Physical Chemistry of Minerals and Solutions 2008/2009

DM Sherman, University of Bristol

Geochemical Modelling

Physics and Chemistry of Minerals and

Solutions
University of Bristol

Objectives of Geochemical Modelling..

Predict the solubilities of chemical components.

Predict change in solution composition after mineral-
water reactions..
Predict mineral stabilities.

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Physical Chemistry of Minerals and Solutions 2008/2009
DM Sherman, University of Bristol

Method..
Define the unique (basis ) species that define the
composition (i.e., the components).
Consider all of the species that might form from that
basis.
Set up the mass-action law for each species.
Set up the mass or charge balance constraint.
Solve the simultaneous equations...

Example: ZnS in 0.1m NaCl, pH = 3

Define a set of basis species (components) that
define the compositional variations of the system:
Zn+2, H2S, Cl-, H+, Na+
Consider all of the other species that might form from
that basis:
ZnS(s) + H+ = Zn+2 + HS-
Zn+2 + Cl- = ZnCl-
Zn+2 + 2Cl- = ZnCl2-
HS- + H+ = H2S

(Note: each equilibrium must be unique so that one

reaction cannot be a sum of two others.)

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Physical Chemistry of Minerals and Solutions 2008/2009
DM Sherman, University of Bristol

Example: Solubility of ZnS

Write mass action expressions for each species:

[Zn +2 ][HS " ] [H + ][HS " ]

= 10"1.46 = 10 " ?
[H ] +
[H2S]

[ZnCl + ] [ZnCl2 ]
= 10"6.3 " 2
= 10"10.33
! [Zn ][Cl ]
+2 "
[Zn ][Cl ]
+2
!

! !

Example: Solubility of ZnS

Write mass conservation for each component

Cltot = [Cl-] + [ZnCl+] + 2[ZnCl2 -] = 0.1 m

Natot = [Na+] = 0.1 m

[H+] = 10-3

Write charge conservation:

2[Zn+2] + [H+] + [ZnCl+] + [Na+]

= [Cl-] + [HS-] + [ZnCl2-]

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Physical Chemistry of Minerals and Solutions 2008/2009
DM Sherman, University of Bristol

Example: Solubility of ZnS

We have 8 unknowns and 8 equations. However, the

equations are non-linear!
Moreover, we are ignoring the activity coefficients
which cannot be determined until we know the
concentrations of all the charged species.
But these cannot be determined until we know the
activity coefficients..!

Popular Computer Programs

PHREEQC (U.S. Geological Survey)

MINTEQ (US EPA)
Geochemists Workbench (University of Illinois)
EQ3 (Lawrence Livermore National Lab)

Page #
Physical Chemistry of Minerals and Solutions 2008/2009
DM Sherman, University of Bristol

ZnS solubility using PHREEQC

Here is the input file for our problem:
TITLE ZnS solubility on 0.1 m NaCl
SOLUTION
pH 3.0
units mol/kgw
Na 0.1
Cl 0.1
EQUILIBRIUM_PHASES
Sphalerite 0.0 1.0
END

We have two blocks: one (SOLUTION) to specify the

initial solution composition and the other
(EQUILIBRIUM_PHASES) to constrain which phases will
be present.

ZnS solubility using PHREEQC

The output file for our problem contains the total dissolved
Zn and the speciation of Zn:

Log Log Log

Species Molality Activity Molality Activity Gamma

Zn 9.439e-06
Zn+2 8.815e-06 3.560e-06 -5.055 -5.449 -0.394
ZnCl+ 5.798e-07 4.501e-07 -6.237 -6.347 -0.110
ZnCl2 3.956e-08 3.956e-08 -7.403 -7.403 0.000
ZnCl4-2 2.656e-09 9.377e-10 -8.576 -9.028 -0.452
ZnCl3- 2.118e-09 1.644e-09 -8.674 -8.784 -0.110

So, we find that total dissolved zinc is 9.4x10-6 m (0.61

ppm) and that most of the Zn is uncomplexed by Cl- (e.g.,
as Zn(H2O)6+2).

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Physical Chemistry of Minerals and Solutions 2008/2009
DM Sherman, University of Bristol

ZnS solubility using PHREEQC

Our calculation uses a thermodynamic database which
contains log K and H for different complex formation and
mineral dissolution reactions:
SOLUTION_SPECIES
1.0000 Zn++ + 1.0000 Cl- = ZnCl+
-llnl_gamma 4.0
log_k +0.1986
-delta_H 43.317 kJ/mol
-analytic 1.1235e+002 4.4461e-002 -4.1662e+003 -4.5023e+001 -
6.5042e+001
# -Range: 0-300
PHASES
Sphalerite
ZnS +1.0000 H+ = + 1.0000 HS- + 1.0000 Zn++
log_k -11.4400
-delta_H 35.5222 kJ/mol # Enthalpy
-analytic -1.5497e+002 -4.8953e-002 1.7850e+003 6.1472e+001
2.7899e+001
# -Range: 0-300

ZnS solubility using PHREEQC

If there is are H values for all our species/minerals,
we can calculate solubilities at temperatures other
than that of the default of 25 C:
TITLE ZnS solubility on 0.1 m NaCl
SOLUTION
pH 3.0
Temp 250
units mol/kgw
Na 0.1
Cl 0.1
EQUILIBRIUM_PHASES
Sphalerite 0.0 1.0
END

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Physical Chemistry of Minerals and Solutions 2008/2009
DM Sherman, University of Bristol

ZnS solubility using PHREEQC

Repeating the
calculation for a number
of different temperatures
we can see how the
solubility of ZnS
changes with T. Note
the slope changes

Batch Reaction Model Example

Input bulk chemistry (PHREEQC)..
This is the water analysis in spring associated with
china clay pits (Cornwall)..

