Professional Documents
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Reactions in PHREEQC
PHREEQC mechanics
Important geochemical reactions
discussion and exercises
Carbonates
Oxidation of organic carbon
Oxidation of pyrite
Aluminosilicate reactions
1
Reaction Calculations
SOLUTION
MIX
REACTION
EQUILIBRIUM EXCHANGE
_PHASES
SURFACE
KINETICS
GAS_PHASE
EQUILIBRATION REACTOR
SOLUTION
EQUILIBRIUM_
PHASES
EXCHANGE
SURFACE
GAS_PHASE
2
SOLUTIONChemical
Composition of a Water
Chemical analysis
pH
Temperature
Major elements Ca, Mg, Na, K, Alkalinity, Cl, SO 4
Trace elements
Nutrients
(Irreversible) REACTION
Add/Remove elements to water
Make a solution 1 m NaCl and 2 m KBr
Start with water
REACTION
NaCl 1
KBr 2
1 mole
EQUILIBRIUM_PHASES
Assemblage of Minerals and Gases
that react to equilibrium
Calcite
CaCO3 = Ca+2 + CO3-2
Equilibrium
K = [Ca+2][CO3-2]
5
CO2
10 moles
Calcite
Dolomite
Fe(OH)3
equilibrium
equilibrium
equilibrium
1 moles
1 moles
0 moles
6
[K
]N
C
a
X
[N
a
C
]
2
2
EXCHANGECation Exchange
Composition
[K
foO
H
s][O
A
]
3
4
SURFACESurface Composition
Trace elements Zn, Cd, Pb, As, P
Sorption onto the surfaces of minerals and
organic matter, usually hydrous ferric oxides
HfoOH + AsO4-3 = HfoOHAsO4-3
Equilibrium:
KINETICSNonequilibrium Reactions
Can affect any chemical constituent
Monod Kinetics
Radioactive decay
Silicate hydrolosis
Organic decomposition
Biological processes
11
RATES
10 Rate = 0.01*TOT(Doc)
20 SAVE rate*TIME
12
SOLID_SOLUTIONSComposition
of one or more solid solutions
Trace elements and isotopes
List of solid solutions
Components of each solid solution
Example SOLID_SOLUTION 21:
Calcite solid solution
Ca[13C]O3
CaCO3
13
14
PHREEQC Reactants
Keyword data blocks define reactants
SolutionsSOLUTION
Irreversible reactionREACTION
Equilibrium minerals and gasesEQUILIBRIUM_PHASES
ExchangersEXCHANGE
SurfacesSURFACE
Kinetic reactionsKINETICS and RATES
Solid solutionsSOLID_SOLUTIONS
PHREEQCReactions
From the shelf
To the beaker
17
EQUILIBRIUM REACTIONS
SURFACE
EXCHANGE
SOLID_SOLUTIONS
EQUILIBRIUM_PHASES
GAS_PHASE
18
NON-EQUILIBRIUM REACTIONS
MIX
REACTION
REACTION_TEMPERATURE
KINETICS
19
CONCEPTUAL MODEL
1. Initial conditionSOLUTION or MIX
2. Add irreversible reactants
REACTION
KINETICS
REACTION_TEMPERATURE
EQUILIBRIUM_PHASES
SURFACE
EXCHANGE
SOLID_SOLUTION
GAS_PHASE
Carbonates
Oxidation of organic carbon
Oxidation of pyrite
Aluminosilicate reactions
21
SOLUTION
MIX
EQUILIBRIUM_PHASES
REACTION
END
SAVE and USE
(GAS_PHASE)
22
Reactions
Implicit redox reactions
23
24
REACTION 1. Exercise
Implicit Redox Reactions
mg/L
R1. Questions
1. Explain the differences between the
initial solution composition and the
reaction (mixed) solution composition,
particularly pH, pe, N(5), N(0), and
N(-3).
