumann, K.G., Juraske, S. and Kasher, R., 1994. Boron isotope application for
tracing sources of contamination on groundwater. Environ. Sci. Technol., 28: 1968-1974.
Vengosh, A., Kolodny, Y., and Spivack, A.J., 1998. Ground-water pollution determined by
boron isotope systematics. In: Application of Isotope Techniques to Investigate
Groundwater Pollution, IAEA-TECDOC-1046, IAEA, Vienna: 17-38.
Verhagen, B.Th., Mazor, E. and Sellshop, J.P.F., 1974. Radiocarbon and tritium evidence for
direct recharge to groundwaters in the Northern Kalahari. Nature, 249: 643-644.
172
References
Verhagen, B.Th., Geyh, M.A., Fröhlich, K. and Wirth, K., 1991. Isotope Hydrological
Methods for the Quantitative Evaluation of Ground Water Resources in Arid and Semi-
arid Areas. Development of a Methodology, Ministry of Economic Cooperation, Bonn:
164 pp.
Vogel, J.C., 1970. Carbon-14 dating of groundwater. In: Isotope Hydrology 1970, IAEA
Vienna: 225-240.
Vogel, J.C., Ehhalt, D., 1963. The use of the carbon isotopes in groundwater studies. In:
Radioisotopes in Hydrology, IAEA Vienna: 383-395.
Wassenaar, L., Aravena, R., Hendry, J. and Fritz, P., 1991. Radiocarbon in dissolved organic
carbon, a possible groundwater dating method: Case studies from western Canada. Water
Res. Res., 27: 1975-1986.
Wakshal, E. and Yaron, F., 1974. 234U/238U disequilibrium in waters of the Judea Group
(Cenomanian-Turonian) aquifer in Galilee, northern Israel. In: Isotope Techniques in
Groundwater Hydrology Vol. II, IAEA Vienna: 151-177.
Walker, G.R., Hughes, M.W., Allison, G.B. and Barnes, C.J., 1988. The movement of
isotopes of water during evaporation from a bare soil surface. J. Hydrol., 97: 181-197.
Weiss, W., Sittkus, A., Stockburger , H., Sartorius, H. and Münnich, K.O., 1983. Large-scale
atmospheric mixing derived from meridional profiles of krypton-85. J. Geophys. Res., 88
(C 13): 8574-8578.
White, D.E., Barnes, I. and O'Neil, J.R., 1973. Thermal and mineral waters of nonmeteoric
origin, California Coast Ranges. Geol. Soc. Am. Bull., 84: 547-560.
Wickman, T. and Jacks, G., 1992. Strontium isotopes in weathering budgeting. In: Y.K.
Kharaka and A.S. Maest (Editors), Water-Rock Interaction: 611-614.
Wigley, T.M.L., Plummer, L.N. and Pearson, F.J., Jr. , 1978. Mass transfer and carbon
isotope evolution in natural water systems. Geochim. Cosmochim. Acta., 42: 1117-1139.
Woods, P.H., 1990. Evaporative discharge of groundwater from the margin of the Great
Artesian Basin near Lake Eyre, South Australia. Unpubl. PhD Thesis, Flinders
University, South Australia
Yechieli, Y., Ronen, D. and Kaufman, A., 1996. The source and age of groundwater brines in
the Dead Sea area, as deduced from 36Cl and 14C. Geochim. Cosmochim. Acta, 60: 1909 -
1916.
Yurtsever, Y. and Payne, B.R., 1979. Application of environmental isotopes to groundwater
investigations in Qatar. Isotope Hydrology 1978 Vol. II, IAEA Vienna: 465-490.
Zimmermann, U., Ehhalt, D. and Münnich, K.G., 1967. Soil water movement and evapotrans-
piration: changes in the isotopic composition of the water. In: Isotopes in Hydrology,
173
References
Zuber, A., 1986. Chapter 1. Mathematical models for the interpretation of environmental
radioisotopes in groundwater systems. In: P. Fritz and J. Ch. Fontes (Editors), Handbook
of Environmental Isotope Geochemistry Vol. 2, Elsevier, Amsterdam: 1-59.
174
LITERATURE
H.Moser Isotopenmethoden in der Hydrologie (1980) Gebr. Borntraeger
W.Rauert (in German language) ISBN 3-443-01012-1 Berlin, Stuttgart
P.Fritz Handbook of Environmental Isotope Elsevier Science Publ.

J.Ch.Fontes Geochemistry ISBN 0-444-41781-8 Amsterdam, Oxford
New York, Tokyo
Vol.1. The Terrestrial Environment A (1980) ISBN 0-444-41780-X
Vol.2. The Terrestrial Environment B (1986) ISBN 0-444-42225-0
Vol.3. The Marine Environment A (1989) ISBN 0-444-42764-3
F.J.Pearson Applied Isotope Hydrogeology, a case study Elsevier Science Publ.

e.a. in Northern Switzerland (1991) Amsterdam, Oxford,
ISBN 0-444-88983-3 New York, Tokyo
I.Clark Environmental Isotopes in Hydrogeology Lewis Publishers

P.Fritz (1997) Boca Raton,
ISBN 1-56670-249-6 New York
F.Gasse Hydrology and Isotope Geochemistry Editions de l'Orstom

Ch.Causse ISBN 2-7099-1377-1 Paris
W.Kaess Tracing in Hydrogeology (1998) Balkema, Rotterdam

ISBN 3-443-01013-X
C.Kendall Isotopes in Catchment Hydrology (1998) Elsevier/North

J.J.McDonnell Holland Publ.Comp.
ISBN 0-444-50155-X Amsterdam
175
Literature
E.Mazor Chemical and Isotopic Groundwater Marcel Dekker Inc.

Hydrology – The applied approach (1998)
ISBN 0-8247-9803-1
P.G.Cook Environmental Tracers in Subsurface Kluwer Acad. Publ.

