Coprecipitation Reactions -

Verification of Computational Methods

in Geochemical Models

John J. Mahoney, Ph.D.

Mahoney Geochemical Consulting LLC
Lakewood, CO

jmahoney@mahoneygeochem.com
Updated and Expanded Version for
Website Viewing
Original Presentation was given in EPA/525/C-00/004,
January 2001 Mining Impacted Pit Lakes 2000
Workshop Proceedings: A Multimedia CD Presentation

Additional slides in italics have been added to the presentation

to clarify certain items
Fate of Metals in Ground-Water Systems

1. Precipitation

2. Adsorption

3. Coprecipitation or Solid Solution Reactions

Coprecipitation Reactions Control
Concentrations in Ground Water
Ra in BaSO4 (Barite)

Sr in CaCO3 (Calcite)

Cd in CaCO3 (Calcite)

Sr in CaSO4 2H2O (Gypsum)

AsO4 in Ca5(PO4)3OH (Apatite)

Al in FeOOH (Goethite)

MoO4 in Ca6Al2(SO4)3(OH)12 24H2O (Ettringite)

Cr(III) in Fe(OH)3 (Ferrihydrite)

Cr(VI) in BaSO4 (Barite)

Clay Minerals
 Coprecipitation Reactions Under-
Under-Utilized
in Applied Models

1. Emphasis on Precipitation and Adsorption Reactions

2. Belief that Standard Models (MINTEQA2, PHREEQE and

PHREEQC) Cannot Perform Coprecipitation Calculations

3. Data Bases for Coprecipitation Reactions Not Provided

in Standard Models

4. Belief That Data Describing Solid Solution Reactions is Too

Limited or Lacking for User’s Problem
Coprecipitation of Cadmium in Calcite

1. Well Documented Process

2. Several Referenced Articles and Numerous

Textbooks Discuss Process

3. Values for Distribution Coefficients (D) Are Large

4. D Values Range from 70 to 1,500

5. Ideal Solution - D Values of 680 or Greater Than

4,000 Reported
 Requirements of Calculation

1. Initial Concentration of Cd (Before Coprecipritation

Reactions)

2. Amount of Calcite That Will Precipitate During Each

Step of Model (Initial and Final Calcium Concentration)

3. Value for Distribution Coefficient

4. Appropriate Equation
Doerner and Hoskins Equation
For coprecipitation in a calcium-
calcium-bearing mineral

   
log  Mei  = λ log  Cai 
 Me   Ca 
 f  f


Where
Mei = initial quantity of trace metal in solution,
Mef = final quantity of metal,
Cai = initial quantity of calcium in solution,
Caf = final quantity of calcium in solution, and
λ = distribution coefficient (D).
Doerner and Hoskins Equation

1. Typically Described in Textbooks

2. Heterogeneous System

3. Limited to Small Values of D

 Riehl Equation
C iTr C 0Cr
C 0Tr =
λ ( C iCr - C 0Cr ) + C iCr

Where

C 0Tr = Concentration of Trace Component (Cd) in

Boundary Layer,
C iTr = Initial Concentration of Trace Component
in Solution,
C iCr = Initial Concentrations of Carrier (Calcium)
in Solution, and
C 0Cr = Concentration of Carrier in Boundary Layer.
 Application of Method
1. Use PHREEQC to Estimate Mass of Calcite that
will Precipitate
2. Comparison of Concentrations from Step 2 to
Step 3 of Model
3. Estimate Concentrations of Cd in Solution
4. Cd Sorbed onto Hydrous Ferric Oxide Before
Coprecipitation Reactions
5. Solve Equation for Cd Concentrations Using
Spreadsheet Program or Calculator
6. Repeat Process for Step 4 (Evapoconcentration)
Introduction to Thermodynamic Model
1. Above method, the Bulk Kd Approach, can be applied using
output from various geochemical models (MINTEQA2, PHREEQE,
and PHREEQC) see Mahoney (1998) for more details
using Bulk Kd approach

Calculations could be performed using a spreadsheet

or even a programmable calculator if amount of
precipitated phase was known

2. After completion of work summarized in Mahoney (1998)

the USGS released version 2.0 of PHREEQC
(Parkhurst and Appelo, 1999) with a thermodynamic
approach to modeling solid solution reactions

