Tuesday

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

EQUILIBRIUM_PHASES Data Block

Mineral or gas
Saturation state
Amount
Example EQUILIBRIUM_PHASES 5:

CO2

Log PCO2 = -2,

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

Exchangeable cations in interlayers of clays

Ca+2 + 2NaX = CaX2 + 2Na+
Equilibrium:

EXCHANGE Data Block Definition

Exchanger name
Number of exchange sites
Chemical composition of exchanger
Example EXCHANGE 5:
CaX2
NaX
Often
X

0.05 moles (X is defined in databases)

0.05 moles
0.15 moles, Equilibrium with solution 1
8

[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:

SURFACE Data Block Definition

Surface nameHfo is Hydrous Ferric Oxide
Number of surface sites
Chemical composition of surface

Example SURFACE 21:

0.001 moles
Hfo_wOH
.00005 moles
Hfo_sOH
Often
Hfo_w 0.001 moles, Equilibrium with solution 1
10

KINETICSNonequilibrium Reactions
Can affect any chemical constituent

Monod Kinetics
Radioactive decay
Silicate hydrolosis
Organic decomposition
Biological processes
11

KINETICS and RATES Data Block

Definitions
Kinetic reaction name
Stoichiometry of reaction
Rate expression (RATES)

Example Kinetics 21:

DOC_decay
Doc -1 CH2O +1

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

GAS_PHASEFinite gas phase in

equilibrium with solution
Gas bubbles that grow
Gas bubbles that fill a finite volume

14

GAS_PHASEComposition of the gas

phase
Fixed volume or Fixed pressure
Initial volume
Initial pressure
Temperature
Partial pressure of each gas
Example GAS_PHASE 1:
Fixed pressure
CO2(g) 0.0
CH4(g) 0.0
15

PHREEQC Reactants
Keyword data blocks define reactants
SolutionsSOLUTION
Irreversible reactionREACTION
Equilibrium minerals and gasesEQUILIBRIUM_PHASES
ExchangersEXCHANGE
SurfacesSURFACE
Kinetic reactionsKINETICS and RATES
Solid solutionsSOLID_SOLUTIONS

Store reactants on shelves by type and number

16

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

3. Add reversible reactants

4. Calculate new composition

5. SAVE compositions if needed
20

Todays Geochemical Reactions

Carbonates
Oxidation of organic carbon
Oxidation of pyrite
Aluminosilicate reactions

21

Todays PHREEQC Data Blocks

SOLUTION
MIX
EQUILIBRIUM_PHASES
REACTION
END
SAVE and USE
(GAS_PHASE)
22

Reactions
Implicit redox reactions

23

MIX: One or more SOLUTIONS

Type solution
number
Type mixing
fraction

24

REACTION 1. Exercise
Implicit Redox Reactions
mg/L

1. Define rainwater as SOLUTION 1 with log partial

pressure of O2 = -0.7 and CO2 = -3.5.
2. Define END.
3. Define MIX by using solution 1 and mixing
fraction 1.
4. Define END.
5. Run.
25

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:

N(-3) has been oxidized to N(5) and N(0).

O(0) has been reduced in the process of oxidizing N(-3).
Oxidation tends to decrease pH.
Redox is defined by O(0)/O(-2) and N(5)/N(0) redox couples, both will give the
same pe.
27

Redox Calculations
Initial solution

Allows redox disequilibria

Total N(5), N(-3), O(0)

Reaction calculations

Complete aqueous redox equilibrium

Can redefine elements for disequilibrium
N, N(5), N(3), N(0), N(-3), Ngas, Amm

28

Reactions
Sequential Reactions

29

SAVE and USE

Save results of reaction calculations

Use previously defined SOLUTIONs,
EQUILIBRIUM_PHASES, REACTIONs, etc
Use previously SAVEd SOLUTIONS,
EQUILBRIUM_PHASES, etc
30

SAVE results from a Reaction Calculation

Index numbers
are used to
keep track
Index numbers
do not need to
be sequential

Note: SOLUTION defines an initial solution

calculation, which is automatically saved.