26
R1. Answers
Initial solution
Reaction solution
pH
4.500
4.216
pe 4.000
16.373
O(0)
4.375e-004
3.781e-004
N(5)
1.692e-005
3.177e-005
N(0)
0
1.126e-016
N(-3)
1.485e-005
0.000e+000
The differences are caused entirely by redox equilibration. Initial solution is in redox
disequilibrium, the reaction solution is in redox equilibrium. In the reaction solution:
Redox Calculations
Initial solution
Reaction calculations
28
Reactions
Sequential Reactions
29
31
32
33
REACTION:
Reactants and stoichiometry
Choose phase
or type formula
Define relative
stoichiometry
Must be charge
balanced
34
35
EQUILIBRIUM_PHASES
Assembly of
minerals/gases
that react to
equilibrium or zero
moles
Define
Mineral/gas
Target saturation
index
Moles present
36
37
ENDdefines a Simulation
Within a simulation
38
Simulation 1
Simulation 2
Simulation 3
No speciation calculation
No reaction calculationNo Reactant defined
39
REACTION 3. Exercise
Sequential Reactions
R3. Questions
1. What is the log pCO2 of the rainwater,
rainwater, in redox equilibrium (the mixture),
the mixture equilibrated with CO2 and calcite,
and after reaction with CO2 and calcite?
2. How many millimoles of calcite and CO2
reacted to make solution 3?
3. How many millimoles of calcite reacted to
make solution 4 from solution 3?
41
R3.
Answers
Question 1.
Solution 1 Rainwater
Solution 2 Rainwater, redox equilibrium
Solution 3 Solution 2 + equilibrium with CO2 and Calcite
Solution 4 Solution 3 + Reaction + equilibrium with Calcite
Solution 1
CO2(g)
-3.50
Question 2.
Phase
Calcite
CO2(g)
43
R5. Answer
SOLUTION_SPREAD
Description Temp
pH
O2(g) -0.7
CO2(g) -3.5
Rainwater
25
4.5
END
MIX 1
1 20
REACTION
H2O
55.5
-19 moles
EQUILIBRIUM_PHASES
CO2(g) -3.5
SAVE solution 2
END
USE solution 2
EQUILIBRIUM_PHASES 2
Calcite 0 10
CO2(g) -2 10
SAVE solution 3
END
USE solution 3
REACTION 1
CO2
1
1 millimoles
EQUILIBRIUM_PHASES 3
Calcite 0 10
SAVE solution 4
END
O(0)
Ca
Mg
Na
0.384
0.043
0.141
0.036
44
REACTIONS in PHREEQC
Initial-solution calculation
Reaction calculation includes any of the following:
MIX
REACTION
REACTION_TEMPERATURE
EQUILIBRIUM_PHASES
EXCHANGE
SURFACE SOLID_SOLUTION
GAS_PHASE
KINETICS
Simulation/END
SAVE
USE
Index numbers
45
Reactions
Dedolomitization
46
Dedolomitization
Anhydrite dissolution
Calcite precipitation
Dolomite dissolution
47
REACTION 6. Exercise
1. Make a ground water with log pCO2 = -2,
equilibrium with calcite and dolomite.
2. React 50 mmol of anhydrite (CaSO4) in
increments of 10 mmol. Maintain equilibrium
with calcite and dolomite, allow anhydrite to
precipitate if it becomes saturated.
REACTION 6. Questions
1. What trends do you expect in water
composition with anhydrite-driven
dedolomitization?
2. Why is the following reaction
misleading?
CaSO4 + CaMg(CO3)2 = 2CaCO3 + Mg+2 + SO4-2
49
Reaction 6. Answers
50
Reaction 6. Answers
Question 1.
Increase in SO4, increase in Ca and Mg, constant or decrease in HCO3,
decrease in pH, SIs near zero for calcite and dolomite.
Question 2.
You do not get a Mg+2 SO4-2 water composition. Ratio of Mg/Ca is
approximately constant at .3 to 1 (depending on K for dolomite).
To get to the final water composition, the net reaction is approximately
37CaSO4 + 16CaMg(CO3)2 = 32CaCO3 + 21Ca+2 + 16Mg+2 + 37SO4-2
Question 3.
System has reached equilibrium and does not change. However, it is not
quite an invariant point.
51
SELECTED_OUTPUT
File name
1. Set file name
(default selected.out)
2. Reset all to false
3. Set pH to true
4. Set Reaction true
52
53
Selected Output
54
Selected
Output File
Open with Excel
Manipulate/plot
data
PFW has built-in
plotting
capability
55
REACTION 8. Questions
Plummer and Sprinkle, 2001
Units are mg/L, S(-2) as H2S
Number
1
4
6
Temp
24.7
31.5
27.2
pH
7.76
7.45
7.48
Ca
Mg
38
100
114
Na
8.1
52
79
K
4
12
265
0.8
2.9
17
Alkalinity
143.9
176.1
177.5
Cl
S(6)
6.9
14
412
Si
12
340
180
Sr
13
21
19
S(-2)
0.081
24
15.3
56
0
1.92
2.6
Reaction 8. Answers
Yes, Increase in Ca, Mg, SO4; decrease
in pH; not much change in alkalinity.
