COMPUTER PROGRAMS IN

GEOTHERMAL GEOCHEMISTRY

Halldr rmannsson
November 2006
Equilibrium system: Aqeous fluid + one or more minerals (optional)
Mass transfer, temperature changes new equilibria
System may be externally buffered

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 Configuration of Reaction Models

Closed system models

Titration models
Fixed fugacity and sliding fugacity
models
Kinetic reaction models
Local equilibrium models
Continuum models

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Polythermal path: Sample at 300C, analyzed at room temperature,
Fluid equilibrated at 25C in calculation and then calculated back to
desired temperature (e.g. 300C)

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Titration model: Reactants gradually added to equilibrium system

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1)equilibrium; 2)isolation, 3) deposition

3)

2)

1) 1)

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 BASICS
Reactions: aA + bB+... cC + dD+..
Q = [aC]c[aB]b../{[aA]a[aB]b..}. At
equilibrium K = Q; or Q/K = 1; or
log/Q/K = 0. aX = activity of species X
mX = molal concentration of species X
(molar = mole/l; molal = mole/kg)
aX = XmX,where X = activity coefficient
Activity of pure phases (solids, solvent)
is 1
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 SYSTEMS
Open system: Can exchange both
matter and energy
Closed system: Can exchange energy,
not matter
Isolated system: Removed from
surroundings
Irreversible process: One direction only
Chemical system: T, P, concentration of
all chemical components

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 PHASE RULE
P + F = C + 2 (Gibbs), where P = No. of
phases, F = No. of independent variables,
C = No. of chemical components
At equilibrium: P = C
Geothermal system: minerals, water,
steam (if present). If both water and
steam are present in the system,
pressure is the only independent variable
and F = 1

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 The standard state
Gibbs energy and enthalpy of substances
cannot be determined, only changes
associated with reactions. By convention, the
standard Gibbs energy and standard enthalpy
of the elements are taken to be zero at 25C
and 1 bar. The standard Gibbs energy and
standard enthalpy of compounds are relative
to the element values and termed standard
free energy of formation and standard
enthalpy of formation and symbolized by G0f
and H0f respectively

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 Gibbs energy
Effects of temperature and pressure I
Gf = G0f + RTlnQ (Equilibrium Q = K)
H0f,i,T = H0f,i,T + a(T-Tr) + b(T2-Tr2) - c(T-
r

1-T -1) + f/3 (T3-T 3) + g/0.5 (T0.5-T 0.5)

r r r
S0i,T = S0i,T + aln(T/Tr) + 2b(T-Tr) - c/2(T-
r

2-T -2) + f/2 (T2-T 2) + g/0.5 (T0.5-T 0.5)

r r r
G=Gibbs energy; S=entropy; H=enthalpy
T=temperature; a, b, c, f, g = constants.
f denotes formation, i ion, r reaction

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 Gibbs energy
Effects of temperature and pressure II

G0r,T,p = G0r,T ,p - S0i,T ,p (T-Tr) + a[T-

r r r r

Tr -T(lnT-lnTr)] + b[(T-Tr )(Tr-T )] +

c[1/Tr - 1/2T - 1/2T2] + f[TTr2 /2- T3 /6-
Tr3 /3] + g[4 T0.5-2T/Tr0.5- 2Tr0.5] +
V0i(P- Pr)
G=Gibbs energy; S=entropy;
T=temperature; b, c, f, g = constants.
f denotes formation, i ion, r reaction, p
pressure
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 EQUILIBRIUM CONSTANT
At 25C and 1 bar (standard state). Use data
tables for G0f, H0f and S0, a, then G0r =
G0f,i where represents the stoichiometric
constant, + for products, - for reactants
Use data tables for G0f,i, H0f,i, S0i (25C and
1 bar), a and f 106 and at other temperature
calculate enthalpy of formation, and the
Gibbs energy from the standard Gibbs
energy, the entropy, a, and f for the
reaction (b, c and g are equal to zero)
and hence equilibrium constant

