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 (Hbner 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 2H, 18O, 34S 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 13C 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 13C 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
13C 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
 Water-Rock Interactions

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 13C 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 & Knzl 1981).
13C

12000 4

DIC concentration (mmol/l)

C age of DIC (yr BP)

-12
calcite saturation Corg oxidation lime dissolution

-14 10000
3
-16 8000
14

3C
1

-18 6000 C 2
DI

-20 4000

IC 1
ofD 2 CH2O +SO 2-
CO2 + H2O + CaCO3
-22 2000 e 4
ag -
H2S + 2 HCO3- Ca++(HCO3-)2
14 C

-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 13C 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 34S and
the corresponding 18O(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

34S
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 34S caused by
those processes can be even several tens of per mill. Sulphide mineral that originate from the
released H2S have very negative 34S. On the other hand, sulphate minerals originating from
the isotopically heavy residual sulphate ions have positive 34S (Smejkal 1978).

46
 Water-Rock Interactions

34S (SO4)

+30

+25

4.9

+20

+15
anhydrite
4.0

+10

1.1
+5
rain
3.2

-5

0 +5 +10 +15 +20

O (SO4)
18

Fig.4.3 Change of both the 34S and 18O 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 18O(S04) versus 34S (Fig.4.3) represents the distribution of the 34S 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 34S and 18O(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