Jeo Term o Metre

GEOCHEMISTRY OF
GEOTHERMAL SYSTEMS

WATER CHEMISTRY
Chemical composition of waters is expressed in terms
of major anion and cation contents.
Major Cations: Na
+
, K
+
, Ca
++
, Mg
++
Major Anions: HCO
3
-
(or CO
3
=
), Cl
-
, SO
4
=
HCO
3
-
dominant in neutral conditions
CO
3
=
dominant in alkaline (pH>8) conditions
H
2
CO
3
dominant in acidic conditions

Also dissolved silica (SiO
2
) in neutral form
as a major constituent

Minor constituents: B, F, Li, Sr, ...
WATER CHEMISTRY
concentration of chemical constituents are
expressed in units of

mg/l (ppm=parts per million)
(mg/l is the preferred unit)

Molality

Molality = no. of moles / kg of solvent
No.of moles = (mg/l*10
-3
)

/ formula weight
WATER CHEMISTRY
Errors associated with water analyses are expressed in
terms of CBE (Charge Balance Error)

CBE (%) = |( z x mc - z x ma ) / (z x mc + z x ma )|* 100

where,
mc is the molality of cation
ma is the molality of anion
z is the charge

If CBE s 5%, the results are appropriate to use in any kind of
interpretation

The constituents encountered in
geothermal fluids
TRACERS
Chemically inert, non-reactive, conservative constituents
(once added to the fluid phase, remain unchanged allowing
their origins to be traced back to their source component -
used to infer about the source characteristics)
e.g. He, Ar (noble gases), Cl, B, Li, Rb, Cs, N2

GEOINDICATORS
Chemically reactive, non-conservative species
(respond to changes in environment - used to infer about the
physico-chemical processes during the ascent of water to
surface, also used in geothermometry applications)
e.g. Na, K, Mg, Ca, SiO2

In this chapter, the main emphasis
will be placed on the use of water
chemistry in the determination of :
+underground (reservoir) temperatures :
geothermometers
+boiling and mixing relations (subsurface
physico-chemical processes)
WATER CHEMISTRY
HYDROTHERMAL
REACTIONS
The composition of geothermal fluids are controlled
by : temperature-dependent reactions between
minerals and fluids
The factors affecting the formation of hydrothermal
minerals are:
temperature
pressure
rock type
permeability
fluid composition
duration of activity
The effect of rock type --- most pronounced at
low temperatures & insignificant above 280C
Above 280C and at least as high as 350C, the
typical stable mineral assemblages (in active
geothermal systems) are independent of rock
type and include
ALBITE, K-FELDSPAR, CHLORITE, Fe-EPIDOTE, CALCITE,
QUARTZ, ILLITE & PYRITE
At lower temperatures, ZEOLITES and CLAY
MINERALS are found.
At low permeabilities equilibrium between rocks
and fluids is seldom achieved.
When permeabilities are relatively high and water
residence times are long (months to years), water
& rock should reach chemical equilibrium.
At equilibrium, ratios of cations in solution are controlled by temperature-
dependent exchange reactions such as:
NaAlSi
3
O
8
(albite) + K
+
= KAlSi
3
O
8
(K-felds.) + Na
+
K
eq.
= | Na
+
| / | K
+
|

Hydrogen ion activity (pH) is controlled by hydrolysis reactions, such as :
3 KAlSi
3
O
8
(K-felds.) + 2 H
+
= K Al
3
Si
3
O
10
(OH)
2
(K-mica)+ 6SiO
2
+ 2 K
+

K
eq.
= | K
+
| / | H
+
|
where,
K
eq.
= equilibrium constant,
square brackets indicate activities of dissolved species (activity is unity
for pure solid phases)
ESTIMATION OF
RESERVOIR
TEMPERATURES
The evaluation of the
reservoir temperatures for
geothermal systems is made
in terms of
GEOTHERMOMETRY
APPLICATIONS
GEOTHERMOMETRY
APPLICATIONS
GEOTHERMOMETRY
APPLICATIONS
One of the major tools for the
exploration & development
of geothermal resources

GEOTHERMOMETRY
Oestimation of reservoir (subsurface)
temperatures
Ousing
Chemical & isotopic composition of
surface discharges from
- wells and/or
- natural springs/fumaroles
GEOTHERMOMETERS
CHEMICAL GEOTHERMOMETERS
utilize the chemical composition
- silica and major cation contents of water
discharges
-gas concentrations or relative
abundances of gaseous components in
steam discharges
ISOTOPIC GEOTHERMOMETERS
based on the isotope exchange reactions
between various phases (water, gas,
mineral) in geothermal systems
Focus of the Course