A.L.Herczeg Hydrology (2000)
(ed.) ISBN 0-7923-7707-9
176
Literature
IAEA PUBLICATIONS
IAEA CONFERENCE PROCEEDINGS
1963 Radioisotopes in Hydrology, Tokyo, 5-9 March 1963, IAEA, Vienna, 459 pp.
(STI/PUB/71) (out of print).
1967 Isotopes in Hydrology, Vienna, 14-18 November 1966, IAEA, Vienna, (in co-operation
with IUGG), 740 pp. (STI/PUB/141) (out of print).
1970 Isotope Hydrology, Vienna, 6-13 March 1970, IAEA, Vienna, (in co-operation with
UNESCO), 918 pp. (STI/PUB/255) (out of print).
1974 Isotope Techniques in Groundwater Hydrology, Vienna, 11-15 March 1974, IAEA,
Vienna, 2 volumes: 504 and 500 pp. (STI/PUB/373) (out of print).
1979 Isotope Hydrology (in 2 volumes), Neuherberg, Germany, 19-23 June 1978, IAEA,
Vienna, (in co-operation with UNESCO), 2 volumes of 984 pp. (STI/PUB/493) ISBN 92-0-
040079-5 and ISBN 92-0-040179-1.
1983 Isotope Hydrology, Vienna, 12-16 September 1983, IAEA, Vienna, (in co-operation
with UNESCO), 873 pp. (STI/PUB/650) ISBN 92-0-040084-1.
1987 Isotope Techniques in Water Resources Development, Vienna, 30 March-3 April
1987, IAEA, Vienna, (in co-operation with UNESCO), 815 pp. (STI/PUB/757) ISBN 92-0-
040087-6.
1992 Isotope Techniques in Water Resources Development, Vienna, 11-15 March 1991,
IAEA, Vienna,(in co-operation with UNESCO), 790 pp.(STI/PUB/875) ISBN 92-0-000192-0.
1993 Isotope Techniques in the Study of Past and Current Environmental Changes in
the Hydrosphere and the Atmosphere, Vienna, 19-23 April 1993, IAEA, Vienna, 624
pp. (STI/PUB/908) ISBN 92-0-103293-5.
1995 Isotopes in Water Resources Management (in 2 volumes), IAEA, Vienna, 20-24
March 1995, IAEA, Vienna, 2 volumes: 530 and 463 pp. (STI/PUB/970) ISBN 92-0-
105595-1 and 92-0-100796-5.
1998 Isotope Techniques in the Study of Environmental Change, Vienna, 14-18 April
1997, IAEA, Vienna, 932 pp. (STI/PUB/1024) ISBN 92-0-100598-9.
1999 Isotope Techniques in Water Resources Development and Management, 10-14 May
1999, IAEA, Vienna, CDRom (IAEA-CSP-2C) ISSN 1562-4153.
177
Literature
SPECIAL IAEA SYMPOSIA

1967 Radioactive Dating and Methods in Low-Level Counting, Monaco, 2-10 March
1967, IAEA, Vienna, 744 pp. (STI/PUB/152) (out of print).
1979 Behaviour of Tritium in the Environment, San Fransisco, USA, 16-20 October 1978,
711 pp. (STI/PUB/498) ISBN 92-0-020079-6.
1981 Methods of Low-Level Counting and Spectrometry, Berlin, Germany, 6-10 April
1981, IAEA, Vienna, 558 pp. (STI/PUB/592) (out of print).
IAEA REPORTS AND TECHNICAL DOCUMENTS (TECDOCS)
Environmental Isotope Data no.1 − no.10: World Survey of Isotope Concentration in

Precipitation, Data from network of IAEA and WMO over period 1953-1991,
published 1969-1994.
Interpretation of Environmental Isotope and Hydrochemical Data in Groundwater
Hydrology, Proc. Adv. Group Meeting, Vienna, 27-31 January 1975, IAEA, Vienna,
1976, 230 pp. (STI/PUB/429) ISBN 92-0-141076-X.
Isotopes in Lake Studies, Proc. Adv. Group Meeting, Vienna, 29 August-2 September 1977,
IAEA, Vienna, 1979, 290 pp. ISBN 92-0-141179-0 (out of print).
Arid Zone Hydrology: Investigations with Isotope Techniques, Proc. Adv. Group
Meeting, Vienna, 6-9 November 1978, IAEA, Vienna, 1980, 265 pp. (STI/PUB/547)
ISBN 92-0-141180-4.
Stable Isotope Standards and Intercalibration on Hydrology and Geochemistry, (R.

Gonfiantini ed.), Report on Consultants' Meeting, Vienna, 8-10 September 1976, IAEA,
Vienna, 1977.
Stable Isotope Hydrology Deuterium and Oxygen-18 in the Water Cycle, (J.R.Gat and
R.Gonfiantini eds.), Monograph by Working Group, IAEA, Vienna, 1981, 340 pp.
(STI/DOC/10/210).
Palaeoclimates and Palaeowaters: A Collection of Environmental Isotope Studies, Proc.
Adv. Group Meeting, Vienna, 25-28 November 1980, IAEA, Vienna, 1981, 207 pp.
(STI/PUB/621) ISBN 92-0-141083-2.
178
Literature
Guidebook on Nuclear Techniques in Hydrology, by Working Group IAEA, Vienna, 1983,

