Physical Chemistry of Minerals and Aqueous Solutions

DM Sherman, University of Bristol

2005/2006

Hydrothermal Solutions and

Ore Deposits
Physical Chemistry of Minerals and Aqueous
Solutions
D.M. Sherman, University of Bristol

Chalcophiles, Lithophiles, Siderophiles..

Lithophile = oxides, silicates
Siderophile = Fe alloys
Chalcophile = sulfides

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Physical Chemistry of Minerals and Aqueous Solutions

DM Sherman, University of Bristol

2005/2006

Hydrothermal Vein Deposits

Hypothermal
(300-600 oC)

Mesothermal
(200-300 oC)

Sulfide Ore Minerals

Molybdenite MoS2
Chalcopyrite,
CuFeS2
Pyrrhotite Fe1-xS
Bornite,
Cu5FeS4
Chalcopyrite CuFeS2
Galena, PbS
Sphalerite, ZnS
Arsenopyrite,
FeAsS
Gangue Minerals
Quartz
Tourmaline
Topaz
Micas

Quartz
Carbonates
Barite

Epithermal
(50-200 oC)
Cinnabar, HgS
Stibnite, Sb2S3
Argentite, Ag2S

Quartz
Chalcedony
Opal
Calcite

Chalcopyrite (CuFeS2)
Primary copper mineral in
porphyry-copper
deposits: sulfides
desseminated in felsic
intrusive rocks.

The most widespread

copper mineral.
Usually meso-to
hypothermal deposits.

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Physical Chemistry of Minerals and Aqueous Solutions

DM Sherman, University of Bristol

2005/2006

Galena (PbS)
Primary ore mineral of Pb.
Primarily found in
mesothermal Mississippi
Valley Pb-Zn deposits.

Simple rocksalt structure.

Forms large cubic crystals.

Sphalerite (ZnS)
Primary ore mineral of Zn.
Primarily found in
mesothermal Mississippi
Valley Pb-Zn deposits.

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Physical Chemistry of Minerals and Aqueous Solutions

DM Sherman, University of Bristol

2005/2006

Molybdenite (MoS2)
Primary molybdenum ore.
High-temperature deposits.
Accessory in granites

Fundamental Questions
How are metals such as Cu, Zn, Au and Pb
concentrated into ore deposits?
What chemical signatures can we use to find
ore deposits?
Are there vast resources at depth that we
havent yet discovered?

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Physical Chemistry of Minerals and Aqueous Solutions

DM Sherman, University of Bristol

2005/2006

Keq vs T
Since lnK = -G0/RT we find,
pK = -(ln K)/2.303 = G0/(2.303RT)
= H0/(2.303RT) - S0/(2.303R)
If we assume H0 and S0 are constant with T, then

pK(T ) = pK(298) +

H 0 1
1

2.303R T 298

Solubility of Sphalerite (ZnS)

Under acidic conditions, we can express the dissolution
of sphalerite as
ZnS + 2H+ = Zn+2 + H2S
For this reaction, pK = 4.44 and H0 = 14.0 kJ/mol at
298 K.
pK = pZn + pH2S - 2pH

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Physical Chemistry of Minerals and Aqueous Solutions

DM Sherman, University of Bristol

2005/2006

Solubility of Sphalerite (cont.)

pK(T ) = pK(298) +

H 0 1
1

= pZn + pH2S 2pH
2.303R T 298

Rearranging gives,

14.0 1
1
pZn = 4.44 +

pH
S
+
2pH

2.303R T 298

Solubility of Sphalerite (cont.)

Elevated temperatures
are not enough to
account for the
solubilities of sulfide
minerals needed to
from ore-deposits.

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Physical Chemistry of Minerals and Aqueous Solutions

DM Sherman, University of Bristol

2005/2006

Nature of Ore-Forming Solutions

Fluid inclusions in mineral grains preserve samples of
hydrothermal solutions. Upon cooling, the
hydrothermal brines separate into solid (usually NaCl,
gas (CO2 + CH4) and aqueous phases.
The temperature at which
the fluid was trapped can
be determined by heating
the sample and measuring
the temperature at which
gas + liquid recombine.

Cl Complexation of Zn
Zn+2 + Cl- = ZnCl+
pK = -0.2; H = 43.3 kJ/mol

Zn+2 + 2Cl- = ZnCl2

pK = -0.25; H = 31.2 kJ/mol

Zn+2 + 3Cl- = ZnCl3pK = 0.02; H = 22.6 kJ/mol

Zn+2 + 4Cl- = ZnCl4-2

pK = -0.86; H = 5.0 kJ/mol

Zn(H2O)6 + nCl = ZnCln + 6H2O

Complexation is driven
by the entropy increase
when solvation waters
are released.