31

USE: Previously defined or SAVEd

USE includes KINETICS, MIX,

REACTION, and
REACTION_TEMPERATURE

Can USE previously SAVEd

EQUILIBRIUM_PHASES,
EXCHANGE,
SOLID_SOLUTION,
SOLUTION, SURFACE, or
GAS_PHASE

32

Initial Solution and Reaction Calculations

33

REACTION:
Reactants and stoichiometry
Choose phase
or type formula
Define relative
stoichiometry
Must be charge
balanced

34

REACTION: Reaction amounts

Steps are a
number of equal
increments
or
Steps are a
specified list
Specify units

35

EQUILIBRIUM_PHASES
Assembly of
minerals/gases
that react to
equilibrium or zero
moles
Define
Mineral/gas
Target saturation
index
Moles present
36

Initial Solution and Reaction Calculations

37

Initial Solution and Reaction Calculations

The END statement

ENDdefines a Simulation
Within a simulation

Every SOLUTION results in an

initial solution calculation (unique
index)
Reaction calculation
SOLUTION + one of each
reactant type before END
Reactants can be keyword
blocks
Reactants be defined by USE
END

Run speciation calculations

Run reaction calculations
Run transport calculations
SAVE results

38

Speciation and Reaction Calculations

The enigmatic END

Simulation 1

Speciation calculation solution 1

Speciation calculation solution 2
Reaction calculation
SOLUTION 1
EQUILIBRIUM_PHASES 2
REACTION 3

Simulation 2

Speciation calculation solution 3

Reaction calculation
SOLUTION 2
EQUILIBRIUM_PHASES 1
REACTION 3

Simulation 3

No speciation calculation
No reaction calculationNo Reactant defined
39

REACTION 3. Exercise

Sequential Reactions

1. Make an unsaturated zone water. Build on

previous exercise with rainwater. Add SAVE
solution 2 after MIX step and before END.
2. After the END, add USE solution 2 and
equilibrate (EQUILIBRIUM_PHASES) with CO2,
log partial pressure 2, and calcite (SI = 0),
save solution as solution 3. END.
3. Use solution 3, add 1 mmol CO2 (REACTION),
equilibrate with calcite
(EQUILIBRIUM_PHASES), save as solution 4.
40

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)

Solution 2 Solution 3 Solution 4

-3.49
-2.00
-1.65

SI log IAP log KT Initial

Final
Delta
0.00 -8.48 -8.48 1.000e+001 9.998e+000 -1.749e-003
-2.00 -20.15 -18.15 1.000e+001 9.998e+000 -1.774e-003

1.74 mmol calcite dissolve.

1.77 mmol CO2 dissolve.
Question 3.
Phase
Calcite

SI log IAP log KT Initial

Final
Delta
0.00 -8.48 -8.48 1.000e+001 9.999e+000 -5.767e-004

0.58 millimoles of calcite dissolve.

42

REACTION 5. Extra Credit Exercise

1. Use MIX and REACTION to evaporate
rainwater 20 fold (at constant pCO2)
before reaction with CO2 and calcite. Hint:
You must remove water and water has
55.5 mol per kg.

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.

You need to use these data blocks: SOLUTION,

EQUILIBRIUM_PHASES, REACTION, USE,
SAVE in two simulations.
48

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

3. How does the water composition

change from step 4 to step 5?

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

Selected Output: Total Molalities

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

1. Are these the trends of dedolomitization?

2. Anything else?

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

Post-oxicNO3-, MnO2, Fe(OH)3 reduction

CH2O + 4Fe(OH)3 + 7CO2 = 4Fe+2 + 8HCO3- + 3H2O

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

REACTION 11a. Exercise

1.

Dilute seawater by 50 percent, equilibrate with

atmospheric oxygen

2.

React diluted seawater with 50 mmol of CH2O in 50

steps of 1 mmol. Equilibrate with .1 moles of
Fe(OH)3(a) and 0.0 mol of mackinawite.
Print moles of reaction (-rxn) and total
concentrations of O(0), C(4), C(-4), Fe(2), Fe(3),
S(6), S(-2) (-totals) and mackinawite (-equi) to the
selected-output file (SELECTED_OUTPUT).
70

REACTION 11a. Questions

1. What sequence of electron acceptors is
used?
2. Where is Fe(3) important?
3. Use Excel to plot the concentrations in the
selected-output file (rxn is the x variable, set
first line rxn from 99 to 0, omit
d_mackinawite).
4. Why is C(4) not a straight line?
5. Why does Fe(2) increase after 30 mmol of
CH2O is reacted.
6. Should a gas bubble form?
7. What trends are observed for sulfate
71
reduction?