CHEMICAL GEOTHERMOMETERS
As applied to water discharges

PART I. Basic Principles & Types
PART II. Examples/Problems
CHEMICAL
GEOTHEROMOMETERS
PART I. Basic Principles &Types
BASIC PRINCIPLES
Chemical Geothermometers are
developed on the basis of temperature
dependent chemical equilibrium
between the water and the minerals at
the deep reservoir conditions
based on the assumption that the water
preserves its chemical composition
during its ascent from the reservoir to
the surface
BASIC PRINCIPLES
Studies of well discharge chemistry and
alteration mineralogy
the presence of equilibrium in several
geothermal fields
the assumption of equilibrium is valid
BASIC PRINCIPLES
Assumption of the preservation of water
chemistry may not always hold
Because the water composition may be
affected by processes such as
cooling
mixing with waters from different reservoirs.
BASIC PRINCIPLES
Cooling during ascent from
reservoir to surface:
CONDUCTIVE
ADIABATIC

BASIC PRINCIPLES
CONDUCTIVE Cooling
Heat loss while travelling through cooler
rocks

ADIABATIC Cooling
Boiling because of decreasing hydrostatic
head

BASIC PRINCIPLES
Conductive cooling
does not by itself change the
composition of the water
but may affect its degree of saturation
with respect to several minerals
thus, it may bring about a modification
in the chemical composition of the
water by mineral dissolution or
precipitation
BASIC PRINCIPLES
Adiabatic cooling (Cooling by
boiling)
causes changes in the composition of
ascending water
these changes include
-degassing, and hence
-the increase in the solute content as a
result of steam loss.

BASIC PRINCIPLES
MIXING
affects chemical composition
since the solubility of most of the
compounds in waters increases with
increasing temperature, mixing with
cold groundwater results in the dilution
of geothermal water
Geothermometry applications are not
simply inserting values into specific
geothermometry equations.
Interpretation of temperatures obtained
from geothermometry equations requires
a sound understanding of the chemical
processes involved in geothermal
systems.
The main task of geochemist is to verify
or disprove the validity of assumptions
made in using specific geothermometers
in specific fields.
TYPES OF CHEMICAL
GEOTHERMOMETERS
SILICA GEOTHERMOMETERS
CATION GEOTHERMOMETERS
(Alkali Geothermometers)
based on the
experimentally determined
temperature dependent
variation in the solubility of silica in water
Since silica can occur in various forms in
geothermal fields (such as quartz,
crystobalite, chalcedony, amorphous silica)
different silica geothermometers have been
developed by different workers
Geothermometer Equation Reference
Quartz-no steam loss T = 1309 / (5.19 log C) - 273.15 Fournier (1977)
Quartz-maximum
steam loss at 100
o
C
T = 1522 / (5.75 - log C) - 273.15 Fournier (1977)
Quartz T = 42.198 + 0.28831C - 3.6686 x 10
-4
C
2
+
3.1665 x 10
-7
C
3
+ 77.034 log C
Fournier and
Potter (1982)
Quartz T = 53.500 + 0.11236C - 0.5559 x 10
-4
C
2
+
0.1772 x 10
-7
C
3
+ 88.390 log C
Arnorsson
(1985) based on
Fournier and
Potter (1982)
Chalcedony T = 1032 / (4.69 - log C) - 273.15 Fournier (1977)
Chalcedony T = 1112 / (4.91 - log C) - 273.15 Arnorsson et al.
(1983)
Alpha-Cristobalite T = 1000 / (4.78 - log C) - 273.15 Fournier (1977)
Opal-CT
(Beta-Cristobalite)
T = 781 / (4.51 - log C) - 273.15 Fournier (1977)
Amorphous silica T = 731 / (4.52 - log C) - 273.15 Fournier (1977)
The followings should be considered :

temperature range in which the equations are
valid
effects of steam separation
possible precipitation of silica
before sample collection
(during the travel of fluid to surface, due to silica oversaturation)
after sample collection
(due to improper preservation of sample)
effects of pH on solubility of silica
possible mixing of hot water with cold water
Temperature Range
silica geothermometers are valid for
temperature ranges up to 250 C
above 250C, the equations depart
drastically from the experimentally
determined solubility curves
Temperature Range

Fig.1. Solubility of quartz (curve A)
and amorphous silica (curve C) as
a function of temperature at the
vapour pressure of the solution.
Curve B shows the amount of silica
that would be in solution after an
initially quartz-saturated solution
cooled adiabatically to 100 C
without any precipitation of silica
(from Fournier and Rowe, 1966, and
Truesdell and Fournier, 1976).