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 Real solution vs. ideal solution
Deviation. Due to interaction between species
in solution
Debye-Hckel theory: Due to existence of an
oppositely charged ionic atmosphere
surrounding each ion, dilution of a solution
involves work against the electrostatic
attraction in addition to the free energy for
dilution for an ideal solution which is
determined only by the decrease of ionic
concentration. The difference between actual
and ideal free energy changes is a measure
of the activity coefficient of the particular ion
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 Debye-Hckel equation
log i= -Azi2I/(1+iB I) + bI
A and B are constants depending on the
temperature and density of the water,
i is the effective electrostatic radius of
ion i and I is the ionic strength of the
solution. b is a constant depending on
the salt content of the solution. The
approximation b = 0 is common, then
the activity coefficient of uncharged
species (zi = 0) is equal to unity; ai = mi
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 ACTIVITY COEFFICIENTS
A=1.8248292381060.5/(T)1.5;
B=50.291586491080.5/(T)0.5; is the
density of water, its dielectric constant,
obtained from steam tables and
Helgeson and Kirkham (1974)
respectively
I = mizi2
Na =4-4.5; Ca =6; Cl =3; SO4 =4 etc.
+ +2 - -2

Assume b=0 X = 1 0

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 AQEOUS SPECIATION
Each analyzed component more than
one species.
Relative abundance described by
dissociation constants
Solve mass balance equations and
equations for dissociation equilibria
Natural waters contain multitude of
species and require extensive
calculations Computer programs
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 AQEOUS SPECIATION - Example

Solution of Na, Ca, Cl and SO4

mNa = mNa + mNaCl + mNaSO4 + mNaOH ; mCa =
+ 0 - 0

mCa + mCaCl + mCaSO4 + mCaOH ; mSO4 =

+2 + 0 +

mSO4 + mHSO4 + mNaSO4 + mCaSO4 ; mCl = mCl

-2 - - 0 -

+ mNaCl + mCaCl . Eight dissociation

0 +

reactions, including that of water, e.g

KNaCl =aNa aCl /aNaCl
0 + - 0

Obtain ionic strength I = [mH+ + mOH- + mNa+

+mCa+2 4+ mCl- + mSO4-2 4 + mNaSO4- + mCaCl+
+ mCaOH++ mHSO4-] by iteration
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 Uncertainty

Chemical analysis sufficiently accurate?

Species in dataset important?
Equilibrium constants accurate enough?
Activity coefficients calculated accurately?
Kinetic rate constants and rate laws apply?
Assumed nature of equilibrium appropriate?
Conceptual model correct?

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Al species as function of pH at 200C in the presence of boehmite,
kaolinite and quartz

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Hvergeri #4 wet steam geothermal well: log(Q/K)
Inflow temperature 181C

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 SPECIATION AND CHEMICAL EQUILIBRIUM
PROGRAMS I
HALTAFALL: Originally written in 1967 for
laboratory operations. More recently modified and
used to calculate speciation of seawater and
estuarine waters
SOLGASWATER: Modification of HALTAFALL for
higher temperature calculations.
REDEQL series: originally written in 1972. Has
undergone numerous modifications and spawned
many other programs, e.g. REDEQL2, MINEQL,
MICROQL etc., some of which are also path
programs
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 SPECIATION AND CHEMICAL EQUILIBRIUM
PROGRAMS II
PHREEQE: Written at the USGS and revised
in the early 1980s. Also a reaction path
program
WATEQ series: Truesdell and Jones (1974).
Revised and modified to give WATEQ2,
WATEQ3, WATEQF, and WATSPEC.
SOLMINEQ88: A revision of an earlier
program SOLMINEQ, developed paralell to
WATEQ. Handles geothermal waters at high
temperature and pressure reasonably well
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 SPECIATION AND CHEMICAL EQUILIBRIUM
PROGRAMS III
EQ3: The largest speciation program of all,
with the largest database. Often used in
conjunction with the reaction path program
EQ6. Cumbersome
SOLVEQ: Under development by Reed and
coworkers since mid-70s. Compact,
powerful and easy to use
WATCH: WATCH1 and WATCH3 in Iceland
1975-1980. Rewritten and modified with a
merger 1990-1992 (Development VDATA)
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 REACTION PATH PROGRAMS
PATH1: First reaction path program 1970 by
Helgeson and coworkers. Now probably
obsolete
PHREEQE, PHREEQC: The latter recently
developed by USGS and can be
downloaded from Internet free of charge.
Good reports but doubts about boiling option
EQ6: Very large, hard to use
CHILLER: Reed and coworkers. Compact,
powerful
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 WATCH I
Input: Component analysis of each
phase, incl. pH and pH-temperature.
Reference temperature (Measured,
geothermometry, arbitrary) + additional
information
Computation: mass balance and mass
action equations solved by iteration
67 aq. species + H+ and OH-

