Kinetic Database

CarbFix Project no.
281348 WP5 – PHREEQC Database
4 CarbFix Report
5 PHREEQC mineral dissolution kinetics database
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17 Date: 30.11.2014
18 Authors: Julien Declercq, Eric H. Oelkers

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Geoscience Environement Toulouse | 14. Av. E. Belin 31400 Toulouse

CarbFix Project no. 281348 WP5 – PHREEQC Database
20 Table of Contents
21
22 Introduction............................................................................................................................................. 7
23 References ....................................................................................................................................... 8
24 Mineral Description ................................................................................................................................. 9
25 Albite ................................................................................................................................................... 9
26 References ..................................................................................................................................... 11
27 Almandine ......................................................................................................................................... 15
28 References ..................................................................................................................................... 16
29 Andesine / Labradorite ...................................................................................................................... 17
30 References ..................................................................................................................................... 18
31 Andradite ........................................................................................................................................... 20
32 References ..................................................................................................................................... 20
33 Anglesite ............................................................................................................................................ 22
34 References ..................................................................................................................................... 22
35 Anhydrite ........................................................................................................................................... 24
36 References ..................................................................................................................................... 24
37 Anorthite ........................................................................................................................................... 26
38 References ..................................................................................................................................... 27
39 Anthophyllite ..................................................................................................................................... 30
40 References ..................................................................................................................................... 30
41 Table and Figure ............................................................................................................................ 31
42 Apatite (fluorapatite) ........................................................................................................................ 32
43 References ..................................................................................................................................... 32
44 Table and Figure ............................................................................................................................ 33
45 Apatite (hydroxylapatite) .................................................................................................................. 34
46 Aragonite ........................................................................................................................................... 35
47 References ..................................................................................................................................... 35
48 As2S3 – Orpiment ............................................................................................................................... 37
49 References ..................................................................................................................................... 37
50 Augite ................................................................................................................................................ 39
2 51 References ..................................................................................................................................... 40
52 Barite ................................................................................................................................................. 41
53 References ..................................................................................................................................... 41

54 Bayerite ............................................................................................................................................. 43
55 References ..................................................................................................................................... 43
56 Biotite ................................................................................................................................................ 45
57 References ..................................................................................................................................... 46
58 Boehmite ........................................................................................................................................... 49
59 References ..................................................................................................................................... 49
60 Bronzite ............................................................................................................................................. 50
61 References ..................................................................................................................................... 50
62 Brucite ............................................................................................................................................... 52
63 References ..................................................................................................................................... 52
64 Bytownite .......................................................................................................................................... 54
65 References ..................................................................................................................................... 54
66 Calcite ................................................................................................................................................ 56
67 References ..................................................................................................................................... 56
68 Celestite ............................................................................................................................................. 59
69 References ..................................................................................................................................... 59
70 Chlorite .............................................................................................................................................. 61
71 References ..................................................................................................................................... 61
72 Christobalite ...................................................................................................................................... 65
73 Chrysotile........................................................................................................................................... 65
74 Cordierite........................................................................................................................................... 66
75 References ..................................................................................................................................... 66
76 Corundum .......................................................................................................................................... 68
77 References ..................................................................................................................................... 68
78 Dawsonite.......................................................................................................................................... 70
79 References ..................................................................................................................................... 71
80 Diaspore ............................................................................................................................................ 73
81 References: .................................................................................................................................... 74
82 Diopside ............................................................................................................................................. 75
83 References ..................................................................................................................................... 76
84 Dolomite ............................................................................................................................................ 78
3 85 References ..................................................................................................................................... 79
86 Enstatite ............................................................................................................................................ 82
87 References ..................................................................................................................................... 82

88 Epidote .............................................................................................................................................. 84
89 References ..................................................................................................................................... 85
90 Fayalite and other non-forsteric olivines .......................................................................................... 87
91 References ..................................................................................................................................... 88
92 Fluorite and other divalent metal fluorides. ..................................................................................... 92
93 References ..................................................................................................................................... 93
94 Forsterite ........................................................................................................................................... 95
95 References ..................................................................................................................................... 96
96 Glauconite ....................................................................................................................................... 101
97 References ................................................................................................................................... 101
98 Glaucophane ................................................................................................................................... 103
99 References ................................................................................................................................... 103
100 Gibbsite ........................................................................................................................................... 105
101 References ................................................................................................................................... 106
102 Goethite........................................................................................................................................... 107
103 References ................................................................................................................................... 107
104 Gypsum............................................................................................................................................ 109
105 References ................................................................................................................................... 109
106 Hematite .......................................................................................................................................... 111
107 References ................................................................................................................................... 112
108 Grossular ......................................................................................................................................... 114
109 References ................................................................................................................................... 114
110 Halite ............................................................................................................................................... 116
111 References ................................................................................................................................... 116
112 Hornblende...................................................................................................................................... 118
113 References ................................................................................................................................... 119
114 Illite .................................................................................................................................................. 121
115 References ................................................................................................................................... 122
116 Ilmenite ........................................................................................................................................... 124
117 References ................................................................................................................................... 124
118 Quartz .............................................................................................................................................. 126
4119 References ................................................................................................................................... 126
120 Jadeite ............................................................................................................................................. 129
121 References ................................................................................................................................... 129

122 Kaolinite........................................................................................................................................... 131

123 References ................................................................................................................................... 132
124 References ................................................................................................................................... 141
125 Magnetite ........................................................................................................................................ 145
126 References ................................................................................................................................... 145
127 References ................................................................................................................................... 152
128 Oligoclase ........................................................................................................................................ 153
129 Prehnite ........................................................................................................................................... 160
130 Pyrophyllite ..................................................................................................................................... 162
131 Rhodochrosite ................................................................................................................................. 164
132 References ................................................................................................................................... 165
133 Serpentine minerals ........................................................................................................................ 166
134 References ................................................................................................................................... 166
135 Siderite ............................................................................................................................................ 168
136 References ................................................................................................................................... 169
137 Smectite - Montmorillonite ............................................................................................................. 171
138 References ................................................................................................................................... 172
139 Sphalerite ........................................................................................................................................ 174
140 References ................................................................................................................................... 174
141 Spodumene ..................................................................................................................................... 176
142 References ................................................................................................................................... 176
143 Staurolite ......................................................................................................................................... 178
144 References ................................................................................................................................... 178
145 Struvite ............................................................................................................................................ 180
146 References ................................................................................................................................... 180
147 Talc .................................................................................................................................................. 181
148 References ................................................................................................................................... 181
149 Tourmaline ...................................................................................................................................... 183
150 References ................................................................................................................................... 183
151 Tremolite ......................................................................................................................................... 185
152 References ................................................................................................................................... 185
5153 Uraninite .......................................................................................................................................... 187
154 References ................................................................................................................................... 187
155 Variscite ........................................................................................................................................... 189

156 References ................................................................................................................................... 189

157 Witherite ......................................................................................................................................... 191
158 References ................................................................................................................................... 191
159 Wollastonite .................................................................................................................................... 193
160 References ................................................................................................................................... 194
161 Zoisite .............................................................................................................................................. 196
162 References ................................................................................................................................... 197
163
164

165 Prediction is hard - Especially about the Future (Attributed to Yogi Berra)
166
167 THIS IS A PRELIMINARY VERSION OF THIS DATABASE; PROOFREADING AND CORRECTIONS BY

168 THE AUTHORS IS STILL BEING UNDERTAKEN. E.H. OELKERS, November 2014
169 Introduction
170
171 The kinetic database is established from a thorough literature review of the existing
172 data on precipitation and dissolution rates. These datasets are assessed and the values for
173 the reaction rate constant (A), the activation energy (Ea), the exponent on the activity of
174 element i (ni) for H, Mg, Si, Na and K, selected when applicable and introduced into the
175 database file. This file is organized by mineral, glass phase and the pH spaces where the
176 experimental measurements were collected, as can be seen in Table 1 where an excerpt
177 from the current database is shown. The reference from which the data was collected is
178 specified in the last column.
179 After the initial development and definition of the minerals and glass phases the
180 database is planned to become a collaborative effort, with each team able to input their
181 results into the database. Therefore it has been organized in an excel spreadsheet to
182 increase the accessibility and modifiability of its content.
183 The software unit will be a stand-alone program coupled with PHREEQC, using the
184 data from the geochemical software and the kinetic database to produce dissolution and
185 precipitation rates. Currently under development using it allows the user to determine
186 dissolution or precipitation rates of the phases defined in the databases. The input from the
187 user is a two staged process where first the conditions and phase dissolved or precipitated
188 are defined in PHREEQC, then the kinetic software is accessed and generates the dissolution
189 or precipitation rates of the specified phase in the previously defined conditions.
190

191 References
192
193 Brantley, S.L., Kubicki, J.D. and White, A.F (2008) Kinetics of Water-Rock interaction. Springer, New
194 York.
195 Marini, L. (2007) Geological Sequestration of Carbon Dioxide: Thermodynamics, Kinetics and Reaction
196 Path Modeling. Elsevier, Amsterdam.
197 Palandri, J.L. and Kharaka, Y.K. (2004) A compilation of rate parameters of water-mineral interaction
198 kinetics for application for geochemical modeling. U.S.G.S., Open File Report 2004-1068.
199 Parkhurst D.L. and Appelo C.A.J. (1999) User’s guide to PHREEQC (Version 2) — A computer program
200 for speciation, batch-reaction, one-dimensional transport, and inverse geochemical
201 calculations, U.S.G.S. Wat. Res. Inv. Report, 99-4259.
202

203 Mineral Description

204
205 Albite
206
207 Feldspars are amongst the most studied silicate minerals from the point of view of
208 mineral dissolution. Dissolution rates of albite (NaAlSi3O8) from 25 °C and up to 225 °C, and
209 various pH have been published by Lagache (1965), Holdren and Berner (1979), Chou and
210 Wollast (1984, 1985), Holdren and Spayer (1987), Knauss and Wolery (1987), Hellmann et al.
211 (1990), Burch et al. (1991, 1993), Casey et al. (1991), Rose (1991) Hellmann (1994, 1995),
212 Chen and Brantley (1997) and Hellmann and Tisserand (2006). The rates are presented for
213 the different temperatures as a function of pH in Figure A1. Oelkers et al. (1994) reported
214 steady state dissolution rates of albite as a function of chemical affinity and thus are not
215 included here. The rates gathered by Lagache at 200 °C were removed from the dataset
216 because stoichiometric metal release was not observed in this experiment.
217 Based on the theoretical framework laid by Oelkers (2001) for the dissolution of
218 multi-oxides minerals steady-state albite dissolution rates were fitted to:
1/ 8
 a3  
219 r  AA . exp  E A / RT   H  (A-1)
 a 3 
 Al 
220 where r signifies the albite steady state dissolution rate, AA refers to a pre-exponential
221 factor equal to 2.38x10-4 mol/cm²/sec1, EA designates an activation energy equal to 66.5
222 kJ/mol, R represents the gas constant, and T denotes absolute temperature. AA and EA
223 were determined from an Arrhenius plot of the data obtained at pH 4 by Chen and Brantley
224 (1997), Chou and Wollast (1985), and Hellmann (1994). The degree to which this equation
225 describes the dissolution rates reported in the literature can be assessed in Figure A1. Rates
226 calculated using Equation A-1 described 75 of 95 reported rates within 0.8 log units with an
227 average uncertainty of 0.2 log units.
228
9

229
10

230 References
231
232 Burch, T.E., Nagy, K.L., Lasaga A.C. (1991) Dependence of albite dissolution and precipitation kinetics
233 at 80ºC. Geol. Soc. Am. Abstr. Prog., 23, A260.
234 Burch, T.E., Nagy, K.L., Lasaga A.C. (1993) Free energy dependence of albite dissolution kinetics at
235 80ºC and pH 8.8. Chem. Geol., 105, 137-162.
236 Casey, W.H., Westrich, H.R. and Holdren, G.R. (1991) Dissolution of plagioclase at pH = 2 and 3. Amer.
237 Mineral. 76, 211-217.
238 Chou, L. and Wollast, R. (1984) Study of the weathering of albite at 25 C and pressure with a fluidized
239 bed reactor. Geochim. Cosmochim. Acta, 48, 2205-2217.
240 Chou, L. and Wollast, R. (1985) Steady-state kinetics and dissolution mechanism of albite. Am. J. Sci.,
241 285, 963-993.
242 Chen, Y. and Brantley, S.L. (1997) Temperature and pH dependence of albite dissolution rate at acidic
243 pH. Chem. Geol. 135, 275-290.
244 Helgeson, H.C., Murphy, W.M. and Aagaard, P. (1984) Thermodynamic and kinetic constraints on
245 reaction rates among minerals and aqueous solutions. II. Rate constants, effective surface
246 area, and the hydrolysis of feldspar. Geochim. Cosmochim. Acta 48, 2405-2432.
247 Hellmann, R., Eggleston, C.M., Hochella, Jr., M.F., Crerar, D.A. (1990) The formation of leach layers on
248 albite surfaces during dissolution under hydrothermal conditions. Geochim. Cosmochim.
249 Acta, 54, 1267-1281.
250 Hellmann, R. (1994) The albite-water system: Part I. The kinetics of dissolution as a function of pH at
251 100, 200 and 300ºC. Geochim. Cosmochim. Acta, 59, 595-611
252 Hellmann, R. (1995) The albite-water system: Part II. The time-evolution of the stoichiometry of
253 dissolution as a function of pH at 100, 200 and 300ºC. Geochim. Cosmochim. Acta, 59, 1669-
254 1697.
255 Hellmann, R., Tisserand, D. (2006) Dissolution kinetics as a function of the Gibbs free energy of
256 reaction: An experimental study based on albite feldspar. Geochim. Cosmochim. Acta, 70,
257 364-383.
258 Holdren, G.R. and Berner, R.A. (1979) Mechanism of feldspar weathering – I. Experimental studies.
259 Geochim. Cosmochim. Acta 43, 1161-1171.
260 Holdren, G.R. and Speyer, P.M. (1987) Reaction rate-surface area relationships during the early
261 stages of weathering. II. Data on eight additional feldspars. Geochim. Cosmochim. Acta 51,
262 2311-2318.
11
263 Lagache, M. (1965) Contribution à l’étude de l’altération des feldspaths, dans l’eau, entre 100 et 200
264 ºC, sous diverses pressions de CO2, et application à la synthèse des minéraux argileux. Bull.
265 Soc. Franç. Minér. Crist., 88, 223-253.