At low T (C)
qtz less soluble
amorph. silica more soluble

Silica solubility is controlled by
amorphous silica at low T (C)
quartz at high T (C)
Effects of Steam Separation
Boiling Steam Separation
volume of residual liquidN
Concentration in liquid7
Temperature Estimate7
e.g.
T = 1309 / (5.19 log C) - 273.15
C = SiO2 in ppm
increase in C (SiO2 in water > SiO2 in reservoir)
decrease in denominator of the equation
increase in T

+ for boiling springs
boiling-corrected geothermometers
(i.e. Quartz-max. steam loss)
SiO2
liquid V1
(1)
V2
V1 <
SiO2
(2)
SiO2
(1)
>
liquid V2
SiO2
(2)
steam
Silica Precipitation
SiO2 N
Temperature EstimateN

e.g.
T = 1309 / (5.19 log C) - 273.15
C = SiO2 in ppm
decrease in C (SiO2 in water < SiO2 in reservoir)
increase in denominator
decrease in T

Effect of pH
Fig. 2. Calculated effect of pH upon the
solubility of quartz at various temperatures
from 25 C to 300 C , using experimental
data of Seward (1974). The dashed curve
shows the pH required at various
temperatures to achieve a 10% increase in
quartz solubility compared to the solubility
at pH=7.0 (from Fournier, 1981).

pH 7
Dissolved SiO2 7 (for pH>7.6)
Temperature Estimate7

e.g.

T = 1309 / (5.19 log C) - 273.15
C = SiO2 in ppm
increase in C
increase in T

Effect of Mixing
Hot-Water High SiO2 content
Cold-Water Low SiO2 content
(Temperature 7 Silica solubility 7)

Mixing (of hot-water with cold-water)
TemperatureN
SiO2 N
Temperature Estimate N
e.g.
T = 1309 / (5.19 log C) - 273.15
C = SiO2 in ppm
decrease in C
increase in denominator of the equation
decrease in T

Process Reservoir Temperature
Steam Separation Overestimated
Silica Precipitation Underestimated
Increase in pH Overestimated
Mixing with cold water Underestimated

(Alkali Geothermometers)

Obased on the partitioning of alkalies between
solid and liquid phases
e.g. K
+
+ Na-feldspar = Na
+
+ K-feldspar

Omajority of are empirically developed
geothermometers
Na/K geothermometer
Na-K-Ca geothermometer
Na-K-Ca-Mg geothermometer
Others (Na-Li, K-Mg, ..)

Na/K Geothermometer

Fig.3. Na/K atomic ratios of
well discharges plotted at
measured downhole
temperatures. Curve A is
the least square fit of the
data points above 80 C.
Curve B is another
empirical curve (from
Truesdell, 1976). Curves C
and D show the
approximate locations of
the low albite-microcline
and high albite-sanidine
lines derived from
thermodynamic data (from
Fournier, 1981).
Na/K Geothermometer
Geotherm. Equations Reference
Na-K T=[855.6/(0.857+log(Na/K))]-273.15 Truesdell (1976)
Na-K T=[833/(0.780+log(Na/K))]-273.15 Tonani (1980)
Na-K T=[933/(0.993+log (Na/K))]-273.15
(25-250
o
C)
Arnorsson et al.
(1983)
Na-K T=[1319/(1.699+log(Na/K))]-273.15
(250-350
o
C)
Arnorsson et al.
(1983)
Na-K T=[1217/(1.483+log(Na/K))]-273.15 Fournier (1979)
Na-K T=[1178/(1.470+log (Na/K))]-273.15 Nieva and Nieva
(1987)
Na-K T=[1390/(1.750+log(Na/K))]-273.15 Giggenbach
(1988)
Na/K Geothermometer
Ogives good results for reservoir temperatures
above 180C.
Oyields erraneous estimates for low
temperature waters
+temperature-dependent exchange equilibrium
between feldspars and geothermal waters is not
attained at low temperatures and the Na/K ratio in
these waters are governed by leaching rather than
chemical equilibrium
Oyields unusually high estimates for waters
having high calcium contents