Reaction 11a. Answers

72

Reaction 11a. Answers

1. O2, Fe(OH)3(a), SO4, CH2O (-> CH4 + CO2).
2. Fe(3) is not important anywhere.
3. See plot.
4. Eventually, the reacted carbon is split between CO2 and CH4.
5. Fe(OH)3 dissolves as pe decreases. Fe is no longer being sequestered in
mackinawite (FeS).
6. Depends on the depth of water, but certainly at atmospheric pressure a bubble
will form. At the end of the reaction (50 mmol CH2O reacted) the partial
pressure of methane is 10^.66 = 4.6 atmospheres. So if the ambient pressure
is less than 4.6 atmospheres (< ~35 m water depth), bubbles should form.
7. Decrease in sulfate, increase in alkalinity and pH. Usually, H2S does not
accumulate in solution, but precipitates as FeS or escapes as a gas. pH
changes are sensitive to Fe and S(-2) reactions.

73

REACTION 11b. Questions

Potomac Estuary Sediments
Units are mmol/L
Number Temp
1
20
5
20

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

1. How are these analyses similar to the

sulfate reduction simulation results?
2. How do these analyses differ from the
simulation results?
74

Reaction 11b. Answers

1. Sulfate decreases, alkalinity
increases, pH increases, ammonium
increases.
2. S(-2) is significant, Fe is negligible.
pH 7.5 not 9.

75

REACTION 14.

Exercise

1. What should happen if organic matter

oxidizes in the presence of barite?
2. Develop a reaction simulation
assuming 1 mmol of organic carbon
reacts.

76

REACTION 14.

Questions

1. What is the barium concentration in mg/L?

2. Are there reactions other than sulfate
reduction?
3. What other reactions could affect barium?

77

Reaction 14. Answers

1. 0.32*137 = 43 mg/L Ba.
2. 0.2 mmol/kgw methane was generated.
3. Cation exchange is a possibility. With
much larger TDIC, witherite (BaCO3) is
a possibility.
78

Sulfate Reduction
Norman Landfill
Cozzarelli

temp C

pH

USGS Reston, VA (avail)

Well
MLSNPD -6
MLS38-6

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

Barium concentration appears insignificant unless

barium is lost to cation exchange or mineral
precipitation.
79

Cape Cod Sewage Plume

units umol/L
pH
Background
343 6/18/96

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

No organic matter or reduced minerals

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

REACTION 16. Questions

1. How would you make the redox table of the
previous slide?
2. Iron is soluble as reduced ferrous iron,
uranium is soluble as oxidized U(6). As
organic carbon reacts, which would you
observe first: (a) increase in iron, (b)
decrease in uranium?
3. Thermodynamically, which nitrogen species
do you expect to see in an oxygenated
ground water? In a methanic water?
84

Reaction 16. Answers

1.

Define equal amounts (1 umol/kgw) of each redox

state Se(6), Se(4); As(5), As(3); etc. in SOLUTION
with pH 7. Look at pe table that is printed.

2.

(a) increase in iron concentration should occur first if

ferric oxyhydroxides are in the system. Equal
Fe(2)/Fe(3) at pe ~ 4, Equal U(4)/U(6) at pe ~ -1.

3.

NO3- in oxic water, NH4+ in methanic water.

However, NO3- generally is reduced to N2
(denitrification), not NH4+. NH4+ does nitrify to NO3-.
85

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

Iron Mountain, California

Sulfide deposits at the top of a mountain

Lots of precipitation
Unsaturated conditions
Tunnels drain

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

Modeling Pyrite Oxidation

FeS2 + 15/4O2 + 7/2H2O = Fe(OH)3 + 2SO4-2 + 4H+

Pick the irreversible reactant: O2 or FeS2

Equilibrium reactions

Oxygen rich environment of a tailings pile

We are going to react up to 50 mmol FeS2

93

REACTION 18. Exercise

1. React the pure water with 10 mmol of pyrite,
maintaining equilibrium with atmospheric
oxygen.
2. React the pure water with 10 mmol of
mackinawite, maintaining equilibrium with
atmospheric oxygen.
3. React the pure water with 10 mmol of
sphalerite, maintaining equilibrium with
atmospheric oxygen.
94

REACTION 18. Questions

1. Write qualitative reactions that explain
the pH of the 3 solutions.
2. What pH buffer starts to operate at
pHs below 3?
3. Run the input file with wateq4f.dat
database. What minerals may
precipitate during pyrite oxidation?

