Mineral Preciptation

Minerals which are precipitated can also

interact with other molecules and ions at
the surface
Attraction between a particular mineral
surface and an ion or molecule due to:
Electrostatic interaction (unlike charges attract)
Hydrophobic/hydrophilic interactions
Specific bonding reactions at the surface

SATURATION INDEX
The thermodynamic state of a mineral relative to a solution

SI < 0, Mineral should dissolve

SI > 0, Mineral should precipitate
SI ~ 0, Mineral reacts fast enough to maintain
equilibrium
Maybe
Kinetics
Uncertainties

Rules for Saturation Indices

Mineral can not dissolve if it is not present
If SI < 0 and mineral is presentthe mineral
could dissolve, but not precipitate
If SI > 0the mineral could precipitate, but not
dissolve
If SI ~ 0the mineral could dissolve or
precipitate to maintain equilibrium

Uncertainties in SI: Analytical data

5% uncertainty in element concentration is
.02 units in SI.

0.5 pH unit uncertainty is 0.5 units in SI of

calcite, 1.0 units in dolomite

1 pe or pH unit uncertainty is 8 units in SI

of FeS for the following equation:

SI(FeS) = log[Fe]+log[SO4-2]-8pH-8pe-log K(FeS)

Non-Equilibrium
Viewing groundwater as a partial equilibrium
system implies that some reactions may not be
equilibrated.
Dissolution-precipitation reactions are certainly in
the non-equilibrium category.
Departures from equilibrium can be detected by
observing the ion activity product (IAP) relative to
the equilibrium constant (K) where
IAP = [C]c[D]d = products
[A]a[B]b reactants

Dissolution-Precipitation
aA + bB = cC + dD
If IAP<K (IAP/K<1) then the reaction is
proceeding from left to right.
If IAP>K (IAP/K>1) then the reaction is
proceeding from right to left.
If the reaction is one of mineral dissolution
and precipitation
IAP/K<1 the system in undersaturated and is
moving towards saturation by dissolution
IAP/K>1 the system is supersaturated and is
moving towards saturation by precipitation

Saturation Index
Saturation index is defined as:
SI = log(IAP/K)
When a mineral is in equilibrium with the
aqueous solution SI = 0
For undersaturation, SI < 0
For supersaturation, SI > 0

Calcite
The equilibrium constant for the calcite dissolution reaction is K =
4.90 x 10-9 log(K) = -8.31
Given the activity coefficients of 0.57 for Ca 2+ and 0.56 for CO32and molar concentrations of 3.74 x 10 -4 and 5.50 x 10-5
respectively, calculate IAP/K.
Reaction: CaCO3 = Ca2+ + CO32IAP = [Ca2+][CO32-] = 0.57x3.37x10-4x0.56x5.50x10-5
[CaCO3]
1.0
= 6.56 x 10-9 and log(IAP) = -8.18
{IAP/K}calcite = 6.56/4.90 = 1.34
log{IAP/K}calcite = 8.31 - 8.18 = 0.13
The solution is slightly oversaturated wrt calcite.

Uncertainties in SI: Equation

Much smaller uncertainty for SI(FeS) with
the following equation :
SI(FeS) = log[Fe]+log[HS-]+pH-log K(FeS)

For minerals with redox elements,

uncertainties are smaller if the valence
states of the elements in solution are
measured.

Uncertainties in SI: Log K

Apatite from Stumm and Morgan:
Ca5(PO4)3(OH) = 5Ca+2 + 3PO4-3 + OH G 0r 5( 553.54) 3( 1018.8) ( 157.3) ( 6338.4) 357kJ / mol
0
357.0
G r
log K Apatite

62.6
RT 5.707

Apatite from Wateq: log K = -55.4

Log Ks especially uncertain for aluminosilicates

Useful Mineral List

Minerals that may react to equilibrium relatively quickly

Carbonates
CO2(g)
Calcite
Dolomite
Siderite
Rhodochrosite
Sulfates
Gypsum
Celestite
Barite
Sulfides
FeS(a)
Mackinawite

CO2
CaCO3
CaMgCO3
FeCO3
MnCO3
CaSO4
SrSO4
BaSO4
FeS
FeS

Phosphates
Hydroxyapatite
Vivianite
Oxyhydroxides
Fe(OH)3(a)
Goethite
Gibbsite
Birnessite
Manganite
Aluminosilicates
Silica gel
Silica glass
Chalcedony
Kaolinite

Ca5(PO4)3OH
Fe3(PO4)2
Fe(OH)3
FeOOH
Al(OH)3
MnO2
Mn(OH)3
SiO2-2H2O
SiO2-H2O
SiO2
Al2Si2O5(OH)

IS.13. Exercise
Examine solution compositions in
spreadsheet speciation.xls.
Calculate saturation indices.
What can you infer about the hydrologic
setting, mineralogy, and possible reactions
for these waters?