Na-K-Ca Geothermometer

Na-K-Ca

T=[1647/ (log (Na/K)+ | (log (\Ca/Na)+2.06)+ 2.47)]
-273.15

a) if |log\Ca/Na)+2.06| < 0, use |=1/3 and calculate TC
b) if |log\Ca/Na)+2.06| > 0, use |=4/3 and calculate TC
c) if calculated T > 100C in (b), recalculate TC using |=1/3

Fournier
and
Truesdell
(1973)
Na-K-Ca Geothermometer
Works well for CO2-rich or Ca-rich environments provided
that calcite was not deposited after the water left the
reservoir

in case of calcite precipitation
Ca N
1647
T = --------------------------------------------------------- - 273.15
log (Na/K)+ | (log (\Ca/Na)+2.06)+ 2.47

Decrease in Ca concentration (Ca in water < Ca in reservoir)
increase in T

For waters with high Mg contents, Na-K-Ca
geothermometer yields erraneous results. For these
waters, Mg correction is necessary
Na-K-Ca-Mg Geothermometer
Na-K-Ca-Mg

T = T
Na-K-Ca
- At
Mg
o
C

R = (Mg / Mg + 0.61Ca + 0.31K) x 100

if R from 1.5 to 5
At
Mg
o
C = -1.03 + 59.971 log R + 145.05 (log R)
2
36711
(log R)
2
/ T - 1.67 x 10
7
log R / T
2

if R from 5 to 50
At
Mg
o
C=10.66-4.7415 log R+325.87(log R)
2
-
1.032x10
5
(log R)
2
/T-1.968x10
7
(log R)
3
/T
2

Note: Do not apply a Mg correction if At
Mg

is negative
or R<1.5.

If R>50, assume a temperature = measured spring
temperature.

T is Na-K-Ca geothermometer temperature in Kelvin
Fournier
and Potter
(1979)

Na-K-Ca-Mg Geothermometer
Fig. 4. Graph for
estimating the
magnesium temperature
correction to be
subtracted from Na-K-Ca
calculated temperature
(from Fournier, 1981)

R = (Mg/Mg + 0.61Ca + 0.31K)x100

UNDERGROUND MIXING OF
HOT AND COLD WATERS
Recognition of Mixed Waters
Mixing of hot ascending waters with cold waters at
shallow depths is common.
Mixing also occurs deep in hydrothermal systems.
The effects of mixing on geothermometers is already
discussed in previous section.
Where all the waters reaching surface are mixed waters,
recognition of mixing can be difficult.
The recognition of mixing is especially difficult if water-
rock re-equilibration occurred after mixing (complete or
partial re-equilibration is more likely if the temperatures
after mixing is well above 110 to 150 C, or if mixing
takes place in aquifers with long residence times).
UNDERGROUND MIXING OF
HOT AND COLD WATERS
Some indications of mixing are as follows:
systematic variations of spring compositions
and measured temperatures,
variations in oxygen or hydrogen isotopes,
variations in ratios of relatively *conservative
elements that do not precipitate from solution
during movement of water through rock (e.g.
Cl/B ratios).
SILICA-ENTHALPY MIXING
MODEL
Dissolved silica content of mixed waters can be used
to determine the temperature of hot-water
component .
Dissolved silica is plotted against enthalpy of liquid
water.
Although temperature is the measured property, and
enthalphy is a derived property, enthalpy is used as
a coordinate rather than temperature. This is
because the combined heat contents of two waters
are conserved when those waters are mixed, but the
combined temperatures are not.
The enthalpy values are obtained from steam tables.
MODEL
Fig. 5. Dissolved silica-
enthalpy diagram showing
procedure for calculating
the initial enthalpy (and
hence the reservoir
temperature) of a high
temperature water that has
mixed with a low
temperature water (from
Fournier, 1981)

MODEL
A = non-thermal component
(cold water)

B, D = mixed, warm water
springs

C = hot water component at
reservoir conditions
(assuming no steam
separation before mixing)
E = hot water component at
reservoir conditions
(assuming steam separation
before mixing)
Boiling
T =100 C
Enthalpy =419 J /g
(corresponds to D in the graph)