439 pp. (STI/DOC/10/91/2)
Stable Isotope Reference Samples for Geochemical and Hydrological Investigations, (R.
Gonfiantini ed.), Report by Advisory Group's Meeting, Vienna, 19-21 September 1983,
IAEA, Vienna, 1984.
Stable and Radioactive Isotopes in the Study of the Unsaturated Soil Zone, Proc. Meeting
on IAEA/GSF Progr., Vienna, 10-14 September 1984, IAEA, Vienna,1985, 184 pp.
(TECDOC-357)
Isotope Techniques in the Study of the Hydrology of Fractured and Fissured Rocks,
Proc. Adv. Group Meeting, Vienna, 17-21 November 1986, IAEA, Vienna, 1989, 306 pp.
(STI/PUB/790)
Stable Isotope Reference Samples for Geochemical and Hydrological Investigations,
Report on Consultants' Meeting, Vienna, 16-18 September 1985, edited by G. Hut,
IAEA, Vienna, 1987.
Use of Artificial Tracers in Hydrology, Proc. Adv. Group Meeting, Vienna, 19-22 March
1990, IAEA, Vienna, 1990, 230 pp. (TECDOC-601)
C-14 Reference Materials for Radiocarbon Laboratories, (K. Rozanski, ed), Report on
Consultants' Meeting, Vienna, 18-20 February 1981, IAEA, Vienna 1991.
Guidelines for Isotope Hydrology, Manuel for Operation of an Isotope Hydrology
Laboratory IAEA, Vienna, 1999 (in prep.)
Isotopes of Noble Gases as Tracers in Environmental Studies, Report by Consultants'
Meeting, Vienna, 29 May-2 June, 1989, IAEA, Vienna, 305 pp. (STU/PUB/859) (out of
print) ISBN 92-0-100592-X
Statistical Treatment of Data on Environmental Isotopes in Precipitation, IAEA, Vienna,
1992, 781 pp. (STI/DOC/10/331)
Isotope and Geochemical Techniques applied to Geothermal Investigations, Proc. Res.
Coord. Meeting, Vienna, 12-15 October 1993, IAEA, Vienna, 1995, 258 pp. (TECDOC-
788)
Reference and Intercomparison Materials for Stable Isotopes of Light Elements, Proc.
Cons. Meeting, Vienna, 1-3 December 1993, IAEA, Vienna, 1995. (TECDOC-825)
Manual on Mathematical Models in Hydrogeology, IAEA, Vienna, 1996, 107 pp.
(TECDOC-910)
179
CONSTANTS
a year = 3.1558×107 s
amu atomic mass unit = 1.660 54×10−27 kg
c velocity of light (in vacuum) = 2.997 925×108 m⋅s−1
cal calorie = 4.184 J
e elementary/electron/proton charge = 1.602 18×10−19 C
eV electronvolt = 1.602 18×10−19 J
g acceleration of free fall = 9.806 65 m⋅s−2
h Planck constant = 6.626 08×10−34 J⋅s
J Joule = 0.2390 cal
k Boltzmann constant = 1.380 54×10−23 J/K
me electron mass = 9.109 39×10−31 kg
mn neutron mass = 1.674 93×10−27 kg
mp proton mass = 1.672 62×10−27 kg
M/E eq. mass/energy equivalence: 1 amu ≡ 931.5 MeV
NA Avogadro constant = 6.022 14×1023 mol−1
π = 3.141 592 6535
R gas constant = 8.314 51 J⋅K−1⋅mol−1
T thermodynamic temperature = t (0C) + 273.15 K
Vm molar volume (= 22.41 L⋅mole−1 at STP)
180
GLOSSARY
The following text books were used for the glossary: Glossary of Geology (1980) and
International Glossary of Hydrology (1998), IHP/OHP-Reports, Koblenz, 243 pp.
Age: → Water age