266 Oelkers, E.H., Schott, J. and Devidal, J.-L. (1994) The effect of aluminum, pH, and chemical affinity on
267 the rates of aluminosilicate dissolution reaction. Geochim. Cosmochim. Acta 58, 2011-2024.
268 Rose, N.M. (1991) Dissolution rates of prehnite, epidote and albite. Geochim. Cosmochim. Acta 55,
269 3273-3286.
270 Stillings, L.L., Drever, J.I., Brantley, S.L., Sun, Y. and Oxburgh, R. (1996) Rates of feldspar dissolution at
271 pH 3-7 with 0-8 mM oxalic acid. Chem. Geol. 132, 79-89.
272 Wollast, R. and Chou, L. (1985) Kinetic study of the dissolution of albite with a continuous flow-
273 through fluidized bed reactor. In The Chemistry of Weathering (Ed. J. I. Drever), 75-96. D.
274 Reidel Publishing Company, New York.
12

275 Table A1: Summary of experimentally measured albite steady-state dissolution rates
276 reported in the literature.
Mineral T, °C pH range Reference
Cleavelandite 80 3, 8.8 Burch et al. (1991)
Cleavelandite 80 8.8 Burch et al. (1993)
Albite 25 2 Casey (1991)
Cleavelandite 25 1.2–7.11 Chou and Wollast (1984)
Cleavelandite 25 1-12.5 Chou and Wollast (1985)
Albite An2 5-90 1, 4.5 Chen and Brantley (1997)
Albite 225 0.8-8 Hellmann et al. (1990)
Albite 100-300 2-10 Hellmann (1994)
Albite 150 8.8 Hellmann and Tisserand (2006)
Albite, Ab 99.07 n.c. n.c. Holdren and Berner (1978)
Cleavelandite n.c. 3 Holdren and Speyer (1987)
Albite, Ab 99.07 25, 70 1.39-11.75 Knauss and Wolery (1986)
Albite 200 7,27 Lagache (1965), recalculated by Helgeson

(1984)
Albite 25 1.4 Rose (1991)
Albite An2 25 3.32 Stillings et al. (1996)
Albite 22 Welch and Ullman (1996)
Albite 25 1-12 Wollast and Chou (1985)
277
278
13

279 Figure A1: Summary of experimentally measured albite steady-state dissolution rates
280 reported in the literature as a function of pH. The results of the model are plotted as the
281 various dashed lines.
-8
25 C Casey et al. (1991)
-9 5 ºC Chen and Brantley (1997)
50 ºC Chen and Brantley (1997)
-10 90 ºC Chen and Brantley (1997)
25 ºC Chou and Wollast (1984)
-11
log r+ (mol/cm2/s)
25 ºC Chou and Wollast (1985)

-12 25 ºC Knauss and Wolery (1986)
70 ºC Knauss and Wolery (1986)
-13
200 ºC Lagache (1965)
-14 100 ºC Hellmann (1994)
200 ºC Hellmann (1994)
-15 300 ºC Hellmann (1994)
25 C Holdren and Speyer (1987)
-16
25 C Rose (1991)
-17 25 C Stillings et al. (1996)
25 ºC Model
-18 100 ºC Model
0 2 4 6 8 10 12 200 ºC Model
pH
282
283
14

284 Almandine
285
286 The dissolution rates of the iron alumina garnet almandine (Fe3Al2Si3O12) was
287 reported by Nickel (1973) and Schott and Petit (1987) at 25 ºC from pH 0.2 to 10.5. Sverdrup
288 (1990) alludes to the existence of additional data at 8 ºC but does not list these. In the
289 absence of additional data to improve existing data fits, these we have adopted the
290 empirical pH power function fit of Palandri and Kharaka (2004) in accord with:
291 ( )
292 ( )
293 ( )
294
295 where rH+, rH2O and rOH- signifies the almandine forward dissolution rate in acidic, neutral
296 and basic solutions and rtt the total dissolution rate, AA, AB and AC refer to pre-exponential
297 factors equal to 2.19x107, 3.02x105 and 8.13x10-12 mol/cm²/s respectively, EA, EB, EC
298 designates an activation energy equal to 94.4, 103.8 and 37.8 kJ/mol, R represents the gas
299 constant, and T denotes absolute temperature. As was the case for andradite in the absence
300 of additional and more extensive data the Palandri and Kharaka fit has been adopted in this
301 study. It should be noted that these activation energies are based on the fit of rates obtained
302 at 8 and 25 ºC, and the rate data at 8 ºC were never directly reported. As the rate data
303 reported by Sverdrup (1990) for andradite and almandine are identical the activation
304 energies are the same. As such the degree to which these activation energies provide
305 accurate rate estimates at substantially higher temperatures is questionable. The degree to
306 which this equation describes the dissolution rates reported in the literature can be assessed
307 in Figure Alm1. Rates calculated using Equation Alm-1 described 8 of 9 reported rates within
308 0.8 log units.
309
15

310 References
311 Nickel, E. (1973) Experimental dissolution of light and heavy minerals in comparison with weathering
312 and intrastratal solution. Contrib. in Sedimentology 1, 1-68.
314 kinetics for application in geochemical modeling. U.S. Geological Survey, Open File Report
315 2004-1068.
316 Schott, J. and Petit, J.C. (1987) New evidence for the mechanism of dissolution of silicate minerals. In:
317 Aquatic Surface Chemistry : Chemical Processes at the Particle-Water Interface. John Wiley
318 and Sons, New York, 293-315.
319 Sverdrup H.U. (1990) The Kinetics of Base Cation Release due to Chemical Weathering. Lund: Lund
320 University Press, 246pp.
321 Table Alm1: Summary of experimentally measured almandine steady-state dissolution rates
Almandine 25 0.2-11 Nickel (1973)
Almandine 25 3-7 Schott and Petit (1987)
323
324 Figure Alm1: Summary of experimentally measured almandine steady-state dissolution rates
325 reported in the literature as a function of pH. The dotted line represents the results of the
326 model.
327
-8
-10
log r+ (mol/cm2/s)
-12
Nickel (1973)
-14
Schott and Petit (1987)
-16
Model (Palandri and
Kharaka, 2004)
-18
16
-20
0 2 4 6 8 10 12
pH
328
329 Andesine / Labradorite

330
331 Andesine (Na0.7Ca0.Al1.3Si2.7O8) and labradorite are two feldspars of the
332 plagioclase solid solution, they are defined as having an anorthite percentage ( )
333 between 30 and 50% for andesine and 50 and 70% for labradorite. Dissolution rates of
334 plagioclase at 25 °C and pH 3 have been published first by Tsuzuki and Suzuki in 1980 who
335 investigated the dissolution kinetics at 230 to 245 C in acidic solutions. Holdren and Spayer
336 followed in 1987 at 25 ºC and pH 3, then Casey et al. (1991) investigated the dissolution
337 kinetics of andesine at pH 2. They were followed by a kinetic study by Oxburgh et al. who
338 dissolved andesine between pH 3 and 7, then Stillings and Brantley (1995) dissolved
339 labradorite at pH 3 ± 0.1. In 1996 Stillings et al. studied the dissolution kinetics of andesine
340 between pH 3 and 7.5 and finally Taylor et al. in 2000 dissolved labradorite at pH 3.1. The
341 rates are presented for the different temperatures as a function of pH in Figure And1.
342 Based on the theoretical framework laid by Oelkers (2001) for the dissolution of
343 multi-oxides minerals steady-state andesine dissolution rates were fitted to:
1/ 8
 a H3  
344 r  AA .(exp  E A / RT    (And-1)
 a 3 
 Al 
345 where r signifies the andesine/labradorite steady-state dissolution rate, AA refers to a pre-
346 exponential factor equal to 2.9x10-5 mol/cm²/sec2, EA designates an activation energy equal
347 to 56 kJ/mol, R represents the gas constant, and T denotes absolute temperature. EA was
348 assumed to be of similar values as the other feldspar and therefore AA was recalculated to fit
349 the data. The degree to which this equation describes the dissolution rates reported in the
350 literature can be assessed in Figure And1. Rates calculated using Equation And-1 described
351 42 of 46 reported rates within 0.8 log units.
352
17

353 References
354
356 Mineral. 76, 211-217.
359 2311-2318.
360 Oxburgh, R. Drever, J.L. and Sun, Y.T. (1994) Mechanism of plagioclase dissolution in acid solution at
361 25 ºC. Geochim. Cosmochim. Acta 58, 661-669.
362 Siegel D.I. and Pfannkuch H.O. (1984) Silicate mineral dissolution at pH 4 and near standard
363 temperatures and pressures. Geochim. Cosmochim. Acta, 48, 197-201.
364 Stillings, L.L. and Brantley, S.L. (1995) Feldspar dissolution at 25 ºC and pH 3: Reaction stoichiometry
365 and the effect of cations. Geochim. Cosmochim. Acta 59, 1483-1496.
366 Stillings, L.L., Drever, J.L., Brantley, S.L., Sun, Y. and Oxburgh, R. (1996) Rates of feldspar dissolution at
367 pH 3-7 with 0-8 M oxalic acid. Chem. Geol. 132, 79-89.
368 Swoboda-Colberg, N.G. and Drever, J.I. (1993) Mineral dissolution rates in plot-scale field and
369 laboratory experiments. Chem. Geol. 105, 51-69.
370 Taylor A.S., Blum J.D., Lasaga A.C. and MacInnis I.N. (2000a) Kinetics of dissolution and Sr release
371 during biotite and phlogopite weathering. Geochim. Cosmochim. Acta 64, 1191-1208.
372 Tsuzuki Y. and Suzuki K. (1980) Experimental study of the alteration process of labradorite in acid
373 hydrothermal solutions. Geochim. Cosmochim. Acta 44, 673-683.
374 Welch, S.A. and Ullman, W.J. (1996) Feldspar dissolution in acidic and organic solutions.
375 Compositional and pH dependence of dissolution rate. Geochim. Cosmochim. Acta 60, 2939-
376 2948
377
18

378 Table And1: Summary of experimentally measured andesine steady-state dissolution rates
Andesine 25 3, 8.8 Casey et al. (1991)
Andesine 25 3 Holdren and Speyer (1987)
Andesine, An46 25 3.1 – 7.3 Oxburgh et al. (1994)
Labradorite 25 4 Siegel and Pfannkuch (1984)
Labradorite 25 3 – 3.12 Stillings and Brantley (1995)
Andesine, An43, An47 25 2.96 – 7.65 Stillings et al. (1996)
Andesine, An30 25 Swoboda-Colberg and Drever (1993)
Labradorite 25 3.08 Taylor et al. (2000)
Andesine 230 - 245 0.4 – 1.7 Tzuzuki and Suzuki (1980)
Andesine, An49 22 3.1 – 9 Welch and Ullman (1996)
380
381 Figure And1: Summary of experimentally measured andesine steady-state dissolution rates
-13 Busenberg and Clemency

(1976)
25 ºC Caroll and Knauss (2001)
Casey et al. (1991)

-14
log r+ (mol/cm2/s)
Oxburgh et al. (1994)
Holdren and Spayer (1987)

-15
Siegel and Pfannkuch (1984)
Stillings and Brantley (1995)

-16
Stillings et al. (1996)
Taylor et al. (2000)

-17
19 0 2 4 6 8 10 12 Model
Welch and Ullman (1993)

pH
384
385

386 Andradite
387
388 The iron calcium-iron garnet andradite (Ca3Fe2(SiO4)3) dissolution was studied by
389 Sverdrup (1990) at 25 ºC from pH 4 to 4.6. The data was fitted by Palandri and Kharaka
390 (2004) to the following equation:
391 ( )
392 ( )
393
394 where rH+ and rH2O signifies the almandine steady-state dissolution rate in acidic, neutral
395 and basic solutions and rtt the total dissolution rate, AA and AB refer to pre-exponential
396 factors equal to 2.19x107and 3.02x105 mol/cm²/s respectively, EA and EB designates an
397 activation energy equal to 94.4 and 103.8 kJ/mol, R represents the gas constant, and T
398 denotes absolute temperature. In the absence of additional and more extensive data the
399 Palandri and Kharaka fit has been adopted in this study. It should be noted that the
400 activation energies of this rate equation are based on the fit of rates obtained at 8 and 25 ºC,
401 and the rate data at 8 ºC were never directly reported. As such the degree to which these
402 activation energies provide accurate rate estimates at substantially higher temperatures is
403 questionable. Note that as the rate data reported by Sverdrup (1990) for andradite and
404 almandine are identical the activation energies are the same. The degree to which this
405 equation describes the dissolution rates reported in the literature can be assessed in Figure
406 Adr1. Rates calculated using Equation Adr-1 described 2 of 2 reported rates within 0.8 log
407 units.
408
409 References
410
20
413 2004-1068.