Enthalpy values (at corresponding temperatures)
are found from Steam Table in Henley et al.(1984)
419 J/g
(100 C)
0
SILICA-ENTHALPY MIXING MODEL
Steam Fraction did not separate before mixing
The sample points are plotted.
A straight line is drawn from
the point representing the
non-thermal component of the
mixed water (i.e. the point with
the lowest temperature and
the lowest silica content =
point A in Fig.), through the
mixed water warm springs
(points B and D in Fig.).
The intersection of this line
with the qtz solubility curve
(point C in Fig.) gives the
enthalpy of the hot-water
component (at reservoir
conditions).
From the steam table, the
temperature corresponding to
this enthalpy value is obtained
as the reservoir temperature
of the hot-water component.

419 J/g
(100 C)
0
SILICA-ENTHALPY MIXING MODEL
Steam separation occurs before mixing
The enthalpy at the boling
temperature (100C) is
obtained from the steam
tables (which is 419 j/g)
A vertical line is drawn from
the enthalpy value of 419 j/g
From the inetrsection point of
this line with the mixing line
(Line AD), a horizantal line
(DE) is drawn.
The intersection of line DE
with the solubility curve for
maximum steam loss (point E)
gives the enthalpy of the hot-
water component.
From the steam tables, the
reservoir temperature of the
hot-water component is
determined.
419 J/g
(100 C)
0
MODEL
In order for the silica mixing model to give accurate results, it
is vital that no conductive cooling occurred after mixing. If
conductive cooling occurred after mixing, then the calculated
temperatures will be too high (overestimated temperatures).
This is because:
the original points before conductive cooling should lie to the
right of the line AD (i.e. towards the higher enthalpy values at
the same silica concentrations, as conductive cooling will
affect only the temperatures, not the silica contents)
in this case, the intersection of mixing line with the quartz
solubility curve will give lower enthalpy values (i.e lower
temperatures) than that obtained in case of conductive
cooling.
in other words, the temperatures obtained in case of
conductive cooling will be higher than the actual reservoir
temperatures (i.e. if conductive cooling occurred after mixing,
the temperatures will be overestimated)
MODEL
Another requirement for the use of enthalpy-silica
model is that no silica deposition occurred before or
after mixing. If silica deposition occurred, the
temperatures will be underestimated. This is because:
the original points before silica deposition should be
towards higher silica contents (at the same enthalpy
values)
in this case, the intersection point of mixing line with
the silica solubility curve will have higher enthalpy
values(higher temperatures) than that obtained in case
of silica deposition
in other words, the temperatures obtained in case of no
silica deposition will be higher than that in case of
silica deposition (i.e. the temperatures will be
underestimated in case of silica deposition)
CHLORIDE-ENTHALPY MIXING
MODEL
Fig.6. Enthalpy-chloride
diagram for waters from
Yellowstone National
Park. Small circles
indicate Geyser Hill-type
waters and smal dots
indicate Black Sand-type
waters (From Fournier,
1981).

MODEL
ESTIMATION OF RESERVOIR
TEMPERATURE

Geyser Hill-type Waters
A = maximum Cl content
B = minimum Cl content
C = minimum enthalpy at
the reservoir

Black Sand-type Waters
D = maximum Cl content
E = minimum Cl content
F = minimum enthalpy at
the reservoir

Enthalpy of steam at 100 C =
2676 J/g (Henley et al., 1984)
MODEL
ORIGIN OF WATERS

N = cold water component
C, F = hot water components

F is more dilute & slightly
cooler than C

F can not be derived from C
by process of mixing
between hot and cold water
(point N), because any
mixture would lie on or
close to line CN.

C and F are probably both
related to a still higher
enthalpy water such as
point G or H.

MODEL
ORIGIN OF WATERS

water C could be related
to water G by boiling

water C could also be
related to water H
by conductive cooling

water F could be related
to water G or water H by
mixing with cold water N

steam
steam
B E
D
C
G
F
H
N
H
cold water reservoir
hot water reservoir
steam hot water
mixed water
residual liquid from boiling
B
hot water undergoing
conductive cooling
mixed water undergoing
conductive cooling
residual liquid undergoing
conductive cooling

ISOTOPES
IN
GEOTHERMAL
EXPLORATION
& DEVELOPMENT
ISOTOPE STUDIES IN
GEOTHERMAL SYSTEMS
At Exploration, Development and
Exploitation Stages

Most commonly used isotopes

Hydrogen (
1
H,
2
H =D,
3
H)
Oxygen (
18
O,
16
O)
Sulphur (
32
S,
34
S)
Helium (
3
He,
4
He)
ISOTOPE STUDIES IN
GEOTHERMAL SYSTEMS
Geothermal Fluids
Sources
Source of fluids (meteoric, magmatic, ..)
Physico-chemical processes affecting the fluid comosition
Water-rock interaction
Evaporation
Condensation
Source of components in fluids (mantle, crust,..)