Decrease in sulfate (number 4 to
number 6) and H2S indicate sulfate
reduction.
Na and Cl indicate mixing with seawater
57
EQUILIBRIUM_PHASE:
Dissolve Only
Force mineral not
to precipitate
58
REACTION 9. Exercise
1. Make a ground water with log pCO2 = -2,
equilibrium with calcite and dolomite.
2. Equilibrate seawater (major ions only) with
calcite and dolomite; allow dolomite only
to dissolve.
3. Mix ground water with seawater in fractions
of .25, 0.5, .75. Maintain equilibrium with
calcite; allow dolomite only to dissolve.
59
REACTION 9. Questions
1. What reaction is calculated for seawater
equilibration with calcite and dolomite?
2. What reactions are calculated for a
carbonate reactions for the groundwater/seawater mixtures?
60
Reaction 9. Answers
1. Calcite precipitates; dolomite does not react, but should
precipitate. Seawater mixing zones have been suggested as a
place where dolomitization could occur, but there is little evidence
for present-day dolomitization. Apparently kinetics of dolomite
formation are too slow, even though it should form according to
thermodynamics.
2. Dolomite is always supersaturated and is not allowed to form by
the problem definition. Calcite dissolves at the .75 ground-water
mixing fraction and precipitates at .5 and .25. Saturation indices
of mixtures are non-linear. Even though the ground water is
saturated and seawater is supersaturated with calcite, 0.75 g-w
mixture is undersaturated with calcite. In this case, it is an activity
coefficient effect; the effect of the decrease in activity coefficients
of the mixture is larger than the effect of the increase in
concentration, which results in a negative saturation index for
calcite and dissolution.
61
Carbonate Reactions
Carbonate ground water
PCO2 -1 to -3.0
Calcite, or calcite and dolomite
CO2 supply in the UZ
Dedolomitization
Anhydrite dissolution
Calcite precipitation
Dolomite dissolution
Other reactions
Sulfate reduction
Ion exchange
Dolomitization
Rare
Seawater mixing can dissolve calcite
62
Reactions
Organic decomposition
63
Organic Decomposition
Sequential removal of electron acceptors,
usually in the sequence:
O2
NO3 MnO2
Fe(OH)3
SO4-2
Organic carbon
64
Redox Environments
OxicDissolved O2 reduction
CH2O + O2 = CO2 + H2O
SulfidicSO4-2 reduction
2CH2O + SO4-2 = 2HCO3- + H2S
MethanicCH4
CH2O = CO2 + CH4
65
Redox Environments
25
20
15
H2
Methanic
Sulfidic
Post-oxic
Oxic
pe
10
5
0
-5
-10
-15
0
10
12
14
pH
66
Redox Sequence at pH 7
Redox couple
pe
O(-2)/O(0)
12.9
N(0)/N(5)
11.8
Se(4)/Se(6)
7.7
Cr(3)/Cr(6)
7.0
N(-3)/N(5)
6.1
Fe(2)/Fe(3)
3.9
Se(-2)/Se(4)
0.4
U(4)/U(6)
0.4
As(3)/As(5)
0.3
V(3)/V(5)
-2.3
N(-3)/N(0)
-3.2
S(-2)/S(6)* (wateq4f.dat)
-3.6
C(-4)/C(4)
-4.4
67
Organic decomposition
REACTION
2CH2O + SO4-2 = 2HCO3- + H2S
WRONG!
REACTION
CH2O -2
SO4-2 -1
HCO3- +2
H2S
+1
5 mmol
RIGHT!
REACTION
CH2O 1
10 mmol
Or perhaps,
REACTION
CH2O 1
Doc -1
10 mmol
68
Organic Decomposition in
PHREEQC
Mole balance of C increases
H and O mole balances increase too, but
equivalent to adding H2O
If there are electron acceptors, C ends up as
CO3-2 species
Electron acceptor effectively gives up O and
assumes the more reduced state
The choice of electron acceptor is
thermodynamic
69
2.