416
417
418 Table Adr1: Summary of experimentally measured andradite steady-state dissolution rates
Andradite 25 4, 4.6 Sverdrup (1990)
420
421 Figure Adr1: Summary of experimentally measured andradite steady-state dissolution rates
423 model.
-8
-9
-10
log r+ (mol/cm2/s)
-11
-12 Sverdrup (1990)
-13 Model (Palandri and

Kharaka, 2004)
-14
-15
-16
0 2 4 6 8
pH
424
21

425 Anglesite
426
427 The lead sulfate anglesite (PbSO4) was studied by Dove and Czank (1995) at
428 temperatures ranging from 25 to 61 ºC and pH ranging from 1.96 to 12.05. Anglesite
429 dissolution kinetics were also quantified by De Giudici et al. (2005) at 25 ºC and pH 1.2 and
430 2.87. In the absence of sufficient data to characterize its dissolution mechanism we have
431 adopted the fit of Palandri and Kharaka (2004) given by:
432 ( )
433 ( )
434
435 where rH+ and rH2O signifies the anglesite steady-state dissolution rate in acidic, neutral and
436 basic solutions and r+ the total dissolution rate, AA and AB refer to pre-exponential factors
437 equal to 3.95x10-5 and 4.55x10-6 mol/cm²/s respectively, EA designates an activation energy
438 equal to 31.3 kJ/mol, R represents the gas constant, and T denotes absolute temperature.
439 The degree to which this equation describes the dissolution rates reported in the literature
440 can be assessed in Figure Ang1. Rates calculated using Equation Ang-1 describes all reported
441 rates within 0.8 log units with an average uncertainty of 0.2 log units.
442
443 References
444
445 Dove P. M. and Czank C. A. (1995) Crystal chemical controls on the dissolution kinetics of the
446 isostructural sulfates; celestite, anglesite and barite. Geochim. Cosmochim. Acta 59, 1907-
447 1915.
448 De Giudici, G., Rossi, A., Fanfani, L. and Lattanzi, P. (2005) Mechanisms of galena dissolution in
449 oxygen-saturated solutions: Evaluation of pH effect o apparent activation energies and
450 mineral-water interface. Geochim. Cosmochim. Acta 69, 2321-2331.
22
453 2004-1068.
454

455 Table Ang1: Summary of experimentally measured anglesite steady-state dissolution rates
Anglesite 25 1.2 – 2.87 De Giudici et al. (2005)
Anglesite 25 - 61 1.96 – 12.0.5 Dove and Czank (1995)
457
458 Figure Ang1: Summary of experimentally measured anglesite steady-state dissolution rates
-9,00
-9,50
De Giudici et al. (2005), 25
log r+ (mol/cm2/s)
C
Dove and Czank (1995), 25
C
-10,00
Dove and Czank (1995), 50
C
Model 25 C (Palandri and
-10,50 Kharaka, 2004)
Kharaka, 2004)
-11,00
1 3 5 7 9 11
pH
461
23

462 Anhydrite
463
464 There is relatively little dissolution rate data available for the anhydrous calcium
465 sulphate anhydrite (CaSO4). Barton and Wilde (1971) reported rates at 25 ºC and pH 6, Dove
466 and Czank (1995) reported rates at 50 ºC and pH 5.7 and Jeschke and Dreybrodt (2001, 2002)
467 reported rates at 10 ºC and pH 6. The rates are presented for the different temperatures as a
468 function of pH in Figure Anh1. Because rates have been reported for one pH at each
469 temperature these data were fit to the pH independent Arrhenius equation:
470 ( )
471 where r+ signifies the anhydrite steady-state dissolution rate, AA refers to a pre-exponential
472 factor equal to 24.4 mol/cm²/s, EA designates an activation energy equal to 52.0 kJ/mol, R
473 represents the gas constant, and T denotes absolute temperature. The EA and AA were
474 recalculated with an Arrhenius fit of the existing data at pH 6±0.3. The degree to which this
476 Anh1. Rates calculated using Equation Anh-1 described 4 of 4 reported rates within 0.8 log
477 units with an average uncertainty of 0.2 log units.
478
479 References
480
481 Barton A. F. M. and Wilde N. M. (1971) Dissolution rates of polycrystalline samples of gypsum and
482 orthorhombic forms of calcium sulphate by the rotating disc method. Transactions of the
483 Faraday Society 67, 3590-3597.
486 1915.
487 Jeschke, A.A., Vosbeck, K., and Dreybrodt, W. (2001) Surface controlled dissolution rates of gypsum
488 in aqueous solutions exhibit nonlinear dissolution kinetics. Geochim. Cosmochim. Acta 65,
489 27– 34.
490
24 Jeschke, A.A. and Dreybrodt, W. (2002)Pitfalls in the determination of empirical dissolution rate
491 equations of minerals from experimental data and a way out: an iterative procedure to find
492 valid rate equations, applied to Ca-carbonates and –sulphates.

495 2004-1068.
496 Table Anh1: Summary of experimentally measured anhydrite steady-state dissolution rates
Anhydrite 25 6 Barton and Wilde (1971)
Anhydrite 50 5.7 Dove and Czank (1995)
Anhydrite 10 6 Jeschke and Dreybrodt (2002)
498
499 Figure Ang1: Summary of experimentally measured anhydrite steady-state dissolution rates
502
-6
Barton and Wilde
-6,5 (1971), 25 C
log r+ (mol/cm2/s)
-7 Model, 25 C
-7,5
Dove and Czank
-8
(1995), 50 C
-8,5
Jeschke and
-9 Dreybrodt (2002), 10
C
0 2 4 6 8 10 12
pH Model, 10 C
503
25

504 Anorthite
505
506 The pure calcium endmember of the plagioclase feldspar solid solution, anorthite,
507 was studied at 25 ºC and pH of 2 and 5.6 and Fleer in 1982, then Holdren and Spayer as part
508 of their series on feldspar measured the dissolution rate of anorthite at pH 3. Casey et al.
509 (1991) measured the dissolution of anorthite at pH 2 and following suite Amrhein and Suarez
510 studied the anorthite dissolution kinetics at pH ranging from 5 to 8. Oelkers and Schott
511 (1995) investigated the feldspar dissolution mechanism by measuring the dissolution rate of
512 anorthite at temperatures ranging from 45 to 95 and pH range of 2.4 to 3.2. Finally Hodson
513 et al. (2003) measured the dissolution of Anorthite at 25 C and pH 2.6. The rates are
514 presented for the different temperatures as a function of pH in Figure Ano1.
515 Those results were fitted to the dissolution equation of feldspar determined by #no#
516 Oelkers and Schott (1995):
1/ 3
 a H3  
517 r  AA .(1  exp  E A / 3RT )   (Ano-1)
 a 3 
 Al 
518 where r signifies the andesine/labradorite steady-state dissolution rate, AA refers to

519 a pre-exponential factor equal to 2.77x10-13 mol/cm²/sec, EA designates an activation energy
520 equal to 18 kJ/mol, R represents the gas constant, and T denotes absolute temperature. EA
521 was assumed to be of similar values as the other feldspar and therefore AA was recalculated
522 to fit the data. The degree to which this equation describes the dissolution rates reported in
523 the literature can be assessed in Figure Ano1. Rates calculated using Equation Ano-1
524 described 39 of 46 reported rates at 25 C within 0.8 log units with an average uncertainty of
525 0.2 log units. The data reported by Fleer (1982) is on par with values measured at 95 ºC and
526 thus were excluded from the model.
527
26

528 References
529
530 Amrhein, C. and Suarez, D.L. (1992) Some factors affecting the dissolution kinetics of anorthite at 25
531 C. Geochim. Cosmochim. Acta 56, 1815-1826.
532 Bailey, A. (1974) Effect of temperature on the reaction of silicates with aqueous solutions in the low
533 temperature range. First International Symposium on Water-Rock interactions. 1976, Praha,
534 375-380.
535 Berg, A. and Banwart, S.A. (2000) Carbon dioxide mediated dissolution of Ca-feldspar: Implications
536 for silicate weathering. Chem. Geol. 163, 25-42.
538 Mineral. 76, 211-217.
539 Fleer, V.N. (1982) The dissolution kinetics of anorthite (CaAl2Si2O8) and synthetic strontium feldspar
540 (Sr) in aqueous solutions at temperature below 100 ºC: application to the geological disposal
541 of radioactive wastes. Ph.D. thesis, Pennsylvania State University.
542 Hodson, M.E. (2003) The influence of Fe-rich coatings on the dissolution of anorthite at pH 2.6.
546 2311-2318.
547 Lasaga A. C. (1998) Kinetic Theory In the Earth Sciences. Princeton University Press, Princeton.
548 Oelkers, H.E. and Schott, J. (1995) Experimental study of anorthite dissolution and the relative
549 mechanism of feldspar hydrolysis. Geochim. Cosmochim. Acta 59, 5039-5053.
552 Stillings, L.L., Drever, J.L., Brantley, S.L., Sun, Y. and Oxburgh, R. (1996) Rates of feldspar dissolution at
553 pH 3-7 with 0-8 M oxalic acid. Chem. Geol. 132, 79-89.
554 Taylor A.S., Blum J.D., Lasaga A.C. and MacInnis I.N. (2000) Kinetics of dissolution and Sr. release
556
27

557 Table Ano1: Summary of experimentally measured anorthite steady-state dissolution rates
Anorthite, An 93 25 4-8 Amrhein and Suarez (1992)
Anorthite 25 2-9 Bailey (1974)
Anorthite 25 2-9 Berg and Banwart (2000)
Anorthite 25 3, 8.8 Casey et al. (1991)
Anorthite 25 2, 5.5 Fleer (1982)
Anorthite 25 2.6 Hodson et al. (2003)
Anorthite 25 3 Holdren and Speyer (1987)
Microcline 25 5 Lasaga (1998)
Anorthite, An96 45, 95 2.4-3.2 Oelkers and Schott (1995)
Anorthite 25 3 – 3.12 Stillings and Brantley (1995)
Anorthite 25 2.96 – 7.65 Stillings et al. (1996)
Anorthite 25 3.08 Taylor et al. (2000)
559
560
28

561 Figure Ano1: Summary of experimentally measured anorthite steady-state dissolution rates
-8 Amrhein and Suarez (1992)

-9
Bailey (1974) Berg and
-10 Banwart (2000)
Casey et al. (1991)
log r+ (mol/cm2/s)
-11
-12 Fleer (1982)
-13 Hodson (2003)

-14
Holdren and Speyer (1987)
-15
Lasaga (1998)
-16
-17 Oelkers and Schott (1995),
45 C
-18 Oelkers and Schott (1995),
0 2 4 6 8 10 12 95 C
Model
pH
564
565
29

566 Anthophyllite
567
568 Dissolution rates of the amphibole anthophyllite (Mg7Si8O22(OH)2) from 25 to 90 °C

569 and pH ranging from 1 to 3.7 have been reported by Chen and Brantley (1998) and at 22 °C
570 with pH ranging from 2 to 9 by Mast and Drever (1987). The values reported by Mast and
571 Drever (1987) are significantly higher than corresponding values presented by Chen and
572 Brantley (1998). As discussed by Chen and Brantley, the difference in rates can be attributed
573 to a non-stoichiometric dissolution. The rate data from Mast and Drever (1987) was,
574 therefore, not included in the fit. The rates are presented as a function of pH in Figure An1.
575 Following the theoretical framework of Oelkers (2001) for the dissolution of multi-
576 oxides minerals steady-state anthophyllite dissolution rates were fit to:
577 ( )( ) (An-1)
578 where r+ signifies the anthophyllite steady state dissolution rate, AA refers to a pre-
579 exponential factor equal to 7.54x10-8 mol/cm²/s, EA designates an activation energy equal to
580 55.8 kJ/mol, R represents the gas constant, T denotes absolute temperature and n signifies
581 a stoichiometric coefficient equal to 0.125. AA and EA were determined from an Arrhenius
582 plot of the data obtained at pH 2 by Chen and Brentley (1998). n was obtained from a fit of
583 the reported anthophyllite rate data and those of tremolite; tremolite has an almost
584 identical structure to anthophyllite with 2 of its Mg replaced by Ca. As such, it is anticipated
585 that these two minerals would have similar dissolution mechanisms. The degree to which
586 this equation describes the dissolution rates reported in the literature can be assessed in
587 Figure An1. Rates calculated using Equation An-1 described 8 of 8 reported rates within 0.8
588 log units.
589
590 References
591
592
30 Chen, Y. and Brantley, S.L. (1998) Diopside and anthophyllite dissolution at 25ºC and 90ºC and acid
593 pH. Chem. Geol. 147, 233-248.
594 Mast, M.A. and Drever, J.I (1987) The effect of oxalate on the dissolution rates of oligoclase and
595 tremolite. Geochim. Cosmochim. Acta 51, 2559-2568.