TITLE China Clay Spring

SOLUTION
units mg/L
density 1.000
pH 6.5
temp 25.0
Si 4
Al 0.05
K 4
END

We want to determine if this water is in equilibrium

with the altered granite.

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Physical Chemistry of Minerals and Solutions 2008/2009
DM Sherman, University of Bristol

Batch Reaction Model Example (Cont.)

First, PHREEQC solves for the solution speciation:
----------------------------Distribution of species----------------------------

Log Log Log

Species Molality Activity Molality Activity Gamma

H+ 3.189e-07 3.162e-07 -6.496 -6.500 -0.004

OH- 3.192e-08 3.166e-08 -7.496 -7.500 -0.004
H2O 5.551e+01 1.000e+00 0.000 0.000 0.000
Al 1.853e-06
Al(OH)4- 1.202e-06 1.192e-06 -5.920 -5.924 -0.004
Al(OH)2+ 4.328e-07 4.292e-07 -6.364 -6.367 -0.004
Al(OH)3 2.000e-07 2.000e-07 -6.699 -6.699 0.000
AlOH+2 1.791e-08 1.732e-08 -7.747 -7.762 -0.015
Al+3 5.940e-10 5.513e-10 -9.226 -9.259 -0.032
H(0) 1.416e-24
H2 7.079e-25 7.079e-25 -24.150 -24.150 0.000
K 1.023e-04
K+ 1.023e-04 1.014e-04 -3.990 -3.994 -0.004
KOH 1.112e-12 1.112e-12 -11.954 -11.954 0.000
O(0) 0.000e+00
O2 0.000e+00 0.000e+00 -44.080 -44.080 0.000
Si 6.657e-05
H4SiO4 6.654e-05 6.654e-05 -4.177 -4.177 0.000
H3SiO4- 3.129e-08 3.103e-08 -7.505 -7.508 -0.004
H2SiO4-2 6.902e-15 6.674e-15 -14.161 -14.176 -0.015

Batch Reaction Model Example (Cont.)

Next, PHREEQC calculates the the Q
saturation index for each possible S.I. = log
K
mineral:
------------------------------Saturation indices-------------------------------

Phase SI log IAP log KT

Al(OH)3(a) -0.56 10.24 10.80

!Al(OH)3
Chalcedony -0.63 -4.18 -3.55 SiO2
Gibbsite 2.13 10.24 8.11 Al(OH)3
H2(g) -21.00 -21.00 0.00 H2
K-feldspar -1.88 0.22 2.09 KAlSi3O8
K-mica 8.00 20.70 12.70 KAl3Si3O10(OH)2
Kaolinite 4.69 12.13 7.43 Al2Si2O5(OH)4
O2(g) -41.12 42.00 83.12 O2
Quartz -0.20 -4.18 -3.98 SiO2
SiO2(a) -1.47 -4.18 -2.71 SiO2

We are oversaturated (SI > 0) in several minerals;

with time, they would precipitate out. However, it is
more complicated than that..

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Physical Chemistry of Minerals and Solutions 2008/2009
DM Sherman, University of Bristol

Batch Reaction Model Example (Cont.)

Now we can let the solution equilibrate with K-feldspar
and see what happens. We constrained the reaction
so that K-mica is not allowed to precipitate out since
that is kinetically slow..
-----------------------------Phase assemblage--------------------------------

Moles in assemblage
Phase SI log IAP log KT Initial Final Delta

K-feldspar 0.00 2.09 2.09 1.000e+01 1.000e+01 -1.107e-04

K-mica 4.20 16.90 12.70 0.000e+00 0.000e+00
Kaolinite 0.00 7.44 7.43 0.000e+00 5.550e-05 5.550e-05

The solution will react with K-feldspar to produce

kaolinite..

Batch Reaction Model Example (Cont.)

Solution composition after reacting with feldspar..
----------------------------Distribution of species----------------------------

Log Log Log

Species Molality Activity Molality Activity Gamma

OH- 2.725e-05 2.685e-05 -4.565 -4.571 -0.006

H+ 3.782e-10 3.728e-10 -9.422 -9.429 -0.006
H2O 5.551e+01 1.000e+00 0.000 0.000 0.000
Al 1.497e-06
Al(OH)4- 1.497e-06 1.475e-06 -5.825 -5.831 -0.006
Al(OH)3 2.917e-10 2.917e-10 -9.535 -9.535 0.000
Al(OH)2+ 7.491e-13 7.381e-13 -12.125 -12.132 -0.006
AlOH+2 3.723e-17 3.511e-17 -16.429 -16.455 -0.026
Al+3 1.500e-21 1.318e-21 -20.824 -20.880 -0.056
H(0) 2.023e-30
H2 1.012e-30 1.012e-30 -29.995 -29.995 0.000
K 2.130e-04
K+ 2.129e-04 2.098e-04 -3.672 -3.678 -0.006
KOH 1.952e-09 1.952e-09 -8.710 -8.710 0.000
O(0) 8.147e-33
O2 4.074e-33 4.074e-33 -32.390 -32.390 0.000
Si 2.875e-04
H4SiO4 2.052e-04 2.052e-04 -3.688 -3.688 0.000
H3SiO4- 8.235e-05 8.115e-05 -4.084 -4.091 -0.006
H2SiO4-2 1.570e-08 1.481e-08 -7.804 -7.830 -0.026

Page #
Physical Chemistry of Minerals and Solutions 2008/2009
DM Sherman, University of Bristol

Summary

Mass-action constraint to relate different species

(simultaneous equilibria).
Mass conservation constraint.
We solve simultaneous non-linear equations.
Kinetic effects can be accounted for by imposing
undersaturation or oversaturation..

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