95

Reaction 18. Answers

1. Question 1

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.

REACTION 20. Extra Credit

Exercise
1. React the pure water with 20 mmol of pyrite,
maintaining equilibrium with atmospheric
oxygen and goethite.
2. Acid mine drainage is usually treated with
limestone. Use the results of part 1 and
equilibrate with O2, goethite, and calcite.

97

REACTION 20.

Questions

1. Write a net reaction for the PHREEQC

results for the low-pH simulation.
2. What are the pH values with and
without calcite equilibrium.
3. Looking at the results of the calciteequilibrated simulation, what additional
reactions should be considered?

98

Reaction 20. Answers

1. 20FeS2 + 75O2 = 19FeOOH + .8Fe(+3) + 27HSO4- + 12SO4-2 + 50H+
2. pHs are 1.4 and 5.8 without and with calcite equilibrium
3. Gypsum is supersaturated, and probably would precipitate.
pCO2 is 1 atmosphere. If O2 reacts to equilibrium with the atmosphere,
logically, CO2 would also.

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

Mines are suboxic

Carbonates are present
Iron oxidizes in stream
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

Kinetics are slow

104

Add Reactant to Phase Boundary

KAlSiO8 is added (or
removed) until
gibbsite equilibrium
is reached
SI is target SI for
Gibbsite
Amount is amount of
KAlSiO8 available

105

REACTION 22. Exercise

Use phreeqc.dat
1. Dissolve just enough Anorthite (CaAl2Si2O8)
to come to equilibrium with gibbsite.
2. Dissolve just enough Anorthite to come to
equilibrium with kaolinite.
3. Dissolve just enough Anorthite to come to
equilibrium with Ca-Montmorillonite.
4. Dissolve Anorthite to equilibrium, allow
gibbsite, kaolinite, and Ca-Montmorillonite
to precipitate.
106

REACTION 22.

Questions

1. Given the thermodynamic data, which

mineral should precipitate first?
2. What is the stable phase assemblage
in a water/anorthite system?
3. Does quartz need to be included in
this calculation?

107

Reaction 22. Answers

1. Gibbsite requires the least amount of
Anorthite to dissolve to become
saturated.
2. Solution, anorthite, gibbsite, kaolinite?!
3. Quartz is undersaturated in all
calculations.

108

Sierra Nevada Springs

mmol/kgw
pH
Ephemeral Spring
Perennial Spring

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

Increase in Ca, Alkalinity, pH

Increase in SiO2
Slight increase in Mg, K, Cl, SO4
109

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

REACTION 24. TEST

Make a soil zone, carbonate ground
water, log PCO2 = -2.0
Titrate the water with by addition of HCl
(use REACTION)
Plot pH vs acid added, assuming
equilibrium with atmospheric CO2
Plot pH vs acid added, assuming no
CO2 escapes from the sample
113

GAS_PHASE
Fixed Volume

Sample plus head space

Isolated UZ water and gas?

Fixed pressure

Lake sediments
A balloon

114

GAS_PHASE
PV = nRT Ideal gas law
Henrys law
Log K = [CO2]/P(CO2)

Fixed pressureVolume varies

Fixed volumePressure varies

115

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

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

REACTION 25. Exercise

React water with 50 mmol of

CH2O(NH3)0.1 in freshwater sediment

1. How is the reacted carbon distributed

in the solution?
2. How would you classify the water in
terms of cations and anions?
3. What other processes should we
consider?
118

Reaction 25. Answers

1. 25 mmol C(-4) (methane); 25 mmol
C(4) (20 mmol CO2, 5 mmol HCO3-)
2. Ammonium bicarbonate water.
3. Gas bubbles
119

REACTION 26. Gas phase

Include a gas phase in the last

simulation
Initial partial pressure of CO2 = 0
Initial partial pressure of CH4 = 0
Fixed pressure is 1.0 atm

1. What is the composition of the gas

phase?
2. What is the volume of the gas phase?
120

Reaction 26. Answers

1. 70% CH4, 30% CO2
2. 0.83 liters

121