596 Table and Figure

597
598 Table An1: Summary of experimentally measured anthophyllite steady-state dissolution

599 rates reported in the literature.
Mineral T, °C pH Reference
range
Anthophyllite 25-90 1-3.7 Chen and Brantley (1998)
Anthophyllite 22 2-9 Mast and Drever (1987)
600
601 Figure An1: Summary of experimentally measured anthophyllite steady-state dissolution

602 rates reported in the literature as a function of pH. The results of the model are plotted as
603 the various dashed lines.
-14
-15
log r+ (mol/cm2/s)
25 ºC Chen and Brantley

(1998)
-16 90 ºC Chen and Brantley
(1998)
22 ºC Mast and Drever
-17 (1987)
25 ºC Model
-18
90 ºC Model
-19
0 2 4 6 8 10
pH
604
605
31

606 Apatite (fluorapatite)

607
608 The phosphate mineral apatite has been studied at 25 C in a limited set of
609 studies. Three studies were reported in Brantley et al. (2008), Guidry and Mackenzy (2003)
610 looked at the dissolution of apatite at pH ranging from 2 to 8.5, Valsami-Jones et al. (1998)
611 studied the dissolution kinetics of apatite between pH 4.2 and 7 and finally Welch and al.
612 (2002) between pH 2.4 and 7.5. In addition Kohler et al. (2005) performed dissolution
613 experiments on apatite at 25 C from pH 3.01 to 8.9, Chaïrat et al. studied the dissolution
614 kinetics of apatite at 25 C and pH between 3 and 11.6 and Harouiya measured the
615 dissolution rate of apatite at 25 C in acidic solutions ranging from 1.08 to 5.6. Fig Ap1
616 summarized the published rates at 25 ºC and Table Ap1 sum up the conditions under which
617 those rates were obtained.
618 The acidic dissolution mechanism was defined by Harouiya et al. (2007) as:
619 r  AA .a Hn  exp  E A / RT  Apa-1
620 where AA stands for a rate constant equal to 4x10-3 mol/cm2/s, aH+ denotes the
621 activity of the the aqueous H+, n designates a reaction order 0.6, EA symbolize an activation
622 energy equal to 46 kJ/mol, σ represents the Temkin’s coefficient equal to 5, R stands for the
623 gas constant and T represent the absolute temperature.
624 The degree to which this equation describes the dissolution rates reported in the
625 literature can be assessed in Figure Apa1. Rates calculated using Equation Apa-1 described
626 66 of 74 reported rates within 0.8 log units with an average uncertainty of 0.2 log units. The
627 data acquired at high pH indicates a flattening of the rates not accounted for in Harouiya’s
628 equation.
629
630 References
631
632 Chaïrat C., Schott J., Oelkers E.H., Lartigue J.-E., Harouiya N., (2007) Kinetics and mechanism of
32
633 natural fluorapatite dissolution at 25 °C and pH from 3 to 12. Geochim. Cosmochim. Acta 71,
634 5901-5912.

635 Guidry, M.W., MacKenzie, F.T. (2003) Experimental study of igneous and sedimentary apatite
636 dissolution: Control of pH, distance from equilibrium, and temperature on dissolution rates.
637 Geochim. Cosmochim. Acta 67, 2949–2963
638 Harouiya, N., Chaïrat, C., Kohler, S.J., Gout, R. and Oelkers, E.H. (2007) The dissolution kinetics and
639 apparent solubility of natural apatite in closed reactors at temperaturtes from 5 to 50 C and
640 pH from 1 to 6. Chem. Geol. 244, 554-568.
641 Köhler, S.J., Harouiya, N., Chaïrat, C., Oelkers, E.H. (2005). Experimental studies of REE fractionation
642 during water–mineral interactions: REE release rates during apatite dissolution from pH 2.8
643 to 9.2. Chem. Geol. 222, 168–182.
644 Valsami-Jones, E., Ragnarsdottir, K.V., Putnis, A., Bosbach, D., Kemp, A.J., and Cressey, G. (1998) The
645 dissolution of apatite in the presence of aqueous metal cations at pH 2–7. Chem. Geo. 151,
646 215–233.
647 Welch, S.A., Taunton, A.E., Banfield, J.F. (2002) Effect of microorganisms and microbial metabolites
648 on apatite dissolution. Geomicrobiol. J. 19, 343–367.
649
650 Table and Figure

651
652 Table Ap1: Summary of experimental conditions for the various apatite steady-state
653 dissolution rates reported in the literature.
Apatite 25 3-11.6 Chaïrat et al. (2007)
Apatite 25 2.2-8.52 Guidry and Mackenzy (2003)
Apatite 5-50 1.08-5.6 Harouiya et al. (2007)
Apatite 25 3.01-8.9 Kohler et al. (2005)
Apatite 25 4.6-7 Valsami-Jones et al. (1998)
Apatite 25 2.4-7.5 Welch et al. (2002)
654
655 Figure Ap1: Summary of experimentally measured apatite steady-state dissolution rates
656 reported in the literature as a function of pH. The results of the model at 25 ºC are plotted in
657
33 dashed line.

-10
25 ºC
-11 Guidry and Mackenzy
(2003)
Valsami-Jones et al. (1998)
log r+ (mol/cm2/s)
-12
Welch et al. (2002)

-13
Harouiya et al. (2007)
-14
Chaïrat et al. (2007)
-15 Kohler et al. (2005)
Model
-16
0 2 4 6 8 10
pH
658
659
660 Apatite (hydroxylapatite)

661
662
34

663 Aragonite
664
665 Morse et al. (1979) studied the dissolution rate of aragonite at 25 ºC and pH 7 as a
666 function of the saturation state. Chou et al. (1989) measured the dissolution rate of
667 aragonite at 25 ºC and pH 4-10. In 1995 Gutjahr et al. studied the dissolution kinetics of
668 aragonite as a function of temperature, from 20 to 70 ºC and for pH values of 7.81 and 9.09.
669 Finally Cubillas et al. (2005) investigated the dissolution rates of mussels, clam, cockles and
670 pure aragonite as a function of pH. The dissolution rate of seashells is 3 orders of
671 magnitudes lower than pure aragonite. A summary of the published measurements
672 conditions are presented in Table Ar1 and the existing rates are depicted in Fig. Ar1.
673 The data was fitted with the equation presented by Busenberg and Plummer (1982)
674 and adapted by Chou et al. (1989), modified to include an activation energy term:
( ) ( ) ( ) ( ) ( )
675 where r signifies the aragonite steady state dissolution rate, AA, AB and AC refers to
676 pre-exponential factors equal to 0.12, 4x10-6 and 1x10-8 mol/cm²/sec respectively, EA, EB and
677 EC designate activation energies equal to 16.0, 46.0 and 46.0 kJ/mol respectively, R
678 represents the gas constant, and T denotes absolute temperature. The degree to which this
680 Ar1. Rates calculated using Equation Ar-1 described 43 of 45 reported rates within 0.8 log
681 units with an average uncertainty of 0.2 log units. The data points by Cubillas on shells differ
682 from the main aragonite values by 3 orders of magnitude despite following a similar
683 mechanism; they were therefore not included in the model.
684 References
685
686 Busenberg, E. and Plummer, L.N. (1982) The kinetics of dissolution of dolomite in CO2-H2O systems at
687 1.5 to 65 ºC and 0 to 1 atm pCO2. Am. J. Sci 282, 45-78.
688 Cubillas, P., Köhler, S., Prieto, M., Chaïrat, C. and Oelkers, E.H. (2005) Experimental determination of
35
689 the dissolution rate of calcite, aragonite, and bivalves. Chem. Geol. 216, 59-77.
690 Chou, L., Garrels, R.M. and Wollast, R. (1989) Comparative study of the kinetics and mechanisms of
691 dissolution of carbonate minerals. Chem. Geol. 79, 269-282.

692 Gutjahr, A., Dabringhaus, H. and Lacman R. (1995) Studies of the growth and dissolution kinetics of
693 the CaCo3 polymorphs calcite and aragonite I. Growth and dissolution rates in water.
694 Morse, J.W., De Kanel, J. and Harris, K. (1979) dissolution kinetics of calcium carbonates in seawater:
695 VII. The dissolution kinetics of synthetic aragonite and pteropod tests. Am. J. Sci. 279, 488-
696 502.
697 Table Ar1: Summary of experimental conditions for the various aragonite steady-state
Aragonite Busenberg and Plummer (1982)
Aragonite, ground clam, 25 5.1-9.8 Cubillas et al. (2005)

cockle, mussel shells
Aragonite 4.5-9.8 25 Chou et al. (1989)
Aragonite 7.81-9.09 20-70 Gutjahr et al. (1995)
Aragonite, Pteropod tests 25 7.25-7.53 Morse et al. (1979)
699
700 Figure Ar1: Summary of experimentally measured aragonite steady-state dissolution rates
702 dashed line.
703
-6
-7 25 C
Cubillas et al. (2005)
-8
log r+ (mol/cm2/s)
Cubillas et al. (2005),

-9 shells
-10 Morse et al. (1979)
-11 Gutjahr et al. (1995)
-12
Chou et al. (1989)
-13
36 Model
-14
2 4 6 8 10 12
pH
704

705 As2S3 – Orpiment

706
707 The monoclinic arsenic sulfide orpiment and As2S3 the amorphous version dissolution
708 rate were studied by Lengke and Tempel (2001, 2002, 2003 and 2005) at pH from 2.3 to 8
709 and temperature of 25 and 30 °C. The data produced was fitted by Palandri and Kharaka
710 (2004) to:
711 ( )
712 ( )
713
714 where rH+ and rH2O signifies the almandine steady-state dissolution rate in acidic,
715 neutral and basic solutions and rtt the total dissolution rate, AA and AB refer to pre-
716 exponential factors equal to 4.9x10-13 and 1.35x10-20 mol/cm²/s respectively, EA designates
717 an activation energy equal to 87.0 kJ/mol, R represents the gas constant, and T denotes
718 absolute temperature. The degree to which this equation describes the dissolution rates
719 reported in the literature can be assessed in Figure Orp1. Rates calculated using Equation
720 Orp-1 described 4 of 4 reported rates within 0.8 log units with an average uncertainty of 0.2
721 log units.
722
723 References
724
725 Lengke M. F. and Tempel R. N. (2001) Kinetic rates of amorphous As2S3 oxidation at 25 to 40°C and
726 initial pH of 7.3 to 9.4. Geochim. Cosmochim. Acta 65, 2241-2255.
727 Lengke M. F. and Tempel R. N. (2002) Reaction rates of natural orpiment at 25 to 40°C and pH 6.8 to
728 8.2 and comparison with amorphous As2S3 oxidation. Geochim. Cosmochim. Acta 66, 3281-
729 3291.
730 Lengke M. F. and Tempel R. N. (2003) Natural realgar and amorphous AsS oxidation kinetics.
37
734 2004-1068.