Ages
(time between recharge-discharge, recharge-sampling)
Temperatures (Geothermometry Applications)
Sources of Geothermal Fluids
+H- & O- Isotopes
Physico-chemical processes affecting the fluid
composition
+H- & O- Isotopes
Sources of components (elements,
compounds) in geothermal fluids
+He-Isotopes (volatile elements)

Sources of Geothermal Fluids and
Physico-Chemical Processes
STABLE
H- & O-ISOTOPES
Stable H- & O-Isotopes
1
H = % 99.9852
2
H (D) = % 0.0148
D/H

16
O = % 99.76
17
O = % 0.04
18
O = % 0.20
18
O /
16
O
(D/H)
sample
- (D/H)
standard
o D () = ----------------------------------- x 10
3
(D/H)
standard

(
18
O/
16
O)
sample
- (
18
O/
16
O)
standard
o
18
O () = -------------------------------------------- x 10
3
(
18
O/
16
O)
standard

Standard = Standard Mean Ocean Water
= SMOW
(D/H)
sample
- (D/H)
SMOW
o D () = ----------------------------------- x 10
3
(D/H)
SMOW

(
18
O/
16
O)
sample
- (
18
O/
16
O)
SMOW
o
18
O () = -------------------------------------------- x 10
3
(
18
O/
16
O)
SMOW


Sources of Natural Waters:

1. Meteoric Water (rain, snow)
2. Sea Water
3. Fossil Waters (trapped in sediments in sedimanary basins)
4. Magmatic Waters
5. Metamorphic Waters

0
0
-40
-80
-120
10 20 30 -10 -20
o O (per mil)
18
o D (per mil)
+
SMOW
Field of
Formation
Waters
Magmatic
Waters
Most igneous
biotites &
hornblendes
Metamorphic
Waters
Ocean
Seepage
precipitation
evaporation
River
H, O
1 16
H, O
1 16
D, O
18
D, O
18
D, O
18
H, O
1 16
H, O
1 16
D, O
18
D, O
18
(D/H) < (D/H)
vapor
water
vapor
<
18 16
O / O
( )
18 16
O / O
( )
water
precipitation
0
-40
-80
-120
-12 -8 -4
0
del- O (per mil)
18
+
SMOW
Condensation
Evaporation
Water-Rock
Interaction
18
Magmatik
Sular
0
-50
-100
-150
-15
-10 -5 0 +5 +10
Larderello
The Geysers
Iceland
Niland
Lassen Park
Steamboat Kaynaklar
o O (per mil)
o D (per mil)
Physico-Chemical Processes:
Latitute
oD o
18
O

Altitute from Sea level
oD o
18
O

Aquifers recharged by precipitation from
lower altitutes higher oD - o
18
O values
OAquifers recharged by precipitation from
higher altitutes lower oD - o
18
O values

Mixing of waters from different aquifers

Boiling and vapor separation
oD o
18
O in residual liquid

Possible subsurface boiling as a
consequence of pressure decrease
(due to continuous exploitation
from production wells)
Monitoring Studies in
Geothermal Exploitation
Aquifers recharged by
precipitation from
lower altitutes higher
oD - o
18
O
Aquifers recharged by
precipitation from
higher altitutes lower
oD - o
18
O
Boiling and vapor
separation
oD o
18
O in
residual liquid
Any increase in oD - o
18
O
values
due to sudden pressure
drop in production wells
recharge from (other)
aquifers fed by
precipitation from lower
altitutes
subsurface boiling and
vapour separation

Monitoring Studies in
Geothermal Exploitation

Monitoring of isotope composition of
geothermal fluids during exploitation can
lead to determination of, and the
development of necessary precautions
against
Decrease in enthalpy due to start of
recharge from cold, shallow aquifers, or
Scaling problems developed as a result of
subsurface boiling