Summary
SOLUTION and SOLUTION _SPREAD

Units
pHratio of HCO3/CO2
peratio of oxidized/reduced valence states
Charge balance
Phase boundaries

Saturation indices
Uncertainties
Useful minerals

Identify potential reactants

Diffusion Rates
Diffusion, Fickian:
First law (steady state):

C
J D
x

Second Law (change w/time):

C
C
D 2
t
x
2

Where J is the flux (concentration area-1 time-1), D is the

diffusion coefficient (area-1 time-1), C is concentration
and t is time.

Mineral diffusion rates

For diffusion controlled rates:
Rd=DA(Cs-C)/r
Where Rd is the diffusion rate (mass volume-1 time-1), D is the
diffusion coefficient (cm2/sec), is porosity, A is the surface
area of the dissolving crystals per volume solution, Cs is the
equilibrium concentration of ion in question, C is
concentration, and r is spherical radius of dissolving
crystals

Diffusion rates are generally the slowest rate

that controls overall dissolution

Transport controlled rates

For systems where water is flowing:

dC
RkfC
dt

Where R is the surface-controlled rate of

dissolution (R=k+[Cs-C]), kf is the flushing
frequency (rate of flow/volume), Cs is the
saturation concentration, and C is conc.
SO at high flow rate dissolution is surface
reaction controlled, at low flow rate it is diffusion
controlled

Zero-order mineral dissolution kinetics

Most silicate minerals (feldspars, quartz
polymorphs, pyroxenes, amphiboles) are
observed to follow zero-order kinetics:
R=Ak+

Log dissolution rate

where A is the surface area and k is the rate constant (mol

cm-3 sec-1) for rate, R, of an ion dissolving from a mineral

pH

Rate and equilibrium

pH dependence of silicate mineral dissolution,
suggests activated surface complex for dissolution:
Q
R k [ H ] [1
]
K eq
n

where n is a constant, p is the average

stoichiometric coefficient, Q is the activity quotient,
and Q/Keq is the saturation index (how far from
equilibrium the mineral is)
Far from equilibrium, Q/Keq < 0.05, simplifies to
R=k+[H+]n

Ligand-assisted dissolution
Thought to be minor for many
aluminosilicates, but key for many other
minerals (ex.: FeOOH minerals)
Similar to surface-complex control, ligands
strongly binding with surface groups on
the mineral surface can greatly increase
rate (and solubility of the ion in solution,
changing the SI)

Mineral precipitation kinetics

How do minerals form?
Ion-ion interaction cluster aggregation
nanocrystal formation crystal growth
(ionic aggregation, ostwald ripening,
topotactic alignment)
What controls the overall rate?

Charged Surfaces
OH
OH
OH2

H+

OH
OH
OH
OH

H+

Mineral surface has exposed

ions that have an unsatisfied
bond in water, they bond to
H2O, many of which rearrange
and shed a H+
S- + H2O SH2O SOH + H+

GOUY-CHAPMAN
DOUBLE-LAYER
MODEL

STERN-GRAHAME
TRIPLE-LAYER
MODEL

Surface reaction vs. transport

control vs. diffusion control
3 possibilities for controlling overall rate of
mineral dissolution:
Surface reaction chemical process at the
mineral surface with a reactant
Diffusion control physical process of
dissolved component(s) diffusing into the bulk
solution
Transport control physical process of
dissolved component(s) being advectively
carried from the mineral surface

General mineral dissolution rates

(surface reaction)
General rate law for minerals:
d [mineral ]
kA[reactant ]
dt

Where k is in something similar to units of mol -1

sec-1 to give a rate, R, in terms of mol cm -3 sec-1
Many ways to write the rate constant units
depending on the rate law (which is almost never
an elementary rxn for minerals), but dissolution
rate for minerals is normalized to surface area as
the primary control on overall rates!