Hydrothermal Geochemistry 28 February 2005

Solubility and deposition of carbonates

References:
Fournier, 1985, Reviews in Economic Geology, v. 2,
Chapter 4
Holland and Malinin, 1979, Geochemistry of Hydrothermal CO2-water systematics
Ore Deposits (Barnes 2), Chapter 9
Rimstidt, 1997, Geochemistry of Hydrothermal Ore
Deposits (Barnes 3), Chapter 10

CO2-water systematics
Carbonate solubility and deposition
Miscibility above CPW, but no
Carbonate solubility is strongly influenced by: rxn between gases
pH, fO2, T, and dissolved salts Hydrothermal solutions rarely
have >20% CO2, so concern
Alkali carbonates (nahcolite, trona) are highly soluble at all T
is with the water-rich portion
and rarely form gangue in ore deposits of the diagram
Trivalent cations (e.g., Fe3+, Al3+, REEs) are only soluble at Low T: primarily solubility of
low pH (form oxyhydroxides at higher pH) CO2 in liquid water
at low pH, most carbonates are very soluble, therefore trivalent Moderate T: critical
carbonates are uncommon phenomena
Leaves divalent cation carbonates, which are moderately High T: relative partial
insoluble pressure of phases

Carbonate Solubility 1
Hydrothermal Geochemistry 28 February 2005

CO2-water systematics At given PCO2, KH increase

with T results in lower [CO2]
Henry’s law coefficients: to ~150°C, higher [CO2] Carbonate equilibria
f CO2 = K H X K H = f CO2 X above 150°C
CO2 dissolves in water to form carbonic acid; solubility is
where X = mole fraction expressed by Henry’s Law:
CO2 in water
at LP, fCO2~PCO2 (Raoult’s
CO2 + H2 O ↔ H2 CO3 (aq ) KH =
[ H CO (aq)]
2 3
law for ideal gases) PCO2
Higher KH = decreasing
solubility of CO2; has Carbonic acid ionizes in two steps:
implications for solubility
of carbonates
H2 CO3( aq ) ↔ H + + HCO3− K1 =
[ HCO ][ H ] = 10
−
3
+

@25° C
[ ]
6. 4

Salting-out coefficients: H2 CO3( aq )

salt increases KH and
decreases CO2 solubility
HCO3− ( aq ) ↔ H + + CO32 − K1 =
[CO ][ H ] = 10
2− +

@25° C
[
3

]
10.3
Salt increases the CPWater
HCO3− ( aq )
but CO2 decreases
CPWater; usually salt
effects dominate

Speciation
diagram for
carbonates

Carbonate Solubility 2
Hydrothermal Geochemistry 28 February 2005

Solubility of carbonates
increases with PCO2, but
generally levels out at
~1 molal CO2

Changes in pK for
carbonate and other acids

Dissolution of carbonates
Strontianite solubility
MCO3 ↔ M 2 + + CO32 − [
KSP = [ M 2 + ] CO32 − ]
Solubility of carbonates is
controlled by:

MCO3 + CO2 + H2 O ↔ M 2 + + 2 HCO3−

[ M 2 + ][ HCO3 − ]2
K=
PCO2

Ksp and CO2 solubility both

decrease with increasing T
(CO2 only to ~200°C), Note reversal of scale:
resulting in retrograde should be PCO2, not T
solubility for most
carbonates

Carbonate Solubility 3
Hydrothermal Geochemistry 28 February 2005

Effects of salts on calcite solubility

Temperature dependence of calcite solubility

Calcite solubility in T-CO2 space

Calcite solubility in T-NaCl space

Carbonate Solubility 4
Hydrothermal Geochemistry 28 February 2005

Golden Cross, NZ: late massive calcite

In alkaline solutions:
Solubility increase is due to
increasing CO3 and increasing
T; no significant effects from
other salts (e.g., KCl)
This is likely due to formation
of carbonate complexes such
as Ca(CO3)46-
Note that solubility under these
conditions is not retrograde

Deposition of carbonates in the geological environment Deposition of carbonates

Degassing (boiling)
Because of the difference in
Four major mechanisms: rate of reactions (dissolution
heating of CO2 in water [slow] vs.
ionization [fast]), boiling
degassing (boiling)
preferentially removes CO2
decreasing salinity
increasing pH Characteristic morphology of
bladed crystals (these may
later be dissolved!)

Heating: MCO3 + CO2 + H2 O ⇔ M 2 + + 2 HCO3−

1. move a cool solution through hotter environment (e.g. collapse
of the hydrothermal system; seafloor systems) [ M 2 + ][ HCO3 − ]2
K=
2. mixing of two solutions PCO2
Texturally often results in massive calcite

Carbonate Solubility 5
Hydrothermal Geochemistry 28 February 2005

Changes in pH
Broadlands calcite well scale: deep boiling fluids
Boiling increases pH by removal
of acid gases
Wallrock reaction results in
consumption of H+ during cation
exchange and formation of
hydrous phases

Redox reactions may operate:

H2SO4 reduction to H2S yields a
weaker acid and increased pH
[note the reverse dissolves
carbonates]

Deposition of carbonates Carbonate morphology

Decreasing salinity Supersaturation in carbonates is harder to achieve, so
Difficult to do morphologies are not as varied as for silica
geologically except by Some morphological changes [crystal chemical variations]
mixing, and mixing will are recognizable
not work because of
the linear mixing
Bladed textures indicate boiling
relationship
Banded textures (e.g.,
malachite, rhodochrosite)
indicate inherent easy
nucleation

Golden Cross, NZ: late bladed

calcite coated by quartz

Carbonate Solubility 6
Hydrothermal Geochemistry 28 February 2005

Dolomitization
Dolomitization is
generally a
function of
Ca:Mg in fluids
Increasing [Mg] in
solution causes
dolomitization

Carbonate Solubility 7