Apparent age: Age determined by any method without consideration of all necessary
corrections and conventions.
Applied hydrology: Branch of hydrology which applies to its application to the filed
connected with water-resources development and management.
Aquiclude: A body of relatively impermeable rock that is capable of absorbing water slowly
but functions as an upper or lower boundary of an aquifer and does not transmit
groundwater rapidly enough to supply a well or spring.
Aquifer: A body of rock that contains sufficient saturated permeable material to conduct
groundwater and to yield economically significant quantities of groundwater to wells and
springs (→ permeability, Sect.1.1).
Aquitard: A confining bed that retards but does not prevent the flow of water from an
adjacent aquifer (leaky confining bed). It does not readily yield water to wells or springs,
but may serve as a storage unit for groundwater (→ Sect.1.1).
Artesian aquifer: A confined aquifer containing groundwater under pressure, high enough to
cause outflow in a well or spring.
Artesian spring: A spring discharging confined water from an underlying aquifer through a
fissure or other opening in the confining bed that overlies the aquifer (→ Sect.3.1.4.1).
Artesian water: In the traditional sense groundwater with a piezometric pressure high
enough to cause outflow from a well or spring (→ confined groundwater).
Artesian well: A well tapping a confined or artesian aquifer in which the static water level
stands above the surface of the ground or at least of the level of the shallow groundwater
(→ confined aquifer).
Artesian recharge: Recharge of groundwater at a rate greater than natural, resulting from the
activities of man, by means of dug basins, drilled wells, or spreading of water across the
land surface.
181
Glossary
Base flow: The part of the discharge, which enters a stream channel from groundwater. This
is the runoff observed during long periods when no precipitation or snowmelt occurs.
Boundary conditions: Set of conditions to be satisfied by the solution of a differential
equation at the boundary (including fluid boundary) of the region in which the solution is
sought.
Brackish water: Groundwater with a total salt concentration of 1000 to 10 000 mg/L.
Capillary fringe: The zone immediately above the water table, where water is drawn upward
by capillary attraction.
Catchment area: The entire area between the recharge and the discharge area
Coefficient of filtration: → hydraulic conductivity (Sect.3.1.1)
Cone of depression: → Pumping cone. Depression, in the shape of a cone with convex
upwards limits, of the piezometric surface which defines the area of influence of a well.
Conceptional hydrological model: Simplified mathematical representation of some or all of
the processes in the hydrological cycle by a set of hydrological concepts expressed in
mathematical notations and linked together in a time and space sequence corresponding
to that occurring in nature. Hydrological conceptional models are used for simulation of
the behaviour of a basin (Sect.3.1.2 and 3.1.3; Volume VI).
Confined aquifer: An aquifer bounded above and below by impermeable beds or by beds of
distinctly lower permeability than that of the aquifer itself; an aquifer containing confined
groundwater.
Confined groundwater: Groundwater under a pressure significantly greater than that of the
atmosphere. If tapped by a borehole, the water level in the borehole rises so that it
corresponds to the pressure height at the point where it was tapped.
Confined groundwater surface: The upper surface of the groundwater body is under a
pressure higher than that of the atmosphere. Identical with the upper surface of a confined
aquifer. If tapped by a borehole, groundwater rises to the piezometric surface.
Confining bed: The formation overlying or underlying a much more permeable aquifer. →
aquiclude, aquitard
Connate water: Water entrapped in the interstices of a sedimentary rock at the time of its
deposition that has been out of contact with the atmosphere for at least an appreciable
part of a geologic period.
Darcy law: → Sect.3.1.1
Diffusion: Process of spreading of a solute as a result of the thermal movement of the
molecules of this solute. → Sect.3.1.2
182
Glossary
Direct runoff: Flow of water entering stream channels promptly. It includes surface flows
and interflow and is used where interflow cannot be separated in hydrological analysis.
This part of surface runoff which reaches the catchment outlet shortly after the rain starts.
Its volume is equal to rainfall excess. Some procedures for its derivation include prompt
subsurface runoff but all exclude base flow.
Distance velocity: (syn. tracer velocity) – Velocity of a tracer defined by the quotient of
distance and time. → filter velocity (Sect.3.1.1).
Drawdown: The distance by which the water level in a well is lowered by the withdrawal of
water.
Effective porosity: The percentage of the total volume of a given mass of soil or rock that
consists of interconnecting interstices through which water or other fluids can travel. →
Sect.1.3.1
Field capacity: amount of water held in a soil after gravitational water has drained away.
→ Sect.1.3.2
Filter velocity: mass transport velocity in volume unit per time and area units calculated by
the Darcy law. → Sect.3.1.1
Fossil water: Water recharged in an ancient geological period and not participating in the
contemporary hydrological cycle.
Free water table: The unconfined groundwater level at which the pressure is equal to the
atmospheric pressure.
Freshwater: Naturally occurring water having a concentration of salt < 1000 mg/L.
Gravitational water: (syn. mobile water) – Water in the unsaturated zone which moves
under the influence of gravitity. → Sect.1.3.1
Groundwater: (a) Subsurface water that is in the zone of saturation. It includes underground
streams. (b) Loosely all subsurface water (excluding internal water) as distinct from
surface water.
Groundwater dating: Determination of the time between the recharge of the groundwater
and its sampling. → Sect.5.2.2
Groundwater divide: Line on a water table or piezometric surface on either side of which the
groundwater flow diverges.
Groundwater level: (syn. groundwater table) – The elevation, at a certain location and time,
of the phreatic or piezometric surface of an aquifer.
Groundwater level: Elevation, at a certain location and time, of the water table or
piezometric surface of an aquifer.
183
Glossary
Groundwater mining: Withdrawal from an aquifer containing fossil groundwater