735 Table Orp1: Summary of experimental conditions for the various As2S3 steady-state
range
As2S3 20-72 6 Lengke and Tempel (2001)
As2S3 22 4.1 Lengke and Tempel (2002)
As2S3 Lengke and Tempel (2003)
As2S3 25 2.5-6.8 Lengke and Tempel (2005)
737
738 Figure Orp1: Summary of experimentally measured As2S3 steady-state dissolution rates
740 dashed line.
-10
-11
log r+ (mol/cm2/s)
-12
-13 Lengke and Tempel (2005)

Lengke and Tempel (2002)
-14 Lengke and Tempel (2003)
-15
-16
0 2 4 6 8 10 12
pH
741
742
38

743 Augite
744
745 The dissolution kinetics of the pyroxene augite were investigated at 22 ºC and a pH of
746 4.1 by Siegel and Pfannkuch (1984), from 20 to 72 ºC at pH 6 by Schott and Berner (1985),
747 and by Sverdrup (1990) at 25 ºC from pH 2.5 to 6.8. A summary of these published rates are
748 presented in Table Au1 and the existing rates are depicted as a function of pH in Fig. Au1.
749 Substantial scatter is apparent among the reported rates at low temperatures and near to
750 neutral pH. Such scatter may be due to a combination of factors including precipitation of
751 secondary phases, and variation in measured surface areas.
752 The fitting of augite dissolution rate data is confounded by the dearth of data and its
753 evident scatter. By analogy with diopside, augite dissolution rates were fitted to:
754 ( ( ) ) (Au-1)
755 where r+ signifies the augite steady state dissolution rate, AA and AB stands for rate
756 constants, EA designates an activation energy, R represents the gas constant, and T denotes
757 absolute temperature. This fit is strongly dependent on the selection of the low temperature
758 neutral pH data. As the structure and chemical formula of augite is similar to diopside, it
759 seems reasonable to assume their dissolution rates would be similar. 25 ºC neutral pH rates
760 of diopside appear to be most consistent with the relatively fast pH 6, 22 ºC rate of Schott
761 and Berner (1985). As such, the fit was forced to pass close to this measured rate to the
762 detriment of the other slower values. Taking this into account yielded values of AA and AB of
763 4.2 mol.cm-2.s-1 and 0.4 mol.cm-2.s-1. A corresponding EA of 83 kJ/mol was determined from
764 an Arrhenius plot of the data obtained at pH 6 by Schott and Berner (1985). The degree to
766 in Figure Au1. Rates calculated using Equation Au-1 described 9 of 13 reported rates within
767 0.8 log units.
768
39
769

770 References
771
772 Schott J. and Berner R.A. (1985) Dissolution mechanism of pyroxenes and olivines during weathering.
773 In: Drever, J.I. (ed.), The Chemistry of Weathering. NATO ASI Series C, Mathematical and
774 Physiscal Sciences. 149, 35-53.
779 Table Au1: Summary of experimental conditions for the various augite steady-state
range
Augite 20-72 6 Schott and Berner (1985)
Augite 22 4.1 Siegel and Pfannkuch (1984)
Augite 25 2.5-6.8 Sverdrup (1990)
781
782 Figure Au1: Summary of experimentally measured augite steady-state dissolution rates
784 dashed line.
-11
Schott and Berner
-12 (1985), 25 C
72 Schott and Berner

-13 64 (1985), 50-72 C
log r+ (mol/cm2/s)
50
Siegel and Pfannkuch
-14 (1984)
Sverdrup (1990)
-15
Model, 25 °C
-16
-17 Model, 50 °C
40 -18 Model, 70 °C
0 2 4 6 8 10
pH
785

786 Barite
787
788 The barium sulphate barite has been studied by Dove and Czank (1995) at
789 temperature ranging from 40 to 90 ºC and pH 2 to 11. The available data is plotted on fig.
790 Bar1. Palandri and Kharaka (2004) fitted those values to following equations:
791 ( )
792 ( )
793
794 where rH+ and rH2O signifies the barite steady-state dissolution rate in acidic, neutral
796 factors equal to 3.16x10-6 and 3.16x10-7 mol/cm²/s respectively, EA designates an activation
797 energy equal to 30.8 kJ/mol, R represents the gas constant, and T denotes absolute
798 temperature. The degree to which this equation describes the dissolution rates reported in
799 the literature can be assessed in Figure Bar1. Rates calculated using Equation Bar-1
800 described 4 of 4 reported rates within 0.8 log units with an average uncertainty of 0.2 log
801 units.
802 References
803
806 1915.
809 2004-1068.
810
41

811 Table Bar1: Summary of experimental conditions for the various barite steady-state
range
Barite 20-72 6 Dove and Czank (1995)
813
814 Figure Bar1: Summary of experimentally measured barite steady-state dissolution rates
816 dashed line.
817
-10
log r+ (mol/cm2/s)
-11
Dove and Czank (1995)
50 C
Model 50 C (Palandri
-12 and Kharaka, 2004)
and Kharaka, 2004)
-13
0 2 4 6 8 10 12
pH
818
42

819 Bayerite
820
821 The aluminum oxide bayerite (β-AlOH3) has been studied by Pulfer et al. (1984) at 25
822 C, pH ranging from 3 to 6.4 and as a function of HNO3 and HF concentration. Nordin et al
823 (1993) measured the bayerite dissolution kinetics at 25 C and pH 3. The available data is
824 plotted on fig. Bar1. The existing values were fitted to the following equation:
825 ( ) ( )
826 where r+ signifies the bayerite steady-state dissolution rate in acidic, neutral and
827 basic solutions, AA refers to pre-exponential factors equal to 34.27x10-7 mol/cm²/s, EA
828 designates an activation energy equal to 55.0 kJ/mol, R represents the gas constant, and T
829 denotes absolute temperature. The degree to which this equation describes the dissolution
830 rates reported in the literature can be assessed in Figure Bay1. Rates containing HF were
831 excluded from the calculation. Rates calculated using Equation Bay-1 described 6 of 7
832 reported rates within 0.8 log units with an average uncertainty of 0.2 log units.
833 References
834
835 Nordin, J.P., Sullivan, D.J., Phillips, B.H. and Casey, W.H. (1999) Mechanisms for fluoride promoted
836 dissolution of bayerite [β-Al(OH)3(s)] and boehmite [γ-AlOOH] : 19F-NMR spectroscopy and
837 aqueous surface chemistry. Geochim. Cosmochim. Acta 63, 3513-3524.
840 2004-1068.
841 Pulfer, K., Schindler, P.W.,Westall, J.C. and Grauer, R. (1984) Kinetics and mechanism of dissolution of
842 bayerite (γ-Al(OH)3) in HNO3-HF solution at 298.2 °K. J. Coll. Inter. Sci. 101, 554-564.
843
844
845
43

846 Table Bay1: Summary of experimental conditions for the various barite steady-state
range
Bayerite 25 3 Nordin et al (1999)
Bayerite 25 3 – 6.4 Pulfer et al. (1984)
848
849 Figure Bar1: Summary of experimentally measured bayerite steady-state dissolution rates
851 dashed line.
852
-13,00
-14,00 Nordin et al. (1999)

log r+ (mol/cm2/s)
-15,00 Pulfer et. al. (1984)
-16,00 Pulfer et. al. (1984) -

HNO3
-17,00 Pulfer et. al. (1984) -
HNO3-HF
-18,00 Model
0 2 4 6 8 10 12
pH
853
854
855
44

856 Biotite
857
858 Dissolution kinetics of the common phyllosilicate mica biotite

859 (KMg2.5Fe0.5AlSi3O10(OH)1.75F0.25) were investigated experimentally by Acker and Bricker
860 (1992), Turpault and Trotignon (1994), Kalinowski and Schweda (1996), Malmström et al.
861 (1996), Malmström and Banwart (1997), Taylor et al. (2000), Murakami et al. (2004), Samson
862 et al. (2005) and Hu and Jun (2012). These authors used a variety of different experimental
863 methods and procedures. Acker and Bricker (1992) used fluidized-bed reactors and flow
864 through columns at 25 ºC at pH 3 to 7 under different oxidizing conditions. Turpault and
865 Trotignon (1994) studied the dissolution of single biotite crystals in batch experiments at 24
866 ºC in 0.1 N HNO3. Kalinowski and Schweda (1996) determined the dissolution kinetics of
867 biotite at pH 1 to 4 and temperature of 22 ºC. Malmström and coworkers (1997) performed
868 biotite dissolution experiments in a fluidized-bed reactor at 25 ºC over the pH range 2-10.
869 The study of Taylor et al. (2000) aimed to quantify both the dissolution kinetics of biotite and
870 the release of Sr and Sr isotopes at pH near 3 and 25 ºC. Murakami et al. (2004) performed
871 biotite dissolution experiments in a batch reactor at 1 bar pCO2, pH 4.6 and 100 ºC. Samson
872 et al. (2005) investigated the transient and quasi steady state dissolution of biotite at 22 - 25
873 ºC at and pH 8 - 14. Hu and Jun (2012) investigated the dissolution kinetics of biotite in batch
874 reactors in conditions relevant for the geological storage of CO2. A summary of these
875 experimental conditions are presented in Table Bi1 and these rates are depicted in Fig. Bi1.
876 Assuming a similar dissolution mechanism for the micas, biotite and phlogopite, the
877 reported dissolution rates were fitted to :
878 ( )( )
(Bi-1)
879 where r+ signifies the biotite steady state dissolution rate, AA refers to a pre-exponential
880 factor equal to 1x10-7 mol/cm²/s, EA designates an activation energy equal to 49.0 kJ/mol, R
881 represents the gas constant, and T denotes absolute temperature and n signifies a
882
45 stoichiometric coefficient equal to 0.125. This activation energy was obtained by McMaster
883 et al. (2008) by direct observation of retreating steps on a biotite surface using AFM, a
884 similar value to the 52±5 kJ/mol determined by Hu and Jun (2012) ; AA , was obtained by the

885 regression of the data shown in Fig Bi1. The degree to which this equation describes the
886 dissolution rates reported in the literature can be assessed in Fig Bi1. Rates calculated using
887 Equation Bi-1 described 38 of 55 reported rates within 0.8 log unit.
888
889 References
890
891 Acker J.G. and Bricker O.P. (1992) The influence of pH on biotite dissolution and alteration kinetics at
892 low temperature. Geochim. Cosmochim. Acta 56, 3073-3092.
893 Boyle, J.R. and Voigt, G.K. (1973) Biological weathering of silicate minerals. Plant and Soil 38, 191-
894 201.
895 Hu, Y. and Jun, Y.-S. (2012) Biotite dissolution in brine at varied temperatures and CO2 pressures : Its
896 activation energy and potential CO2 intercalation. Langmuir (Just Accepted).
897 Kalinowski, B.E. and Schweda, P. (1996) Kinetics of muscovite, phlogopite, and biotite dissolution and
898 alteration at pH 1-4, 25 C. Geochim. Cosmochim. Acta 60, 367-385.
899 Lin, F.-C. and Clemency, C.V. (1981) The kinetics of dissolution of muscovites at 25 and 1 atm CO2
900 partial pressure. Geochim. Cosmochim. Acta 45, 571-576.
901 McMaster, T.J., Smits, M.M., Haward, S.J., Leake, J.R., Banwart, S. and Ragnarsdottir, K.V. (2008) High
902 resolution imaging of biotite dissolution and measurements of activation energy. Miner.
903 Mag. 72, 115-120.
904 Malmström M. and Banwart S. (1997) Biotite dissolution at 25 ºC: The pH dependence of dissolution
905 rate and stoichiometry. Geochim. Cosmochim. Acta 61, 2779-2799.
906 Malmström M., Banwart S., Lewenhagen J., Duro L., Bruno J. (1996) The dissolution of biotite and
907 chlorite at 25 ºC in the near-neutral pH region. J. Contam. Hydrol. 21, 201-213.
908 Mehmel, M. (1938) Ab und umbau am Biotit. Chemie der Erde 11, 307-332.
909 Murakami T., Ito J.-L., Utsonomiya S., Kasama T., Kozai N. And Ohnuki (2004) Anoxic dissolution
910 processes of biotite: Implications for Fe behavior during Achaean weathering. Earth Planet.
911 Sci. Lett. 224, 117-129.
912 Samson S.D., Nagy K.L. and Cotton W.B., III (2005) Transient and quasi-steady-state dissolution of
913 biotite at 22-25 C in high pH, sodium, nitrate, and aluminate solutions. Geochim. Cosmochim.
914 Acta 69, 399-413.
915
917 Taylor A.S., Blum J.D., Lasaga A.C. and MacInnis I.N. (2000) Kinetics of dissolution and Sr release

919 Turpault M.P. and Trotignon L. (1994) The dissolution of biotite single crystals in dilute HNO3 at 24 ºC:
920 Evidence of an anisotropic corrosion process of micas in acidic solutions. Geochim.
921 Cosmochim. Acta 58, 2761-2775.
922
923 Table Bi1: Summary of experimental conditions for the various biotite steady-state
range
Biotite 25 3-7 Acker and Bricker (1992)
Biotite 25 1.5 Boyle and Voigt (1973)
Biotite 25 1-4 Kalinowski and Schweda (1996)
Biotite 25 2.5-5 Lin and Clemency (1981)
Biotite 25 2-10 Malmström et al. (2006, 2007)
Biotite 25 4.2-5.6 Mehmel (1938)
Biotite 100 4.6 Murakami et al. (2004)
Biotite 22-25 8-14 Samson et al. (2005)
Biotite 25 4, 4.5 Swoboda-Colberg and Drever (1993)
Biotite 25 ~3 Taylor et al. (2000a)
Biotite 24 1 Turpault and Trotignon (1994)
925
926
47

927 Figure Bi1: Summary of experimentally measured biotite steady-state dissolution rates
929 dashed line.
-11
Acker and Bricker (1992)
25 ºC
-12 Boyle and Voigt (1973)
Kalinowski and Schweda