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 WATCH II

Initial I obtained from major cations s at pH

temperature (Debye-Hckel) and equations
solved species distribution. Proper I obtained
for this new distribution and used to recompute s
and species concentrations at pH-temperature.
weak acid anions + complexes weighted by
acceptable no. of protons obtained pH at
reference temperature after optional addition of
steam phase. All calculations repeated several
times. Equilibrium gas pressures computed

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 WATCH III

Output: Species concentrations at reference

temperature + activity coefficients (s ). Ionic
balance, geothermometer temperatures,
partial pressures of gases
Can also compute: species concentrations,
solubility products after cooling or adiabatic
boiling
Three models: Wet steam with excess
enthalpy; hot (unboiled) water wells; boiling
hot springs (steam, gas removed)

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 WATCH IV
NEW DEVELOPMENTS UNDERWAY
Mass transfer
Fluid mixing
Steam separation
Mineral precipitation
Structure of database
External database open to users
Additional minerals
Additional aqueous species
Redox reactions
Contained in database
Those used chosen by user
Maybe
Additional geothermometers
Isotopes

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 SOLVEQ

Input: Program GEOCAL (interactive)

SOLRUN file
Mass balance and mass action equations solved
by Newton-Rapphson numerical technique, pH at
reference temperature calculated from pH at pH-
temperature; forced equilibration capability
Types: Temperature changes, pH changes,
alkalinity, including gas analysis, computing pH
and concentrations by forcing equilibrium with
specific minerals/gases, oxidized waters

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 CHILLER
Heterogeneous chemical equilibria under
conditions of changing composition,
temperature, pressure, enthalpy and
combinations of these.
Types: Cooling/heating, boiling/condensing
(enthalpy constraint, isothermal/isobaric,
preset T-P curve, P as f(T), condensation),
fluid-fluid mixing, water-rock reactions,
evaporation, oxidation, box-1, porosity
If no aqueous phase GASWORKS

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Table 1. Chemical composition (in mg/kg) of Austarasel
spring water used for titration with rock and volcanic gas, and
of springwater from Sandabotnar spring

Spring pH/C SiO2 Na K Ca Mg CO2 SO4 H2S Cl F TDS 1)

Austa- 7.62/ 26.4 7.8 1.1 8.7 5.0 40.0 5.7 0.0 2.9 0.05 164
rasel 23
Sand- 7.10/ 29.4 11.5 1.2 13.8 6.3 70.2 5.6 0.0 3.0 0.12 93
abotnar 22
1)
TDS: Total dissolved solids

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Table 2. Chemical composition of rock used for the titration (%)

SiO2 Al2O3 Fe2O3 FeO MnO MgO CaO Na2O K2O H2O CaCl2 CaF2
50.0 13.7 5.0 7.0 0.1 6.0 10.0 3.0 0.15 3.0 0.005 0.006

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Table 3. Chemical composition of gas (mole %) used for the
titration

CO CO2 HCl H2 H2O H2S SO2 S2 HF

0.70 9.54 0.10 2.78 81.56 0.76 3.64 0.19 0.05

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 Table 5. Selected components in fluid at W/R = 10 and
gas fraction = 0.07 compared to those observed in fluids
from wells KG-8 and KJ-13,Krafla
Sample Volc. KG-8 Volc. KJ-13
rock rock
tC 205 205 295 310
pH 7.48 7.17 6.76 7.83
Cl 19.89 26.35 41.4 27.4
HS 5.39 58.4 11.8 294
SiO2 251.5 383.6 564.7 523.4
Ca 0.41 1.42 0.45 0.42
Na 299.9 193.2 187.6 134.4