(Sect.3.2.1).
Groundwater overexploitation: Withdrawal of a groundwater reservoir in excess of the
average rate of replenishment.
Groundwater recharge → Recharge
Groundwater table: (syn. groundwater level, phreatic surface) – The surface within the zone
of saturation of an unconfined aquifer along which the pressure is atmospheric.
Head, total: The sum of the elevation head, the pressure head, and the velocity head at a
given point in an aquifer.
Histogram: Univariate frequency diagram with rectangles proportional to the area to the class
frequency, erected on a horizontal axis with width equal to the class interval.
Hydraulic conductivity (K): (syn. permeability coefficient) – A coefficient of
proportionality describing the rate at which water can move through a permeable
medium. The density and kinematic viscosity must be considered in determining the
hydraulic conductivity. It has a dimension of velocity. → Sect.1.3.3
Hydrological cycle: Succession of stages through which water passes from the atmosphere to
the earth and returns to the atmosphere: evaporation from the land or sea or inland water,
condensation to form clouds, precipitation, accumulation in the soil or in bodies of water,
and re-evaporation. → Volume I
Hydrological regime: Variations in the state and characteristics of a water body which are
regularly repeated in time and space and which pass through phases, e.g. seasonal. →
Sect.1.4.2
Hydrosphere: That part of the earth covered by water and ice. → Volume I
Intermediate zone: That part of the unsaturated zone below the root zone and above the
capillary fringe. → Sect.5.1
Infiltration coefficient: Ratio of infiltration to rainfall.
Interflow: That portion of the precipitation which has not passed down to the water table, but
is discharged from the unsaturated zone by lateral movement during and immediately
after a precipitation event. The water moving as interflow discharges directly into a
stream channel or lake.
Intermittent spring: Spring, which discharge occurs only during certain periods and ceases
at other periods. → Sect.3.1.4.1
Juvenile water: A term applied to water that is known to have been derived directly from
magma and that is thought to have come to the Earth’s surface for the first time.
184
Glossary
Karst: Limestone and dolomite areas that possess a topography peculiar to and dependent
upon underground solution and the diversion of surface waters to underground routes. →
Sect.1.4.2.4
Leaky aquifer: Aquifer overlain and/or underlain by a relatively thin semi-pervious layer,
through which flow into or out of the aquifer can take place.
Magmatic water: Water brought to the earth's surface from great depths by the upwards
movement of intrusive igneous rocks. → Chapter 6
Modern water: The groundwater directly recharged after 1963/64 labeled by higher activities
of nuclear-bomb-produced tritium and radiocarbon. → Sect.5.2.2.1 and 5.2.2.2
Moisture content or soil humidity: The weighted moisture content is expressed by the ratio
of the mass of water Mw to the total mass or to the mass of the solid Mt. The volumetric
humidity or volumetric water content is the ratio of the volume of water Vw to the total
volume of the sample Vt. → Sect.5.1.1
Observation well: Well used for measuring the static head of groundwater, and specially to
observe the frequency and magnitude of changes in head or another physical or chemical
parameter. → Sect.3.1.4.2
Perched groundwater: Unsaturated groundwater separated from an underlying main body of
groundwater by an unsaturated zone (Sect.5.1).
Permeability: The property or capacity of a porous rock, sediment, or soil for transmitting a
fluid; it is a measure of the relative ease of fluid flow under unequal pressure. The
expressions “permeable” and “impermeable” have a relative meaning. An intercalation of
the same permeability between layers of lesser permeability can act as an aquifer while
between more permeable layers; it can act as an aquiclude. → Sect.1.3.3
Phreatic surface: The surface between the zone of saturation and the zone of aeration at
which the pressure is equal to that of the atmosphere.
Phreatic water: A term that originally was applied only to water that occurs in the upper part
of the zone of saturation under water-table conditions, but has come to be applied to all
water in the zone of saturation, thus making it an exact synonym of groundwater.
Piezometer: A pipe sealed along its length, open to water flow at the bottom and open to the
atmosphere at the top, that is used to measure the piezometric head at the point of an
aquifer to which it reaches.
Piezometric head: (a) The elevation to which water of a given aquifer will rise in a
piezometer. (b) The sum of the elevation and the pressure head in a liquid expressed in
units of height.
Piezometric surface: (syn. potentiometric surface) – The surface to which water would rise
in piezometers reaching into the same aquifer. In general, the piezometric surface is not
185
Glossary
horizontal and plane but curved and it reflects the distribution of the hydraulic potential,
i.e. of the mechanical energy of water within the aquifer at the depth reached by the
piezometers. → Sect.1.3.4
Playa: Lake bed found in arid or desert regions in the lower part of a enclosed valley whose
drainage is centripetal or inward. The lake is usually dry, except after heavy rains storms,
when it may be covered by a thin sheet of water which quickly disappears through
evaporation and/or infiltration.
Porosity: The total porosity is defined by the ratio of the total volume of water Vw and gas Vg
available for water to the total volume of the sample Vt. This parameter may vary in case
of refraction or expansion of the solid matrix (clays, gypsum). The effective porosity is
defined by Vw / Vt. → Sect.1.3.1
Potential evaporation: Quantity of water valour which could be emitted by a surface of pure
water in the existing conditions.
Potentiometric surface: → Piezometric surface
Pumping cone: The area around a discharging well where the hydraulic head in the aquifer
has been lowered by pumping. → cone of depression
Pumping test: (syn. aquifer test) – A test made by pumping a well for a period of time and
observing the change in hydraulic head in the aquifer. A pumping test may be used to
determine the capacity of the well and the hydraulic characteristics of the aquifer.
Recharge: Direct recharge is related to the seepage of rainwater through the unsaturated
zone into the aquifer. Indirect recharge is the recharge via rivers, lakes and other
superficial water resources. Artificial recharge is the seepage of e.g. river water into a
superficial sand bed where it recharge an exploited aquifer.
Residence time: Period during which water or a substance remains in a component part of the
hydrological cycle. → Sect.3.1.2
Return flow: Any flow returns to a stream channel or to the groundwater after use.
Root zone: The zone from the land surface to the depth penetrated by plant roots. The root
zone may contain part or all of the unsaturated zone, depending upon the depth of the
roots and the thickness of the unsaturated zone (Sect.5.1).
Runoff: The total amount of water flowing in a stream. It includes overland flow, return flow,
interflow and base flow.
Safe yield: Amount of water (in general, the long-term average amount) which can be
withdrawn from a groundwater basin or surface water system without causing undesirable
results.
Salt water: Water of which salt concentration exceeds 10 g/L.
186
Glossary
Saturated zone: −> Zone of saturation.