The rest of the presentation evaluated the thermodynamic

approach used in PHREEQC (version 2)
 Thermodynamic Model

Ca 2 + + CO32 - CaCO3
(Ca 2 +)(CO32 -) = Kcc (CaCO3 )

Cd 2 + + CO32 - CdCO 3
(Cd 2 +)(CO32 -) = Kota (CdCO3 )

Where
(CdCO3 ) and (CaCO3 ) represent the activities of
the solids (no solid solution),
Kcc = solubility product constant for calcite,
Kota = solubility product constant for otavite, and
(Ca 2 +), (Cd 2 +) and (CO32-) represent activities in solution.
 Exchange Reaction

Cd 2 + + CaCO3(s) CdCO3(s) + Ca 2 +

(CdCO 3 )s (Cd 2 +)
= Kx
(CaCO3 )s (Ca 2 +)

Where
(CdCO3 )S and (CaCO3 )S = the activities of the components
in the solid solution, and
Kx = Kcc / Kota
 Distribution Coefficient
[Cd 2 + ]
XCdCO3 =D
XCaCO3 [Ca 2 + ]

Where
XCdCO3 = mole fraction of cadmium in
solid solution
XCaCO3 = mole fraction of calcium in
solid solution
[Cd 2 +] and [Ca 2 +] = molalities of cadmium and calcium
in solution, and
D = the Distribution Coefficient
Activity Coefficient in Solid

λCdCO3XCdCO3 = (CdCO )S3

λCaCO3XCaCO3 = (CaCO )S3

Where
λCaCO3and λCdCO3 represent the rational
activity coefficients in the solid
Ideal Solid Solution

λCdCO3 = 1
and

λCdCO3 D = K x
 Non Ideal Solid Solutions

1nλCdCO3 = X2CaCO3 [a0 - a1 (3XCdCO3 - XCaCO3 ) + …]

1nλCaCO3 = X2CdCO3 [a0 - a1 (3XCaCO3 - XCdCO3 ) + …]

Where
a0 and a1 are the Guggenheim Nondimensional Parameters
 Regular Solid Solution

HM = XCdCO3XCaCO3W

Where
HM = enthalpy of mixing
W = the ion interaction parameter

D= Kxexp[ - (1 - (2XCdCO3) W /(2.303RT)], and

W /(2.303RT) = a0
Additional Issues - Calculation of
a0
Mole fraction term (XCdCO3) in following equation needs
to be kept in mind when calculating a0

D = Kxexp[ - (1 - (2XCdCO3) W /(2.303RT)],

In general the value for XCdCO3 will be small because the amount of trace
metal in the initial solution will be a small fraction of amount of carrier that
will
precipitate.

112µg/L of cadmium in solution and a net removal of 40 mg/L of calcium

by calcite precipitation results in
XCdCO3 of 0.001 for the solid solution if all cadmium is removed from
solution
Additional Issues - Solubility
Products and Distribution
Coefficients
Various values for the Kota have been
presented in the literature and these values
have found their way into different databases

Users should assure that the values for Kota or

any other Ksp value for the trace element
phase produce an internally consistent value
for D and hence a0
 Comparison of Riehl Equation with PHREEQC Solid Solution
Calculations
Method Distribution a0 Cain Cafinal Cdin Cdfinal
Coefficient Moles/L Moles/L Moles/L Moles/L
Riehl 0.1 0.01 9.30E-05 2.00E-06 1.77E-07
PHREEQC 0.1 8.85 0.01 9.63E-05 2.00E-06 1.66E-07
Riehl 1 0.01 9.63E-05 2.00E-06 1.93E-08
PHREEQC 1 6.54 0.01 9.63E-05 2.00E-06 2.26E-08
Riehl 2 0.01 9.63E-05 2.00E-06 9.68E-09
PHREEQC 2 5.84 0.01 9.63E-05 2.00E-06 1.10E-08
Riehl 5 0.01 9.63E-05 2.00E-06 3.88E-09
PHREEQC 5 4.92 0.01 9.63E-05 2.00E-06 3.30E-09
Riehl 10 0.01 9.63E-05 2.00E-06 1.94E-09
PHREEQC 10 4.23 0.01 9.63E-05 2.00E-06 2.27E-09
Riehl 70 0.01 9.63E-05 2.00E-06 2.78E-10
PHREEQC 70 2.28 0.01 9.63E-05 2.00E-06 3.24E-10
Riehl 680 0.01 9.63E-05 2.00E-06 2.86E-11
PHREEQC 680 0 0.01 9.63E-05 2.00E-06 3.32E-11
Riehl 1510 0.01 9.63E-05 2.00E-06 1.29E-11
PHREEQC 1510 -0.8 0.01 9.63E-05 2.00E-06 1.49E-11
Riehl 1510 0.1 9.60E-05 2.00E-06 1.27E-12
PHREEQC 1510 -0.8 0.1 9.60E-05 2.00E-06 1.49E-12
 Comparison of Solid Solution Models
1.00E+00
Cadmium Concentration (ppm)