(Scaling)
Vapour Separation
Volume of (residual) liquid
Concentration of dissolved components
in liquid
Liquid will become oversaturated
Component (calcite, silica, etc.) will
precipitate
Scaling
Dating of Geothermal Fluids
3
H- &
3
He-ISOTOPES
Dating of Geothermal Fluids
Time elapsed between Recharge-
Discharge or Recharge-Sampling
points (subsurface residence residence
time)

3
H method
3
H-
3
He method

TRITIUM (
3
H)
3
H = radioactive isotope of Hydrogene (with a short half-life)
3
H forms

Reaction of
14
N isotope (in the atmosphere) with cosmic rays

14
7
N + n
3
1
H +
12
6
C

Nuclear testing

3
H concentration
Tritium Unit (TU)
1 TU = 1 atom
3
H / 10
18
atom H

3
H
3
He + |
Half-life = 12.26 year
Decay constant () = 0.056 y
-1
3
H Dating Method
3
H concentration level in the atmosphere has
shown large changes
n between 1950s and 1960s (before and
after the nuclear testing)
Particularly in the northern hemisphere

Before 1953 : 5-25 TU
In 1963 : "3000 TU

3
H Dating Method
3
H-concentration in groundwater < 1.1 TU
Recharge by precipitations older than nuclear testing

3
H-concentration in groundwater > 1.1 TU
Recharge by precipitations younger than nuclear
testing

N=N
0
e
-t 3
H
0
(before 1963) ~ 10 TU
3
H=
3
H
0
e
-t
= 0.056 y
-1

t = 2003-1963 = 40 years

3
H ~ 1.1 TU

3
H Dating Method
APPARENT AGE

3
H=
3
H
0
e
-t

3
H = measured at sampling point
3
H
0
= measured at recharge point
(assumed to be the initial tritium concentration)

= 0.056 y
-1

t = apparent age

3
H
3
He
Dating Method
3
He =
3
H
0

3
H (D = N
0
-N)
3
H=
3
H
0
e
-t
(N =

N
0
e
-t
)
3
H
0
=
3
H e
t
3
He =
3
H e
t
-
3
H =
3
H (e
t

1)

t = 1/ * ln (
3
He/
3
H + 1)

3
He &
3
H present-day concentrations measured in water sample

Geothermometry Applications
Isotope Fractionation Temperature Dependent
Stable isotope compositions
utilized in Reservoir Temperature estimation
Isotope geothermometers
Based on: isotope exchange reactions between phases
in natural systems
(phases: watre-gas, vapor-gas, water-mineral.....)
Assumes: reaction is at equilibrium at reservoir
conditions
Isotope Geothermometers
12
CO
2
+
13
CH
4
=
13
CO
2
+
12
CH
4
(CO
2
gas - methane gas)

CH
3
D + H
2
O = HDO + CH
4
(methane gas water vapor)

HD + H
2
O = H
2
+ HDO (H
2
gas water vapor)
S
16
O
4
+ H
2
18
O = S
18
O
4
+ H
2
16
O (dissolved sulphate-water)

1000 ln o
(SO4 H2O)
= 2.88 x 10
6
/T
2
4.1
(T = degree Kelvin = K )
Isotope Geothermometers
Regarding the relation between mineralization
and hydrothermal activities
Mineral Isotope Geothermometers
Based on the isotopic equilibrium between
the coeval mineral pairs
Most commonly used isotopes: S-isotopes

Suphur (S)- Isotopes
32
S = 95.02 %
33
S = 0.75 %
34
S = 4.21 %
36
S = 0.02 %

(
34
S/
32
S)
sample
- (
34
S/
32
S)
std.
o
34
S () = -------------------------------------------- x 10
3
(
34
S/
32
S)
sample

Std.= CD
=S-isotope composition of troilite (FeS) phase in Canyon Diablo Meteorite
S-Isotope Geothermometer

A
34
S = o
34
S
(mineral 1)
- o
34
S
(mineral 2)

A
34
S

= Ao
34
S= A (10
6
/T
2
) + B
Pyrite-Galena
800 400 200 150 100
50
0
4
8
12
4
8
0
0
0 2
4
4
2
6 8 10 12
Sphalerite-Galena
Pyrite-Sphalerite
Temperature C
0
10 / T ( K )
6
2
-2
0

Jeo Term o Metre

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