Secondary porosity: The porosity developed in a rock after its deposition or emplacement,
through such processes as solution or fracturing.
Storage coefficient: (syn. storativity) – Volume of water an aquifer releases from or takes
into storage per unit surface area of the aquifer per unit change of head.
Subsurface water: (syn. subterranean water, underground water, groundwater) – Water in the
lithosphere in solid, liquid, or gaseous form. It includes all water beneath the land surface
and beneath the bodies of surface water.
Time series: Set of observations, in order, taken at successive points of time, commonly at a
fixed interval.
Tracer velocity: → Distance velocity, Sect. 3.1.1
Transmissivity: The rate at which water of prevailing density and viscosity is transmitted
through a unit width of an aquifer or confining bed under a unit hydraulic gradient. It is a
function of properties of the liquid, the porous media, and the thickness of the porous
media. → Sect.1.3.3
Turnover rate: Ratio of the annual average groundwater recharge, expressed in volume, to
the average groundwater storage of an aquifer. → Sect.3.1.2
Turnover time: Time required for supplying a volume equal to the total water reserve in a
surface or groundwater reservoir, at the average rate of natural inflow or replenishment.
→ Sect.3.1.2
Unconfined aquifer: An aquifer containing unconfined groundwater. → phreatic water
Unconfined groundwater: Groundwater that has a free water table, i.e. water not confined
under pressure beneath impermeable rocks. → phreatic water
Unconfined groundwater level: The groundwater level at which the pressure is equal to the
atmospheric pressure, i.e. the surface of groundwater in an unconfined aquifer. →
phreatic water
Unsaturated zone: The zone between the land surface and the water table. It includes the
root zone, intermediate zone, and capillary fringe. The pore spaces contain water at less
than atmospheric pressure, as well as air and other gases. Saturated bodies, such as
perched groundwater, may exist in the unsaturated zone. Also called zone of aeration and
vadose zone. → zone of aeration, Sect.5.1
Vadose water: any water that occurs in the unsaturated zone. → Sect.5.1
Velocity: → Distance velocity
Zone of aeration: (syn. unsaturated zone) – A subsurface zone containing water under
pressure less than that of the atmosphere. It bears water held by capillary forces and air or
187
Glossary
gases generally under atmospheric pressure. This zone is limited above by the land
surface and below by the surface of the zone of saturation, i.e. the water table. The zone
is subdivided into the belt of soil water, the intermediate belt and the capillary fringe. →
Sect. 5.1
Zone of saturation: A subsurface zone in which all the interstices are filled with water under
pressure greater than that of the atmosphere. → Sect. 5.2.
188
SYMBOLS
c solute concentration in water ε enrichment or depletion = α − 1
d thickness λ radioactive decay constant
d deuterium excess ρ density of liquid or vapour
f residence-time distribution function σ standard deviation
g acceleration due to gravity το tortuosity
h height ∆ difference
k distribution coefficient ?? volumetric water content, humidity,
m thickness field capacity
q deposition rate Σ sum
r residual fraction
s slope
t age, time
t mean residence time SUBSCRIPTS
v velocity aqu aquifer
x proportion for mixing; x coordinate atm atmospheric
y horizontal axis, y coordinate avg average
z length, distance; z coordinate bnd bound
A area; amplitude;specific cap capillary
activity = disintegrations/s char characteristic
D diffusion or dispersion coefficient diff diffusion
H relative humidity; enthalpy dis discharge
J flux of solute disp dispersion
K hydraulic conductivity ef evaporation front
M mass eff effective
NSat saturated water vapour density equ equilibrium
MIX mixed sample eva evaporation
Q discharge, recharge, evaporation gas gas
rate in input
R atomic ratio between a rare and the init initial
abundant isotope of an element isot isotope species
S storage coefficient or degree of kin kinetic
saturation liq liquid
T temperature mob mobile
T1/2 half-life out output
V volume por pores
X end-member of mixing rec recharge
Y mixed sample res feed soil water
α equilibrium fractionation factor rock rock
αkin kinetic fractionation factor sol solid
β compressibility of the rock, water spl sample
δ relative deviation of an isotope std standard
ratio tot total
from that of a standard trac tracer
189
190
SUBJECT INDEX
AMS 101
2
H 66 anion exclusion 42, 51, 97
3
H 96 anthropogenic disturbance 37
3
He 96 Antilebanon mountains 151
4
He 22, 113 aquiclude 177
11
B 89 aquifer 177
13
C 72 artesian 11
14
C 18, 100 confined 4, 13, 25, 178
14
N 18, 75 leaky 31, 180
18
O 66 perched 180
32
Si 107 open 25
34
S 18, 79 phreatic 4, 31, 180
36
Cl 107 unconfined 25, 182
39
Ar 109 aquitard 177
81
Kr 110 argon-39 109
85
Kr 111 arid regions 7
86
Sr 17, 48, 92 Azraq springs 38
129
I 112
222
Ra 114
226
Ra 114
b
234
U 115 
234
U/238U 115 base flow 8, 177
Berlin geothermal field, Salvador 140
Black Triangle, Czech Republic 94
a black-box model 30
 Bohemian Massiv 47
absorption 42 boron isotopes 89
accelerator mass spectrometry ⇒ AMS boundary conditions 177
Ad Rhuma springs 106 Botswana 59, 157
admixture brackish water 177
seawater 46 by-pass flow 53
surface water 71
adsorption 42
advection 51
c
age 
absolute 74, 101, 116, 153, 182 capillary fringe 177
apparent 19, 177 182 carbon dioxide
conventional 107, 182 biogenic 74
determination 95 magmatic 74
groundwater 95 carbon isotopes
model 182 stable 72
relative 153, 182 radioactive 18, 100
retention 2 carbonate-CO2 system 43, 103
alluvial plain 12, 14 catchment area 178
altitude effect 69, 71 CFC ⇒ chlorofluorocarbon
amount effect 68 Cheb, Czech Republic 86, 87
chemical reactions
191
Index
carbonate 43, 74 dug well 98, 153

organic matter 44
sulfur compounds 46
chlorine isotopes
e
stable 89 
radioactive 107 effective porosity 178, 181
chlorine-36 107 El Tatio geothermal field 161
chlorofluorocarbon 22, 100, 111, 187 evaporation rate 59
coefficient exchange;
filtration 178 ion 43
infiltration 179 isotopic 41, 123
storage 4, 181
colloids 21, 46 f
conceptional model 178 
conductivity, hydraulic 5, 26, 27, 177 FA (fulvic acids) 102, 189
confined fallout 58, 189
aquifer 178 fertiliser 77
bed 178 field capacity 4, 178
groundwater 178 Fijeh springs, Syria 151
connate water 178 filtration velocity 27
continental effect 69, 72 flow
convection 51 direction 6, 36, 108
correction of 14C groundwater age laminar 25
Gonfiantini model 74, 103 line 6
geochemical modelling 44, 107 macropore 53
Oeschger model 44, 106 modelling 25, 32
Cyprus 71, 73 net, arid regions 5, 7
net, humid regions 7
d velocity 26
 fluid
Dahna dune field, Saudi Arabia 56 geothermal 109, 119
Darcy history 130
law 26 origin 130
velocity 27 formation water 82, 130, 159
dating 95 fossil groundwater 179
DCT⇒ Diablo Canyon Iron Meteorite fractionation factor, isotopic 76, 119, 138
(standard) 79 freshwater 179
decay constant 31 fulvic acid 101, 189
dehydration 41, 50
delta value 17 g
denitrification 41 
desulfurication 41 Galapagos geothermal field 115, 159
deuterium 66 gases, noble 22
deuterium excess 66, 188 geohydraulics 25
Diablo Canyon Iron Meteorite (standard) 79 unsaturated zone 50
DIC 18, 102 geothermal oxygene-isotope shift 189
diffusion 17 geothermometry, isotopic 120, 125
discharge 32, 64 carbon dioxide – methan 126
dispersion 25, 51 sulphate-water geothermometer 129
dissolved inorganic carbon ⇒ DIC water-hydrogen geothermometer 128
DOC 102 Geyser geothermal field 139
Dortmund, Germany 114 Gonfiantini correction model 74, 103
drawdown 178 grain size 4
dual-pathway flow 9, 32, 53 Great Artesian Basin 12, 65, 70, 90, 108, 111,
192
Index
114 infiltration coefficient 179