1.00E-03 Riehl Equation

1.00E-06
PHREEQC
Model
(Red dashes)

1.00E-09
Doerner and Hoskins Equation

1.00E-12
0.1 1 10 100 1000 10000
Distribution Coefficient (D)
 Conclusions
Coprecipitation Reactions

1. Important Process to Control Metals in Aqueous

Systems

2. Numerous Methods Available to Estimate Effect

3. Results in Significant Decreases in Concentrations

4. Failure to Consider Can Produce Concentrations

That are Unrealistically High and May Cause
Regulatory Scrutiny
 Conclusions
Bulk Methods
1. Bulk Methods Easy to Apply

2. Textbook Examples

3. Iterative Approach Requires Shifting Between

Model Concentrations and Spreadsheet

4. Distribution Coefficients Available for Many Systems

5. Riehl Equation Most Appropriate for Predicting

Concentrations for Systems with Large
Distribution Coefficients
 Conclusions
Thermodynamic Approach

1. Uses Single Program - Does Not Require Calculations

Outside of Program

2. Usually Requires Detailed Evaluation and Understanding

of System to Estimate Value for a0

3. PHREEQC (v2) Method Produces Final Concentrations

Comparable to Riehl Equation Values
 SEE ALSO

1. Mahoney, J.J., 1998, Incorporation of coprecipitation reactions in

predictive geochemical models: in Proceedings of Tailings and Mine
Waste '98, Fort Collins, Colorado, p. 689-697. A.A. Balkema pubs.

2. Mahoney, J.J., 2001, Coprecipitation reactions – verification of

computational methods in geochemical models: in Mining Impacted
Pit Lakes 2000 Workshop Proceedings: a Multimedia CD Presentation.
(Workshop held April 4–6, 2000 Reno, NV) United States
Environmental Protection Agency Office of Research and
Development. EPA/625/C-00/004. Session 4.
Example Input File for Kd = 70
TITLE Example 10.--Solid solution of otavite and calcite.
PHASES # Fix-H+ not included because of space limits
Otavite
CdCO3 = CO3-2 + Cd+2
log_k -11.31
Calcite
CaCO3 = CO3-2 + Ca+2
log_k -8.48
SOLUTION 1
-units mmol/kgw
pH 8.0
Ca 3.45
Cd 0.002
END
USE SOLUTION 1
EQUILIBRIUM_PHASES 1
CO2(g) -2.0 10
Calcite 0.0 0.0
Fix_H+ -8.0 Na(OH) 20.0
SOLID_SOLUTIONS 1
Ca(x)Cd(1-x)CO3
-comp Calcite 0.00
-comp Otavite 0.00
-Gugg_nondim 2.28
REACTION 2
Ca 0.01
END
Example Output File for Kd = 70
(portion)

-------------------------------Phase assemblage--------------------------------
Moles in assemblage
Phase SI log IAP log KT Initial Final Delta
Calcite 0.00 -8.48 -8.48 0.000e+00 0.000e+00
CO2(g) -2.00 -20.15 -18.15 1.000e+01 9.988e+00 -1.250e-02
Fix_H+ -8.00 -8.00 0.00
Na(OH) is reactant 2.000e+01 2.000e+01 -9.843e-07

--------------------------------Solid solutions--------------------------------
Solid solution Component Moles Delta moles Mole fract
Ca(x)Cd(1-x)CO3 1.00e-02
Calcite 1.00e-02 1.00e-02 1.00e+00
Otavite 2.00e-06 2.00e-06 2.00e-04
For Further Information Contact

John Mahoney, Ph.D.

Principal Geochemist
Mahoney Geochemical Consulting LLC
Lakewood, CO
jmahoney@mahoneygeochem.com
Cell - 720 224 3292