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The Rangingar heating system

Laugaland, Holt
D = -75.2 Kaldrholt
18O = -10.41 D = -68.3
pH = 9.8/22 18O = -9.74
pH = 10.4./22.5
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LAUGALAND-KALDRHOLT. MIXING
Laugaland Kaldrholt 1*(L) +1*(K)
water (L) water (K)
t C 98.4 67.0 84.9
pH/C 9.8/22 10.4/22.5 9.1/84.9
SiO2 ppm 97.2 89.0 93.3
Ca ppm 3.0 2.3 2.2
Mg ppm 0.003 0.012 0.00005
CO2 ppm 21.0 13.8 19.9
Deposit Tremolite, Tremolite, Tremolite
calcite calcite 0.04 mg
Advice: Go ahead with mixing (calcite
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 EARTHQUAKES 2000
Rifts near Laugaland.
Mixing of Laugaland and
Kaldrholt water caused no
deposition but cold water intrusion
due to earthquakes caused
magnesium silicates to be
deposited from Laugaland water

Kaldrholt
Well
damaged
by
earthquakes

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 GRNDALUR

River Grndals close to Nearby lfusdalur well 7.

planned well site. Liquid discharge: 40-50 l/s

By Krafla power station, North Iceland stream has been coloured white
by deposition of silica and magnesium silicates after mixing with
separator water
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 GRNDALUR

Flow from hotspring towards river Grndals. Extensive cooling

in rapids
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RIVER GRNDALS-WELL WATER MIXING -
ASSUMPTIONS I
Not direct information. Flows into river
Varm and its flow is 13.66% of the total
in river Varm. Hence extremes 185 l/s
to 1677 l/s. Mean flow 306 l/s.
Borehole discharge water flow assumed
50 l/s with reference to flow in nearby
wells.
Chemical composition of well water
assumed to be that of the nearby
lfusdalur well 7, but of river water like
that of river Varm
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RIVER GRNDALS-WELL WATER MIXING -
ASSUMPTIONS II

Calculations made for the extreme cases of

50 l/s well water, and the maximum 1667 l/s
river water, and the minimum 185 l/s river
water, i.e. 1*rw + 0.03*ww and 1*rw +
0.27*ww
In nearby lkelduhls well 32 l/s were
discharged into river Thver after flowing
through a pond and then forming a waterfall.
Cooled to 30C when it reached the river.
Hence mixing temperature of 50C assumed
but 75C upper extreme
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RIVER GRNDALS-WELL WATER.
MIXING. RESULTS I
River water Well water 1*(R)
(R) (W) +0.27*(W)
t C 11.4 75.0 23.6
pH/C 7.9/11.4 9.2/23 8.4/23.6
SiO2 ppm 38.0 390 102
Ca ppm 14.6 2.2 11.8
Mg ppm 4.13 0.00 0.06
CO2 ppm 35.1 17.0 14.1
Deposit Talc 0.21 Talc 98 %
mg Calcite 2%
Total 1.31 mg
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 RIVER GRNDALS-WELL WATER.
MIXING. RESULTS II
Well flow River flow Talc Calcite
l/s l/s deposit g/s deposit g/s
50 185 3.1 0.07
50 238 4.0 0
50 333 4.7 0
50 1667 6.1 0
Temperature of well discharge water made no difference, whether
it was 50C or 75C. Advice: Deposition not likely to cause
visual disturbance.
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 Speciation of Al+++ in Olkaria I station outfall

100

80

AlF++
% of aluminium

60 AlF2+
AlF3(aq)
AlF4-
40 AlO2-
HAlO2(aq)

20

0
2,0 3,0 4,0 5,0 6,0 7,0 8,0 9,0 10,0
pH

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 Thank you

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