groundwater 179 initial 14C activity 16, 103
abstraction 179 initial specific activity 18
age 18 input function 16, 20
artesian 177 interflow 32, 179
confined 178 iodine-129 112
connate 178 ion exchange 43
dating 18, 179 irrigation return flow 181
discharge 32 isotope fractionation factor 76, 138
divide 179 isotope production ⇒ production
head1 79
level 179
mining 35, 37, 39 j
old 19 
origin 65 juvenile water 180
overexploitation 37, 179
phreatic 180
oxidation of organic matter 44, 105
k

shallow 11, 49
karst system 9, 12, 113
recharge regime 10
kinematic dispersion 52
table 179
krypton-81 110
unconfined 182
krypton-85 111
groundwater regime 10, 35
h l


Larderello geothermal field 143, 146, 166
half-life 18
latitude effect 190
Hamad region 37
leaching of salt 72
Harz mountains 83
leaky aquifer 31, 110, 153
heat loss 134, 141
liquid-vapour separation 137
helium isotopes 113
low-temperature systems 49
high temperature systems 119
histogram 179
Höxter 75 m
humid regions 7 
humidity, soil 180 macropore flow 53
hydraulic conductivity 6, 178 magmatic water 180
hydraulic gradient 5 Massif Central 93, 166
hydrogen isotopes matrix diffusion 105, 191
stable 66 mean residence time 8
radioative 96 Mediterranean
hydrogeology 8 Meteoric Water Line 66, 191
hydrograph 33, 68 slope 63, 67
hydroisochron 5 Meteoric Water Line 66
hydrological cycle 179 methane
regime 179 genesis 44
hydrosphere 179 isotopic geothermometer 127
microbial processes 41, 82
i Milk River aquifer 109, 164, 166
mixing line 20, 71, 76, 84, 93, 130

model
IAEA
age 102, 191
global network (www.iaea.or.at) 97
black-box 30
incongruent precipitation 96
compartmental 31
193
Index
conceptional 31, 177 permeability 5, 180

dispersion 30 phreatic aquifer 180, 182
exponential 25, 29 piezometer 180
flow 32 piezometric surface 180
hydrochemical 74 piston-flow model 25, 28
lump-parameter 30, 97 planning isotope studies 152
piston-flow 25, 28 plant water extraction 54, 65
two-component 20, 28, 71, 82, 93, 131 platform sediments 12
three-component 21, 28, 42, 71 playa 180
moisture content 180 Pleistocene palaeowater 70
MRT ⇒ mean residence time pluvial period 36, 38
multi-isotope study 151 pMC 101
multi-stage steam separation 135 pollution studies 90
MWL ⇒ meteoric water line pore water 53
porosity 2
effective 178, 181
n total 181
 secondary 181
NETPATH 43, 74 potential evaporation 181
Ngawha geothermal field 123, 124, 162 potentiometric surface 180
nitrification 41, 75 production, isotopic
nitrogen isotopes 18, 75 cosmogenic 102
mineralisation of organic nitrogen 75 subsurface 19, 96, 107, 108, 111
biological fixation 77 production well 34
noble gases 22 pumping
non-steady state cone 178, 181
recharge-discharge 13, 36, 104 test 5, 71, 181
anthropogenid disturbance 37
palaeoclimatic change 36
northern India 58 r
Nubian Sandstone Basin 12 
nuclear-weapon test 16 radioactive decay 18
radiocarbon 18, 100
radium/radon 114
o radon 114
 reactions, chemical
observation well 180 carbonate 43
Oeschger correction 106 organic matter 44
origin of groundwater 65 sulfur compounds 46
oxidising zone 115, 117 recharge
oxygen isotopes 66 area 69, 103
geothermal δ18O-shift 121, 131 artesian 177
artificial 181
p direct 181
indirect 181
 temperature 22, 23
palaeoclimate effect 36, 69 recharge rate
palaeohydrology 37 mass balance methd 54, 58
palaeogroundwater 36 temperature 22
Holocene 70 tracer-peak displacement method 55
Pleistocene 70 3
H-interface method 99
Palinpinon geothermal field 146 reducing zone of aquifers 115
Pelat 57 regime, hydrological 10, 179
percent modern carbon ⇒ pMC regional flow systems 192
perched aquifer 34, 180 re-injecting thermal waste water 141
194
Index
reservoir correction 19, 103, 105 mixing 84