72
73
pH
Ca
7.23
7.45
Mg
4.7
4.4
Na
25.3
22.2
K
216
190
Alkalinity
5.9
6.4
5.3
24
Cl
S(6)
257
223
Fe
10
0.5
S(-2)
0.009
0.005
N(-3)
1
3.4
0.35
2.27
75
REACTION 14.
Exercise
76
REACTION 14.
Questions
77
Sulfate Reduction
Norman Landfill
Cozzarelli
temp C
pH
DO
(ppm)
(mg/L)
chemet.
field
lab
0.04
166.00
0.11
514.00
field
16.6
ND
field
7.01
6.78
Si
Fe 2+
Mn2+
Sr2+
(mg/L)
(mg/L)
(mg/L)
(mg/L)
lab
8.70
16.80
lab
0.13
19.30
lab
1.94
0.90
2+
Ca
lab
1.06
9.87
Mg
2+
(mg/L)
Na
(mg/L)
lab
52.60
232.00
lab
91.80
606.00
Ba2+
SiO2
NO3
(mg/L)
(mg/L)
lab
0.14
7.12
lab
18.60
35.90
Cl
(mg/L)
lab
2.50
14.40
(mg/L)
IC
lab
0.05
3.48
NH4
(mg/L)
IC
lab
181.0
1026.6
SO4 2(mg/L)
IC
lab
113.60
0.10
Br
Alk
(HCO3)
mg/L
lab
626
2,642
(mg/L)
IC
lab
0.79
7.54
DOC
(ppm)
(mg/L)
Chemet.
field
lab
2.1
2.9
15.0
158.7
O(0)
5.6
6.48
Ca
250
0
Mg
29
483
Na
31
235
K
200
2202
C(4)
10
272
Cl
28
1259
S(6)
140
1593
Fe
86
296
Mn
P
0.64
2.3
571
9.4
105
Iron reduction
No sulfate reduction
Blue Plains, Washington D.C.
Potomac River Sediment Pore Water
units mmol/L
pH
V28, 1 cm
V28, 36 cm
7.02
7.14
Ca
Mg
1.8
3.1
Na
0.8
1.4
K
0.8
1
Alkalinity
meq/L
0.2
6.8
0.5
24.9
Iron reduction
Minor sulfate reduction
Intense methanogenesis
Cl
S(6)
0.6
0.8
Fe
S(-2)
N(-3)
0.033
0.43
0.7
17.8
80
Central Oklahoma
-units mg/L
Description
Num
ber
Temp
pH
O(0)
Ca
Mg
Na
Alkali
nity
Cl
S(6)
as CaCO3
City of Jones 13N-01W34 CAB
17.5
7.4
4.1
42
21
12
1.5
196
12
8.1
N(5)
N(-3)
as N
as N
0.49
81
Organic Decomposition
Sources
O2Atmosphere, DO negligible
NO3Atmosphere, ag chemicals
Fe(3)Iron oxyhydroxides
SO4Seawater, atmosphere, gypsum
Organic carbonCH4 and CO2
Organic carbon can be absent
82
Redox Sequence at pH 7
Redox couple
pe
O(-2)/O(0)
12.9
N(0)/N(5)
11.8
Se(4)/Se(6)
7.7
Cr(3)/Cr(6)
7.0
N(-3)/N(5)
6.1
Fe(2)/Fe(3)
3.9
Se(-2)/Se(4)
0.4
U(4)/U(6)
0.4
As(3)/As(5)
0.3
V(3)/V(5)
-2.3
N(-3)/N(0)
-3.2
S(-2)/S(6)* (wateq4f.dat)
-3.6
C(-4)/C(4)
-4.4
83
2.
3.
Reactions
Sulfide oxidation
86
87
Sulfide Oxidation
Pyrite/Marcasite are most important reactants
Need Pyrite, Oxygen, Water, and bugs
Oxidation of pyrite and formation of ferric
hydroxide complexes and minerals generates
acidic conditions
88
89
Picher, Oklahoma
Flat topography
Mines 200 to 500 ft below land surface
Saturated after dewatering ceased
Cut off the supply of oxygen
90
Simplified Reactions
High pH
FeS2 + 15/4O2 + 4HCO3- = Fe(OH)3 + 2SO4-2 + 4CO2 + 1/2H2O
Or
FeS2 + 15/4O2 + 7/2H2O = Fe(OH)3 + 2SO4-2 + 4H+
Low pH
FeS2 + 15/4O2 + 1/2H2O = Fe+3 + SO4-2 + HSO4-
91
Additional reactions
Hydrous ferric oxides
Ferrihydrite
Goethite
Jarosite
Aluminum hydroxides
Alunite
Carbonates
Gypsum
92
Equilibrium reactions
93
95
Pyrite oxidation:
FeS2 + xO2 + yH2O -> Fe+3 + 2SO4-2 + H+
In addition, a little ferric iron hydrolizes to make additional H+:
Fe+3 + H2O = FeOH+2 + H+
With net acid production to give pH 2.