-13 (1996)
log r+ (mol/cm2/s)
Lin and Clemency (1981)
-14 Malmstrom et al. (1997)
Mehmel (1938)
-15
Nickel (1973), 70C
-16 Samson et al. (2005)
Swoboda-Colberg and
-17
Drever (1993)
-18
Turpault and Trotignon
0 2 4 6 8 10 12 14
(1994)
pH Model
930
48

931 Boehmite
932
933
934 References
935
936 Nordin, J.P., Sullivan, D.J., Phillips, B.H. and Casey, W.H. (1999) Mechanisms for fluoride promoted
937 dissolution of bayerite [β-Al(OH)3(s)] and boehmite [γ-AlOOH] : 19F-NMR spectroscopy and
938 aqueous surface chemistry. Geochim. Cosmochim. Acta 63, 3513-3524.
939
49

940 Bronzite
941
942 Dissolution rates of bronzite from 25 °C at pH ranging from 1 to 6.1 was measured by
943 Grandstaff (1977) and Schott and Berner (1983). These rates are summarized in Table Br1
944 and presented at 25 ºC as a function of pH in Figure Br1.
945 As bronzite is identical in structure and close in composition it seems reasonable to

946 expect its rates to closely follow that of enstatite. In accord with Oelkers and Schott (2001)
947 enstatite dissolution rates are consistent with
948 ( ) ( ) (Br-1)
949 where r+ signifies the steady state forward dissolution rate, AA refers to a pre-exponential
950 factor equal to 4.9x10-7 mol/cm²/sec, EA designates an activation energy equal to 48.5
951 kJ/mol, R represents the gas constant, and T denotes absolute temperature. EA was
952 assumed to be equal to that of enstatite and AA was estimated in the present study as to
953 provide a fit with the experimental values. The degree to which this equation describes the
954 dissolution rates reported in the literature can be assessed in Figure Br1. Rates calculated
955 using Equation Br-1 described 9 of 9 reported rates within 0.8 log units.
956
957 References
958
959 Grandstaff, D.E. (1977) Some kinetics of bronzite orthopyroxene dissolution. Geochim. Cosmochim.
960 Acta, 41, 1097-1103.
961 Schott, J. and Berner, R.A. (1983) X-Ray photoelectron studies of the mechanism of iron silicate
962 dissolution during weathering. Geochim. Cosmochim. Acta, 47, 2233-2240.
963
50

964 Table Br1: Summary of experimentally measured bronzite steady-state dissolution rates
range
Bronzite 25 2 – 6.1 Grandstaff (1977)
Bronzite 25 1, 1.5, 6 Schott and Berner (1983)
966
967 Figure Br1: Summary of experimentally measured bronzite steady-state dissolution rates
-13
Bronzite
dissolution
-14 25 ºC
log rate (mol/cm2/s)
-15 Grandstaff (1977)
Schott and Berner

-16 (1983)
Model
-17
0 2 4 6 8 10
970 pH
971
51

972 Brucite
973
974 Dissolution rates of brucite from 25 °C and up to 90 °C at pH ranging from 1 to 3.7

975 have been published by Pokrovsky (2004) and at 22 °C with pH ranging from 2 to 9 by Mast
976 and Drever (1987). The rates are presented for the different temperatures as a function of
977 pH in Figure An1.
978 Following the theoretical framework laid by Oelkers (2001) for the dissolution of
979 multi-oxides minerals steady-state anthophyllite dissolution rates were fitted to:
æ a2 ö
1/8
r = AA .exp ( -EA / RT ) ç H ÷
+
980
ç a 2+ ÷ (Bru-1)
è Mg ø
981 where r signifies the brucite steady state dissolution rate, AA refers to a pre-exponential
982 factor equal to 1.7x10-3 mol/cm²/sec3, EA designates an activation energy equal to 46 kJ/mol,
983 R represents the gas constant, and T denotes absolute temperature. AA was provided by
984 Marini (2007) and EA was determined to be intermediate between the values proposed by
985 Jordan (1996) and Vermilyea (1969). The degree to which this equation describes the
986 dissolution rates reported in the literature can be assessed in Figure A1. Rates calculated
987 using Equation Bru-1 described 12 of 14 reported rates within 0.8 log units with an average
988 uncertainty of 0.2 log units.
989
990
991 References
992
993 Jordan, G., Rammensee, W. (1996) Dissolution rates and activation energy from dissolution of brucite
994 (001): A new method based on the microtopography of crystal surfaces. Geochim.
995 Cosmochim. Acta 60, 5055-5062.
996 Pokrovsky, O.S., Schott, J. (2004) Experimental study of brucite dissolution and precipitation in
997 aqueous solution: Surface speciation and chemical affinity control. Geochim. Cosmochim.
998
52 Acta 68, 31-45.
1. Ea was recalculated and falls between the values determined by Jordan (1996) on brucite and Vermilyea
(1969) on MgO

999 Pokrovsky, O.S., Schott, J., Castillo, A. (2005a) Kinetics of brucite dissolution at 25 C in the presence
1000 of organic and inorganic ligands and divalent metals. Geochim. Cosmochim. Acta 69, 905-918.
1001 Vermilyea, D.A. (1969) The dissolution of MgO and Mg(OH)2 in aqueous solutions. J. Electrochem.
1002 Soc. 116, 679-728.
1003 Table B1: Summary of experimentally measured brucite steady-state dissolution rates
range
Brucite 25 2.7 Jordan and Rammensee (1996)
Brucite 25 1-3.7 Pokrovsky and Schott (2004)
Brucite 25 Pokrovsky et al. (2005a)
Brucite Vermilyea (1969)
1005
1006 Figure B1: Summary of experimentally measured brucite steady-state dissolution rates
-9,00
-10,00
log r+ (mol/cm2/s)
-11,00
Pokrovsky et al. (2004)
-12,00
Model
-13,00
Jordan and Rammensee
(1996)
-14,00
-15,00
0 2 4 6 8 10 12
pH
1009
53
1010
1011

1012 Bytownite
1013
1014 Bytownite, a calcium-rich member of the plagioclase solid solution, usually falls
1015 between An70 and An90. Holdren and Speyer (1987) measured the dissolution rate of
1016 bytownite at 25 C and pH 3, Casey et al. (1991) studied bytownite dissolution kinetics at 25 C
1017 and pH 2, Oxburgh et al. (1993) reported dissolution rates at 25 ºC and for a pH ranging from
1018 3.1 to 7.2 and Stilling and Brantley (1995) investigated the dissolution kinetics of bytownite
1019 at 25 C and 3.1<pH<4.7. The experimental conditions for those studies are summarized in
1020 Table Byt1 and the rates are presented at 25 ºC as a function of pH in Figure Byt1.
1021 Following the theoretical framework laid by Oelkers (2001) for the dissolution of
1022 multi-oxides minerals steady-state bronzite dissolution rates were fitted to:
1023 ( ) ( ( )) Byt-1
1024 where r signifies the bytownite steady state dissolution rate, AA refers to a pre-exponential
1025 factor equal to 2.7x10-13 mol/cm²/s, n stands for the reaction order of 0.33, EA designates an
1026 activation energy equal to 18 kJ/mol, R represents the gas constant, and T denotes absolute
1027 temperature. The degree to which the model fits the data can be assessed with the help of
1028 Figure Byt1. Rates calculated using Equation Byt-1 described 20 of 23 reported rates within
1029 0.8 log units with an average uncertainty of 0.2 log units.
1030
1031 References
1032
1034 Mineral. 76, 211-217.
1037 2311-2318.
1038 Oxburgh, R. Drever, J.L. and Sun, Y.T. (1994) Mechanism of plagioclase dissolution in acid solution at
54
1039 25 ºC. Geochim. Cosmochim. Acta 58, 661-669.

1042 Table Byt1: Summary of experimentally measured bytownite steady-state dissolution rates
Bytownite 25 5.65 Busenberg and Clemency (1976)
Bytownite 25 2 Casey et al. (1991)
Bytownite 25 3 Holdren and Spayer (1987)
Bytownite 25 3.1-7.2 Oxburgh et al. (1993)
Bytownite 25 3.1-4.7 Stillings and Brantley (1995)
Bytownite 22 3.2 – 7.2 Welch and Ullman (1993)
Bytownite 5-35 3.2, 5.65 Welch and Ullman (1993)
1044
1045 Figure By1: Summary of experimentally measured bytownite steady-state dissolution rates
1047 dotted line.
-12 Busenberg and Clemency

25 ºC (1976)
Casey et al. (1991)
-13
log r+ (mol/cm2/s)

-14
Oxburgh et al. (1993)
-15 Stillings and Brantley

(1995)
-16

-17
0 2 4 6 8 10 12 Model
pH
1048
1049
55

1050 Calcite
1051
1052 Calcite (CaCO3) dissolution kinetics has been extensively studied in the past (Table
1053 Ca1). A summary of the published measurements conditions are presented in Table Ca1 and
1054 the existing rates are depicted in Fig. Ca1.
1055 The data was fitted with the equation presented by Busenberg and Plummer (1982)
1056 and adapted by Chou et al. (1989), modified to include an activation energy term:
( ) ( ) ( ) ( ) ( )
1057 where r signifies the calcite steady state dissolution rate, AA, AB and AC refers to pre-
1058 exponential factors equal to 2.13x10-2, 3.47x10-3 and 1.17x10-2 mol/cm²/s respectively, EA, EB
1059 and EC designate activation energies equal to 16.0, 46.0 and 46.0 kJ/mol respectively, R
1060 represents the gas constant, T denotes absolute temperature and n a reaction order equal
1061 to 0.33. Activation energies were determined by Sjöberg and Rickard (1984). The degree to
1063 in Figure Ca1. Rates calculated using Equation Ca-1 described 43 of 45 reported rates within
1064 0.8 log units.
1065
1066
1067 References
1068
1069 Arakaki, T., Mucci, A. (1995) A continuous and mechanistic representation of calcite reaction-
1070 controlled kinetics in dilute solutions at 25 ºC and 1 atm total pressure. Aquat. Geochem. 1,
1071 105-130.
1072 Arvidson, R.S., Ertan, I.E., Amonette, J.E., and Luttge, A. (2003) Variation in Calcite dissolution rates: a
1073 fundamental problem? Geochim. Cosmochim. Acta 67, 1623-1634.
56
1076 Cubillas, P., Köhler, S., Prieto, M., Chaïrat, C. and Oelkers, E.H. (2005) Experimental determination of
1077 the dissolution rate of calcite, aragonite, and bivalves. Chem. Geol. 216, 59-77.

1078 Davis, K.J., Nealson, K.H. and Luttge, A. (2007) Calcite and dolomite dissolution rates in the context of
1079 microbe-mineral surface interactions. Geobio. 5, 191-205.
1080 Gutjahr, A., Dabringhaus, H. and Lacman R. (1995) Studies of the growth and dissolution kinetics of
1081 the CaCO3 polymorphs calcite and aragonite I. Growth and dissolution rates in water.
1082 Hales, B., Emerson, S. (1996) Calcite dissolution in sediments of the Ceara Rise : In situ measurements
1083 of porewater O2, pH and CO2(aq) . Geochim. Cosmochim. Acta 61, 501-514.
1084 Jordan, G., Rammensee, W. (1997) Dissolution rates of calcite (1014) obtained by scanning force
1085 microscopy: Microtopography-based dissolution kinetics on surfaces with anisotropic step
1086 velocities. Geochim. Cosmochim. Acta 62, 941-947.
1087 MacInnins, I.N., Brantley, S.L (1992) The role of dislocations and surface morphology in calcite
1088 dissolution. Geochim. Cosmochim. Acta, 56, 113-1126.
1089 Oelkers, E.H., Golubev, S.V., Pokrovsky, O.S., Bénézeth, P. (2011) Do organic ligands affect calcite
1090 dissolution rates? Geochim. Cosmochim. Acta, 75, 1799-1813.
1091 Plummer, L.N., Wigley, T.M.L., Parkhurst, D.L. (1978) The kinetics of calcite dissolution in CO2-water
1092 systems at 5 C and 60 C and 0.0 to 1.0 atm CO2. Am. J. Sci. 278, 179-216.
1093
1094 Table Ca1: Summary of experimentally measured calcite steady-state dissolution rates
25 4.7-5.9 Araki and Mucci (1995)
Arvidson et al. (2003)
Chou et al. (1989)
Davis et al. (2007)
Gutjahr et al. (1995)
3 Hales and Emerson (1996)
Jordan and Rammensee (1998)
McInnis and Brantley (1992)

57
Oelkers et al. (2011)
Plummer et al. (1978)

1096
1097 Figure Ca1: Summary of experimentally measured celestite steady-state dissolution rates
1099 dotted line.
1100
-6
Araki and Mucci (1995)
-7
25 ºC Arvidson et al. (2003)
Chou et al. (1989)
-8 Cubillas et al. (2005) Mussel
Davis et al. (2007)
log r+ (mol/cm2/s)
Gutjahr et al. (1995)