reservoir effect 102 oxidation of sulphides 82
retention, specific 3 sulphate reduction 44, 46, 81
return flow 181 terrestrial sulphate 82
rocks surface
consolidated sedimentary 9 equipotential 5
crystalline 11 piezometric 4, 180
igneous 8 potentiometric 181
karstified 12 runoff 178
metamorphic 9
sedimentary 11
unconsolitated 10
t
volcanic 11 
root zone 181 temperature effect 66
runoff, direct 32, 178 The Geysers geothermal field 147
time series 98, 181
Tongonan geothermal field 132
s tracer 15
 balance method 53
safe yield 181 bomb 15
Sahara desert 64, 70, 160 chemical 20
salination processes 72, 109 colloids 21
saline water 181 conservative 20, 66
sampling 35, 151 environmental 15
saturated zone 65 historical 15
seasonal isotope variation 68 noble gases 22
sedimentary rocks 11 non-conservative 17
separated vapour 123, 137 radioactive isotopes 18
sewage 76, 90, 92 stable isotopes 17
Showashinzan Volcano, Japan 134 peak displacement 51, 53, 55, 58, 73
silicon-32 107 tracer velocity 178
SMOW ⇒ transmissivity 182
Vienna Standard Mean Ocean Water tritium
solute transport 51, 53 peak 55, 96
specific yield 2, 4 ingrowth techniqe 101
spring input function 16, 99
artesian 34, 177 time-series 98
barrier 34 unit 97
descending 34 tritium/helium method 100
intermittent 33, 180 true water age 103
perennial 33 TU 97
periodic 33 turnover
steady-state condition 36, 50 time 97, 182
steam rate 182
loss 134
separation, single-step 135
separation, continuous 137, 145
u
separation, multi-stages 136 
storage coefficient 4, 181 U/He method 113
storativity 181 unconfined aquifer 182
Stripa mine 48, 89, 94 unsaturated zone 49, 182
strontium isotopes 17, 48, 92 uranium isotope ratio 115
sulphur isotopes 18, 79 uranium/helium 114
atmospheric sulphate 81
marine sulphate 81
195
Index
mineral 73
v mobile 49, 179
 retentative 50
vadose water 182 saline 181
velocity subsurface 181
actual 26 table, free 179
apparent 38 vadose 182
Darcy 27 waste 76, 90, 141
distance 178 water-rock interaction 41, 123
filtration 27, 179 weathering studies 94
tracer 26, 178 well
Vienna Standard Mean artesian 34, 177
Ocean Water (standard) 66 construction 35
volumetric humidity 3, 180 drilled 34
volumetric water content 3, 180 dug 34, 98
V-SMOW (standard) ⇒ observation 36, 180
Vienna Standard Mean Ocean Water production 34
w y
 
Wairakai geothermal field, Phillipines 139 Yellowstone field 128, 135, 169
water
andesitic 121, 131, 135
basaltic water 131 z
brackish 177 
connate 178 Zhangzhou geothermal field 129, 166
constitutive 50 zone
formation 82, 130, 159 aeration 182
fossil 179 intermediate 179
gravitational 179 root 181
juvenile 121, 180 saturated 65, 181, 182
magmatic 121, 180 transition 133
meteoric 121 unsaturated 49, 182
modern 180
196

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ENVIRONMENTAL

Principles and Applications

Environmental Isotopes in the Hydrological Cycle

Paris / Vienna, March 2000

Hannover, February 2000

1 HYDROGEOLOGY AND AQUIFER CHARACTERISTICS 1

2 TRACERS AND TRANSPORT 15

5 APPLICATIONS TO LOW-TEMPERATURE SYSTEMS 49

6 APPLICATIONS TO HIGH-TEMPERATURE SYSTEMS 119

7 PLANNING AND PERFORMANCE OF MULTIPLE ISOTOPE STUDIES 151

IAEA PUBLICATIONS 177

SUBJECT INDEX 191

1.2 OCCURRENCE OF GROUNDWATER IN ROCKS

1.3 GEOHYDRAULIC PARAMETERS

Vtot = Vgas + Vliq .

(Vtot) is the specific retention (also capillary porosity)

Vtot Vsol Vsol

0 0.001 0.01 0.1 1 10 100

clay silt sand gravel cobbles

1.3.2 STORAGE, STORAGE COEFFICIENT

S = g ⋅ d (n eff ⋅ β liq + β rock )

1.3.3 PERMEABILITY AND HYDRAULIC CONDUCTIVITY

1.3.4 FLOW NETS

1.4.1 HYDROGEOLOGICAL PROPERTIES OF ROCKS

1.4.1.1 IGNEOUS ROCKS

1.4.1.2 METAMORPHIC ROCKS

1.4.1.3 CONSOLIDATED SEDIMENTARY ROCKS

1.4.1.4 UNCONSOLIDATED SEDIMENTS

1.4.2 HYDROGEOLOGICAL STRUCTURES - GROUNDWATER REGIMES

1.4.3 CRYSTALLINE REGIONS

1.4.3.1 VOLCANIC ROCKS

1.4.3.2 FOLDED SEQUENCES OF SEDIMENTARY ROCKS

dissolved solids. Groundwater often consists of components of different residence times

1.4.3.3 KARSTIFIED ROCKS

1.4.3.4 PLATFORM SEDIMENTS

1.4.3.5 ALLUVIAL PLAINS AND FANS, RIVER DELTAS, GLACIOFLUVIAL SEDIMENTS

well 1 river well 2

2.1 TYPES OF TRACERS

2.2 TYPES OF TRACER EXPERIMENTS

2.3 ISOTOPES IN GROUNDWATER

2.3.1 STABLE ISOTOPES

2.3.2 RADIOACTIVE ISOTOPES

where T1/2 is the half-life of the given radionuclide (Fig.2.2).

100 reservoir effect =

sea water -30

may reflect storm-driven changes in chemistry or flow rates.

2.3.5 NOBLE GASES

3.1 STEADY-STATE GROUNDWATER FLOW

3.1.1 DARCY VELOCITY AND TRACER VELOCITY

The hydraulic conductivity K or coefficient of filtration has the dimension of a velocity as

10-8 10-6 10-4 10-2 100 102

3.1.2 PRINCIPAL GROUNDWATER FLOW MODELS

hydrological data, conceptional and lumped-parameter models have specifically been

n tot (0) ⋅ d char

C out ( t ) = C init ⋅ e − λ⋅t (3.6)

3.1.3 CONSIDERATIONS ABOUT MODELLING

3.1.4 GROUNDWATER DISCHARGE

base flow Qbase

3.1.4.2 PRODUCTION WELLS