Mackinawite oxidation:
FeS + 2.25O2 + H+ -> Fe+3 + SO4-2 + .5H2O
But a majority ferric iron hydrolizes
Fe+3 + xH2O = Fe(OH)x+y + H+
With a net acid production that give pH 4.
Sphalerite oxidation:
ZnS + 2O2 -> Zn+2 + SO4-2
Zinc hydrolosis is minimal
Zn+2 + H2O = ZnOH+ + H+
Net result is pH 7.
2. HSO4-/SO4-2
3. Iron oxyhydroxides, goethite (and often Fe(OH)3(a)) and jarosite. There is also a
potassium jarosite and other solid solutions of jarosites. Aluminum has
96
analogous minerals named alunite.
97
REACTION 20.
Questions
98
99
Picher Oklahoma
Abandoned Pb/Zn Mine
mg/L
temp
Admiralty
SW site 8
pH
15
30
Al
Admiralty
SW site 8
1.4
3.7
O(0)
Ca
5.7
3
Cd
0.01
0.002
Mg
490
420
Cu
Fe
0.008
Na
250
110
Pb
300
54
K
89
46
Mn
0.04
0.14
Alkalinity Cl
6.5
260
3.6
0
S(6)
28
8
Zn
5.3
5.2
150
100
3200
2100
Pyrite Oxidation
Requires
Pyrite/Marcasite
O2
H2O
Bacteria
Produces
Ferrihydrite/Goethite, jarosite, alunite
Gypsum if calcite is available
Evaporites
Possibly siderite
Acid generation
Pyrite > FeS > ZnS
101
Reactions
Aluminosilicate reactions
102
Aluminosilicate Reactions
Disseminated calcite important in silicate terranes
Bowen/Goldich reaction series
More stable
Olivine
Pyroxene (augite)
Amphibole (hornblende)
Biotite mica
Ca-Feldspar
Plagioclase
Na-Feldspar
K-Feldspar
Muscovite
Quartz
103
Aluminosilicates
Primary minerals react to form gibbsite,
kaolinite, smectite, zeolites, SiO2
Thermodynamic data is not reliable
Compositional uncertainties
Range of stabilities
Difficult to measure aluminum
105
REACTION 22.
Questions
107
108
Ca
6.2
6.8
Mg
Na
K
0.078
0.029
0.134
0.26
0.071
0.259
Alkalinity
0.028
0.328
0.04
0.895
Cl
S(6)
0.014
0.03
Si
0.01
0.025
0.273
0.41
Tuesday Summary
MIX
EQUILIBRIUM_PHASES
REACTION
110
Summary
Carbonate minerals and CO2
Dedolomitization
Organic decomposition
Sulfate reduction
Other electron acceptors O2, NO3, FeOOH,
CH2O
Sulfide oxidation
Aluminosilicate reactions
111
Next
GAS_PHASE (optional)
EXCHANGE
SURFACE
KINETICS
Inverse modeling
Transport modeling
112
GAS_PHASE
Fixed Volume
Fixed pressure
Lake sediments
A balloon
114
GAS_PHASE
PV = nRT Ideal gas law
Henrys law
Log K = [CO2]/P(CO2)
115
7.02
7.14
Ca
Mg
1.8
3.1
Na
0.8
1.4
K
0.8
1
Alkalinity
meq/L
0.2
6.8
0.5
24.9
Cl
S(6)
0.6
0.8
Fe
S(-2)
N(-3)
0.033
0.43
0.7
17.8
Iron reduction
Minor sulfate reduction
Intense methanogenesis
116
GAS_PHASE
Pick gas components
Initial moles in the
gas phase are
calculated ideal gas
law using:
Pressure
Initial volume
Initial temperature
Partial pressures of
components
117
121