-9
Hales and Emerson (1996)
Jordan and Rammensee (1998)
-10 MacInnis and Brantley (1992)
-11 Oelkers et al. (2011)
Plummer et al. (1978)
-12 Pokrovsky et al. (2003)
Rickard and Sjoberg (1983)
-13 Schott et al. (1989)
Shiraki et al. (2000)
-14 Sjöberg and Rickard (1984)
1 3 5 7 9 11 Sjöberg and Rickard (1985)
Model
pH
1101
1102
58

1103 Celestite
1104
1105 The strontium sulphate celestite (SrSO4) has been studied by Dove and Czank (1995)
1106 at temperature ranging from 32 to 140 ºC and pH 3.8 to 12.0. The available data is plotted on
1107 fig. Cel1. Palandri and Kharaka (2004) fitted those values to following equations:
1108 ( )
1109 where rH+ signifies the barite steady-state dissolution rate in acidic solutions, AA refers to
1110 pre-exponential factors equal to 5.4e-9 mol/cm²/s, EA designates an activation energy equal
1111 to 6.08 kJ/mol, R represents the gas constant, and T denotes absolute temperature. The
1112 degree to which this equation describes the dissolution rates reported in the literature can
1113 be assessed in Figure Cel1. Rates calculated using Equation Cel-1 described all reported rates
1114 within 0.8 log units.
1115 References
1116
1119 1915.
1122 2004-1068.
1123
1124
59

1125 Table Cel1: Summary of experimentally measured celestite steady-state dissolution rates
range
Celestite 25 2.7 Dove and Czank (1995)
1127
1128 Figure Cel1: Summary of experimentally measured celestite steady-state dissolution rates
1129 reported in the literature at 50 ºC as a function of pH and at pH 5.7 as a function of
1130 temperature. The results of the model are plotted as the dotted line.
-9
-9
50 C pH 5.7
-9,5
log r+ (mol/cm2/s)
log r+ (mol/cm2/s)
-9,5
-10 -10
Dove and Czank (1995) Dove and Czank (1995)

-10,5 -10,5
Model (Palandri and Kharaka,
Kharaka, 2004)
2004)
-11 -11
0 2 4 6 8 10 12 25 50 75 100 125 150
pH Temperature ( ºC)
1131
1132
60

1133 Chlorite
1134
1135 A limited amount of studies have investigated the dissolution kinetics of chlorite at
1136 25 ºC, Ross (1967) published chlorite dissolution rate at pH 0, Kodama and Schnitzer (1973)
1137 reported rates gathered near pH 3. Sverdrup (1990) investigated the dissolution of chlorite
1138 at pH 2.5 to 5, May (1995) studied the dissolution rate at pH 5 and Malmström et al. (1996)
1139 at pH 8.2. Rochelle et al. (1996) reported rates measured at pH 7.7 to 12.5 and Salmon and
1140 Malmström (2001) at pH 3.5. In 2003 Hamer et al. measured rates from 3 to 4.5, Brandt et
1141 al. (2003) from pH 1.89 to 5.3 and Gustafsson and Puigdomenech (2003) from 2 to 12. Finally
1142 Lowson et al. (2005, 2007) investigated the dissolution of Fe-rich chlorite under far from
1143 equilibrium conditions from pH of 3 to 10.5 at 25 ºC. The experimental conditions for those
1144 studies are summarized in Table Ch1 and the rates are presented at 25 ºC as a function of pH
1145 in Figure Ch1.
1146 We have fitted the published data on chlorite on the equation developed by Lowson
1147 et al. (2005):
1 / 3.7
 a H3  
1148 r  AA .   (Ch-1)
 a 3 
 Al 
1149 where r signifies the chlorite steady state dissolution rate, AA refers to a pre-exponential
1150 factor equal to 10-14.896 mol/cm²/sec, R represents the gas constant, and T denotes absolute
1152 the literature can be assessed in Figure Ch1. Rates calculated using Equation Ch-1 described
1153 88 of 94 reported rates within 0.8 log units with an average uncertainty of 0.2 log units.
1154
1155 References
1156
1157 Brandt, F., Bosbach, D., Krawczyk-Bärsch, E., Arnold, T., Bernhard, G. (2003) Chlorite dissolution in
1158 the acid pH-range: A combined microscopic and macroscopic approach. Geochim.
1159
61 Cosmochim. Acta, 67, 1451-1461.
1160 Gustafsson, Å.B. and Puigdomenech, I. (2003) The effect of pH on chlorite dissolution rates at 25 ºC.
1161 Mat. Res. Symp. Proc. 757, 649-655.

1162 Hamer, M., Graham, R.C., Amrhein, C., Bohzilov, K.N. (2003) Dissolution of ripidolite (Mg, Fe-Chlorite)
1163 in organic and inorganic acid solutions. Soil Sci. Soc. Am. J., 67, 654-661.
1164 Kodama, H. and Schnitzer, M. (1973) Dissolution of chlorite minerals by fulvic acid. Can. J. Soil Sci. 53,
1165 240-243.
1166 Lowson, R.T., Brown, P.L., Comarmond, M.-C.J., Rajaratnam, G. (2005) The kinetics of chlorite
1167 dissolution as a function of pH and at 25 ºC. Geochim. Cosmochim. Acta, 69, 1687-1699.
1168 Lowson, R.T., Brown, P.L., Comarmond, M.-C.J., Rajaratnam, G. (2007) The kinetics of chlorite
1169 dissolution. Geochim. Cosmochim. Acta, 71, 1431-1447.
1170 Malmström, M., Banwart, S., Lewenhagen, J., Duro, L., Bruno, J. (1996) The dissolution of biotite and
1171 chlorite at 25 ºC in the near-neutral pH region. J. Contam. Hydrol., 21, 201-213.
1172 May, H., Acker, J.G., Smyth, J.R., Bricker, O.P., Dyar, M.D. (1995) Aqueous dissolution of Low-Iron
1173 Chlorite in dilute acid solutions at 25 ºC. 32nd Ann. Meeting Clay Minerals Society.
1176 2004-1068.
1177 Rochelle, C.A., Bateman, K., Macgregor, R., Pearce, J.M., Savage, D., Wetton, P.D. (1996)
1178 Experimental determination of chlorite dissolution rates. Materials Research Society
1179 Symposium.
1180 Ross, G.J. (1967) Kinetics of acid dissolution of an orthochlorite mineral. Can. J. Chem., 45, 3031-
1181 3034.
1182 Salmon, S.U. and Malmström, M.E. (2001) Mineral weathering Rates in Mill Tailings From
1183 Kristinenberg. Northern Sweden. In Eleventh Ann. V.M. Goldschmidt Conference, Abstract #
1184 3375. LPI Contribution No. 1088, Lunar and Planetary Institute, Houston (CD-ROM).
1185 Sverdrup, H.U. (1990) The kinetics of base cation release due to chemical weathering. Lund
1186 University Press, Lund.
1187 Swoboda-Colberg, N.G. and Drever, J.I (1993) Mineral dissolution rates in plot-scale field and in
1189
62

1190 Table Ch1: Summary of experimentally measured chlorite steady-state dissolution rates
Chlorite 25 1.89-5.3 Brandt et al. (2003)
Chlorite 25 2-12 Gustafsson and Puigdomenech (2003)
Ripidolite 25 2-4.5 Hamer et al. (2003)
Chlorite 25 3 Kodama and Schnitzler (1973)
Chlorite 25 3.1-10.44 Lowson et al. (2005)
Chlorite 25-45 3.1-10.34 Lowson et al. (2007)
Chlorite 25 8.2 Malmström et al. (1996)
Chlorite 25 5 May et al. (1995)
Chlorite 25 7.7-12.5 Rochelle et al. (1996)
Orthochlorite 25 -0.3 Ross (1967)
Chlorite 25 3.5 Salmon and Malmström (2001)
Chlorite 25 2.5-5 Sverdrup (1990)
Chlorite 25 4, 4,5 Swoboda-Colberg and Drever (1993)
1192
1193
63

1194 Figure Ch1: Summary of experimentally measured chlorite steady-state dissolution rates
1196 dotted line.
-12 Brandt et al. (2003)
25 ºC Gustafsson and Puigdomenech (2003)
-13 Hamer et al. (2003)

Kodama and Schnitzler (1973)
log r+ (mol/cm2/s)
-14 Lowson (2007)

Lowson (2005)
-15 Malmström et al. (1996)
May (1995)
-16 Rochelle et al. (1996)
Ross (1967)
-17 Salmon and Malmström (2001)
Sverdrup (1990)
-18 Swoboda-Colberg and Drever (1993)
-1 1 3 5 7 9 11 13
Model
pH
1197
1198
64

1199 Christobalite
1200
1201 Chrysotile
1202
1203
65

1204 Cordierite
1205
1206 The dissolution rates of the magnesium iron aluminum cyclosilicate cordierite were
1207 studied by Sverdrup (1990) and these data are plotted in fig. Cor1. In the absence of a
1208 mechanistic model Palandri and Kharaka (2004) fit these rates assuming they are controlled
1209 by two parallel reactions, one proton promoted, and one water promoted in accord with :
1210 ( )
1211 ( )
1212 which can be summed to yield the overall forward rate using
1213
1214 where rH+ and rH2O signifies the cordierite steady-state dissolution rate in response to the
1215 proton and water promoted mechanisms, respectively, and r+ the total forward dissolution
1216 rate, AA and AB refer to pre-exponential factors equal to 1.12x1012 and 5.75x10-11 mol/cm²/s
1217 respectively, EA designates an activation energy equal to 113.3 and 28.3 kJ/mol respectively,
1218 R represents the gas constant, and T denotes absolute temperature. The degree to which
1219 these equations describes the measured can be assessed in Figure Cor1. Rates calculated
1220 using Equation Cor-1 described all 8 of the reported rates within 0.8 log units.
1221
1222 References
1223
1226 2004-1068.
1229
66
1230

1231 Table Cor1: Summary of experimental conditions for the various cordierite steady-state
range
Cordierite 25 2-6 Sverdrup (1990)
1233
1234 Figure Cor1: Summary of experimentally measured barite steady-state dissolution rates
1236 dotted line.
-8
-9
-10
log r+ (mol/cm2/s)
-11
Kharaka, 2004)
-13
Sverdrup (1990)
-14
-15
-16
0 2 4 6 8 10 12
pH
1237
1238
67

1239 Corundum
1240
1241 Corundum (Al2O3) is a crystalline form of aluminum oxide. Caroll-Webb and Walther
1242 (1988) studied the dissolution kinetics of corundum at 25 ºC as a function of pH (0.99 –
1243 11.21). The experimental conditions for this study are summarized in Table Co1 and the
1244 rates are presented at 25 ºC as a function of pH in Figure Co1.
1245 The data was fitted using the dissolution mechanisms defined by Palandri and
1246 Kharaka (2004):
1247 ( )
1248 ( )
1249 ( )
1250 where ri represents the corundum dissolution rate in acidic, neutral and basic conditions
1251 while rtt stands for the overall dissolution rate. AA, AB and AC refer to pre-exponential factors
1252 equal to 6.45x10-9, 4.36x10-12 and 1.94 mol/cm²/s respectively, EA, EB and EC designate
1253 activation energies equal to 47, 61 and kJ/mol, R represents the gas constant, and T denotes
1254 absolute temperature.
1255 The degree to which this model describes the dissolution rates reported in the
1256 literature can be assessed with the help of Figure Co1.
1257
1258 References
1259
1260 Caroll-Webb, S.A. and Walter, J.V. (1988) A surface complex reaction model for the pH dependence
1261 of corundum and kaolinite dissolution rates. Geochim. Cosmochim. Acta, 52, 2609-2623.
68
1264 2004-1068.
1265

1266
1267
1268 Table Co1: Summary of experimentally measured corundum steady-state dissolution rates
1270
Corundum 25 0.99-11.21 Caroll-Webb and Walter (1988)
1271
1272
1273 Figure Co1: Summary of experimentally measured corundum steady-state dissolution rates
1275 dotted line.
-14
-14,5
25 C
-15
log r+ (mol/cm2/s)
-15,5
-16 Caroll-Webb and Walther