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Physical Chemistry of Minerals and Aqueous Solutions

DM Sherman, University of Bristol

2005/2006

Cl Complexation of Zn
We can combine the reaction
ZnS + 2H+ = Zn+2 + H2S (pKZnS; HZnS)
with each complexation reaction
Zn+2 + nCl- = ZnCln2-n (pKn; Hn)
to get the reactions
ZnS + 2H+ + nCl = ZnCln2-n + H2S
with pK = pKZnS + pKn and H = HZnS + Hn

Cl Complexation of Zn
H 0 1
1

2.303R T 298

pK(T ) = pK(298) +

= pZnCln

2n

+ pH2S 2pH - npCl

To a close approximation, pCl = pCltot. Rearranging

gives

pZnCln

2n

= pK(298) +

H 0 1
1

pH2S + 2pH + npCl
2.303R T 298

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Physical Chemistry of Minerals and Aqueous Solutions

DM Sherman, University of Bristol

2005/2006

Solubility of Sphalerite: Cl complexation

Cl-complexation of Zn
greatly enhances the
solubility of ZnS at
high temperature.

Caution: we assumed
that H0 was constant
with T.

Entropy and Complexation

The complexation of metals at high temperature is
driven by the increased translation entropy resulting
from the breakdown of the metal hydration sphere:
Zn(H2O)6 + Cl- = ZnCl(H2O)3+ + 3H2O
Zn(H2O)6 + 2Cl- = ZnCl20 + 6H2O
(Hydration numbers are derived from molecular dynamics
simulations.)

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Physical Chemistry of Minerals and Aqueous Solutions

DM Sherman, University of Bristol

2005/2006

The Continuum Model of Aqueous

Solutions
Born (1920) theory of solvation free energyG:

Where:

q2e2 1
G =
1
2R

R = Born radius of cation with charge q

= dielectric constant of the solvent

for HKF Equation of State used to predict stability

Basis
constants of complexes at high P,T.

Changes in Dielectric Constant of Water

with P and T
We expect decreased
solvation of ions with
increasing T.
This will favor metal
complexation by Cl-.
Pressure should
enhance solvation.

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Physical Chemistry of Minerals and Aqueous Solutions

DM Sherman, University of Bristol

2005/2006

HKF Equation of State (cont.)

The heat capacity and volume of a species depend on T
and P as:

1 2
c2
C (P,T) = c1 +
+ TX + 2TY T 1 2
(T )2
T P
T P
0
p

Vp0 (P,T) = a1 +

1
a2
a
a4
+ 3 +
Q + 1
P + T (P + )(T )
P T

Where c1, c2, a1, a2, a3 and a4 are parameters for the
particular solute species

HKF Equation of State (cont.)

is the Born coefficient of the ion,
2

1
1
1 2 2
Y = 2 , Q = 2 , X = 2 2
T P
P T
T P P P
And, finally, and are parameters for the solvent.

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Physical Chemistry of Minerals and Aqueous Solutions

DM Sherman, University of Bristol

2005/2006

Precipitation of Sulfides
Given the general reaction
ZnS + 2H+ +nCl = ZnCln2-n + H2S
ZnS will precipitate when H+ is consumed:
2H+ + CaCO3 (calcite) = CO2 + Ca+2 + H2O
3KAlSi3O8 (feldspar) + 2H+ =
6SiO2 + 2K+ + KAl3Si3O10(OH)2 (muscovite)

Volcanogenic Massive Sulfide Deposits

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Physical Chemistry of Minerals and Aqueous Solutions

DM Sherman, University of Bristol

2005/2006

Convergent Plate Boundaries

Porphyry Deposits

Ore zone: CuCl2 + FeCl2 +

2H2S = CuFeS2 + 4H+ + 4 Cl-

Argillic: 2KAl3Si3O10(OH)2 + 2H+ +

3H20 = 3Al2Si2O5(OH)4 + 2K+
Phyllic: 3KAlSi3O8 + 2H+ =
KAl3Si3O10(OH)2 + 6SiO2 + 2K+
Potassic

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Physical Chemistry of Minerals and Aqueous Solutions

DM Sherman, University of Bristol

2005/2006

Summary
Sulfide minerals are extremely insoluble.
Hydrothermal solutions contain high concentrations of NaCl.
Complexation of metals by Cl- (and possibly HS-) greatly
enhances the solubility of sulfides at high temperature
Precipitation of sulfide minerals occurs either by cooling,
boiling or by a drop in pH when fluids react with host rock
(e.g., carbonates).

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