(1988)
-16,5 Model
-17
-17,5
-18
0 2 4 6 8 10 12
pH
1276
1277
69

1278 Dawsonite
1279
1280 The mineral dawsonite (NaAlCO3(OH)2) has been suggested to play a significant role
1281 as a CO2 storage host in saline alkaline aqueous solutions. Following the work of Ferrante et
1282 al. (1976) and Bénézeth et al. (2007) the thermodynamic stability of dawsonite is well
1283 known. Dissolution rates of natural dawsonite have been studied by Hellevang et al. (2005)
1284 at 80 ºC and pH ranging from 3 to 10. Those findings were subsequently refined by Hellevang
1285 et al. (2009) who measured dawsonite reactivity at 22, 60 and 77 ºC and within the pH range
1286 of 0.5<pH<5.
1287 The rate data obtained in Hellevang et al. (2009) suggests a 77 ºC pH 4 rate of
1288 approximately 10-10.7 moles/cm2/s. This is more than two orders of magnitude higher than
1289 the 10-12.8 moles/cm2/s reported by Hellevang et al. (2005). One likely explanation for the
1290 large difference in estimated rates between the 2009 study and the 2005 study by Hellevang
1291 et al. (2005) lays in an overestimation of the BET surface area used in the surface area
1292 normalization in Hellevang et al. (2005) and therefore the rates were underestimated. Other
1293 reasons such as differences in the reactivity of natural dawsonite (Hellevang et al., 2005)
1294 compared to synthetic (Hellevang et al., 2009) cannot be excluded. The data reported by
1295 Hellevang et al. (2005) is inconsistent with the later study and was therefore not included in
1296 our fit.
1297 The experimental conditions for those studies are summarized in Table Da1 and the
1298 rates are presented at 25 ºC as a function of pH in Figure Da1. The experimental data was
1299 fitted by Declercq (2010) to:
( )
( )
1300 (Daw1)
70
1301 where rH+ and rH2O signifies the dawsonite steady-state dissolution rate in acidic and neutral
1302 solutions and rtt the total dissolution rate, AA and AB refer to pre-exponential factors equal
1303 to 2.7x102and 4.2x10-5 mol/cm²/s respectively, EA and EB designates an activation energy

1304 equal to 63.8 and 49.4 kJ/mol, R represents the gas constant, and T denotes absolute
1306 the literature can be assessed in Figure Da1. Rates calculated using Equation Da-1 described
1307 18 of 18 reported rates within 0.8 log units.
1308 References
1309
1310 Bénézeth, P., Palmer, D.A., Anovitz, L.M. and Horita, J. (2007). Dawsonite synthesis and reevaluation
1311 of its thermodynamic properties from solubility measurements: implications for mineral
1312 trapping of CO2. Geochim. Cosmochim. Acta 71, 4438-4455.
1313 Declercq, J. (2010) Dissolution rates and Mechanisms; Experiments on Alteration and Reactivity of
1314 Glasses and Carbonates. Series of dissertation, University of Oslo 943.
1315 Ferrante, M.J., Stuve, J.M. and Richardson, D.W. (1976). Thermodynamic data for synthetic
1316 dawsonite. US Bureau of Miners Report Investigation 8129, Washington, DC.
1317 Hellevang, H., Aagaard, P., Oelkers, E.H. and Kvamme, B. (2005). Can dawsonite permanently trap
1318 CO2? Environ. Sci. Technol. 39, 8281–8287.
1319 Hellevang, H., Declercq, J., Kvamme, B. and Aagaard, P. (2009) The dissolution rates of dawsonite at
1320 pH 0.9 to 5 and temperatures of 22, 60 and 77 ºC. Applied Geochem. 25, 1575-1586.
1321
1322
71

1323 Table Da1: Summary of experimentally measured dawsonite steady-state dissolution rates
1325
Dawsonite, natural 80 3-10 Hellevang et al. (2005)
Dawsonite, Synthetic 22, 60, 77 0.9 - 5 Hellevang et al. (2009)
1326
1327
1328 Figure Da1: Summary of experimentally measured dawsonite steady-state dissolution rates
1330 dotted line.
-6
-7
-8
-9
log r+ (mol/cm2/s)
-10 Hellevang et al. (2005), 80 C

Hellevang et al. (2009), 22C
-11
-12
-13 Model, 25 C
-14 Model, 77 C
-15
-16
0 2 4 6 8 10
pH
1331
72

1332 Diaspore
1333
1334 The dissolution rate of the aluminum hydroxide diaspore (AlO(OH)) has been studied
1335 by Chang et al. (1979). In the absence of additional data to improve existing data fits, these
1336 we have adopted the empirical pH power function fit of Palandri and Kharaka (2004) in
1337 accord with:
1338 ( )
1339 ( )
1340
1341 where rH2O and rOH- signifies the almandine forward dissolution rate in neutral and
1342 basic solutions and rtt the total dissolution rate, AB and AC refer to pre-exponential factors
1345
1346
73

1347 References:
1348
1349 Chang B.-T., Pak L.-H., and Li Y.-S. (1979) Solubilities and rates of dissolution of diaspore in NaOH
1350 aqueous solutions. Bull. Chem. Soc. Japan 52, 1321-1326.
1351
1352 Table Dia1: Summary of experimentally measured diaspore steady-state dissolution rates
Diaspore 25 Chang et al. (1979)
1354
1355 Figure Dia1: Summary of experimentally measured diaspore steady-state dissolution rates
1357 dotted line.
-6
-8
log r+ (mol/cm2/s)
-10
-12

Kharaka, 2004)
-16
-18
-20
6 8 10 12
pH
1358
74

1359 Diopside
1360
1361 Dissolution rates of the clinopyroxene diopside were reported at 22 °C and with pH
1362 ranging from 1 to 6 by Schott et al. (1981) then Eggleston et al. (1989) published kinetic data
1363 on diopside dissolution at 25 ºC and pH of 1. Knauss et al. (1993) measured dissolution rates
1364 at 25º, 50 º and 70 ºC. Brantley and Chen (1995) reported dissolution rates at 25º and 90 ºC
1365 with pH of 1 to 3.8. More recently Golubev et al. (2005) investigated the effect of CO2 on the
1366 dissolution kinetics of diopside dissolution at 25 º C and pH from 1 to 11.7. Stockmann et al.
1367 investigated the dissolution rates at 25º and 70 ºC with pH ranging from 4.3 to 8.5. Daval et
1368 al. (2010) reported rates acquired at 90 ºC and pH close to 5. The rates acquired at 25 C are
1369 presented as a function of pH in Figure Di1. The values reported by Schott et al. (1981) are
1370 several orders of magnitude faster than the data produced by the other authors; it was not
1371 thus included in the model. The experimental conditions for those studies are summarized in
1372 Table Di1 and the rates are presented at 25 ºC as a function of pH in Figure Di1.
1373 Following the definition of an equation describing the dissolution mechanism of

1374 pyroxenes by Oelkers (2001) diopside dissolution rates were fitted to:
1375 ( ( ) ) (Di-1)
1376 where r+ signifies the diopside steady state dissolution rate, AA and AB stands for rate
1377 constants, EA designates an activation energy, R represents the gas constant, and T denotes
1378 absolute temperature. AA and AB were determined to be 9.97x10-7 and 0.2x10-6 while an EA
1379 of 48.14 kJ/mol was calculated from an Arrhenius plot of the data obtained by Knauss et al.
1380 (1993) at pH 2. The degree to which this equation describes the dissolution rates reported in
1381 the literature can be assessed in Figure Di1. Rates calculated using Equation Di-1 described
1382 62 of 72 reported rates within 0.8 log units with an average uncertainty of 0.2 log units.
75

1383 References
1384
1385 Brantley, S.L. and Chen, Y. (1995) Chemical weathering rates of pyroxenes and amphiboles. In: White,
1386 A.F. and Brantley S.L. (Eds.), Chemical Weathering Rates of Silicate Minerals. Am. Mineral. 85,
1387 1767-1783.
1388 Daval, D., Hellmann, R., Crovisier, J., Tisserand, D., Martinez, I., Guyot, F. (2010). Dissolution kinetics
1389 of diopside as a function of solution saturation state: Macroscopic measurements and
1390 implications for modeling of geological storage of CO2. Geochim. Cosmochim. Acta 74, 2615–
1391 2633.
1392 Eggleston, CM, Hochella Jr., MF., Parks, G.A. (1989) Sample preparation and aging effects on the
1393 dissolution rate and surface composition of diopside. Geochim. Cosmochim. Acta 53, 797-804
1394 Golubev, S.V., Pokrovsky, O.S., Schott, J. (2005) Experimental determination of the effect of dissolved
1395 CO2 on the dissolution kinetics of Mg and Ca silicates at 25 ºC. Chem. Geol. 217, 227-2538
1396 Knauss, K.G., Nguyen, S.N., Weed, H.C., (1993) Diopside dissolution kinetics as a function of pH, CO2,
1397 temperature, and time. Geochim. Cosmochim. Acta 57, 285-294.
1398 Oelkers, E.H. (2001)?
1399 Schott, J., Berner, R.A., Sjöberg, E.L. (1981) Mechanism of pyroxene and amphibole weathering - I.
1400 Experimental studies of iron-free minerals. Geochim. Cosmochim. Acta 45, 2123-2135.
1401 Stockmann, G., Wolff-Boenisch, D., Gíslason, S.R., Oelkers, E.H. (2008) Dissolution of diopside and
1402 basaltic glass: the effect of carbonate coating. Miner. Mag. 72, 135-139.
76

1403 Table Di1: Summary of experimentally measured diopside steady-state dissolution rates
Diopside 25, 90 1.2-3.6 Brantley and Chen (1995)
Diopside 90 5 Daval et al. (2010)
Diopside 25 1 Eggleston et al. (1989)
Diopside 25 1-11.75 Golubev et al. (2005)
Diopside 25-70 2-12.1 Knauss et al. (1993)
Diopside 22 1-6 Schott et al. (1981)
Diopside 25, 70 4.3-8.5 Stockmann et al. (2008)
1405
1406 Figure Di1: Summary of experimentally measured diopside steady-state dissolution rates
1408 dotted and dashed lines.
-11
Brantley and Chen (1995)
Diopside
Eggleston et al. (1989)
-12 Golubev et al. (2005)
Golubev et al. (2005) + CO2

log r+ (mol/cm2/s)
-13 Knauss et al. (1993), 25 ºC
Knauss et al. (1993), 70 ºC
Stockmann et al. (2007), 25 ºC
-15 Stockmann et al. (2007), 70 ºC
Model, 25 ºC
-16 Model, 70 ºC
0 2 4 6 8 10 12
77 pH
1409
1410

1411 Dolomite
1412
1413 The study of dolomite (CaMg(CO3)2) dissolution started with Busenberg and Plummer
1414 (1982) at temperature ranging from 5 to 65 ºC and pH from 1 to 10 and fixed pCO2. Chou et
1415 al. (1989) used continuous flow through reactor to study dolomite dissolution at 25 ºC and in
1416 the pH range 3 to 10. Orton and Unwin (1993) investigated the dissolution kinetics of
1417 dolomite and reported transport rates at 25 ºC and pH 3-4 through a channel-flow method,
1418 Gautelier et al. (1999) reported rates at 25, 50 and 80 ºC and pH ranging from -0.39 to 4.44.
1419 Lüttge et al. (2002) used vertical scanning interferometry to study dolomite dissolution at pH
1420 3 and 25 ºC. Pokrovsky et al. (1999) and Pokrovsky and Schott (2001) performed
1421 measurements of the steady state of dolomite dissolution at 25 ºC as a function of pH (5-12).
1422 Gautelier et al. (2007) reported rates at 80 ºC as a function of chemical affinity. The
1423 experimental conditions for those studies are summarized in Table Do1 and the rates are
1424 presented at 25 ºC as a function of pH in Figure Do1.
1425 We based our rate law on the one defined by Busenberg and Plummer (1982) who
1426 followed the interpretative guidelines of Plummer et al. (1978) for calcite:
1427 (Do-1)
1428 and added an activation energy term for each dissolution mechanism. The pre-exponential
1429 factors were recalculated to fit the data:
1430 [ ( )] ( ) ( ) (Do-2)
1431 where r+ signifies the dolomite steady state dissolution rate, AA, AB and AC refer to pre-
1432 exponential factor equal to 1.49x10-2, 1x10-2 and 2.2x10-7 mol/cm²/s respectively, EA , EB and
1433 EC designate an activation energy equal to 29.0, 34.8 and 52.2 kJ/mol respectively, R
1434 represents the gas constant, T denotes absolute temperature and n is a reaction order equal
1435 to 0.75. The activation energies were determined from an Arrhenius plot of the data
1436 reported by Gautelier et al. (1999). The degree to which this equation describes the
1437 dissolution rates reported in the literature can be assessed in Figure Do1. Rates calculated
78
1438 using Equation Do-2 described 85 of 87 reported rates within 0.8 log units.
1439

1440
1441 References
1442
1443 Busenberg, E. and Plummer, L.N. (1982) The kinetics of dissolution of dolomite in CO2-H2O systems at
1444 1.5 to 65 ºC and 0 to 1 atm pCO2. Am. J. Sci 282, 45-78.
1447 Gautelier, M., Oelkers, E.H. and Schott, J. (1999) An experimental study of dolomite dissolution rates
1448 as a function of pH from -0.5 to 5 and temperature from 25 to 80 ºC. Chem. Geol. 157, 13-26.
1449 Gautelier, M., Schott, J. and Oelkers, E.H. (2007) An experimental study of dolomite dissolution rates
1450 at 80 ºC as a function of chemical affinity and solution composition. Chem. Geol. 242, 509-
1451 517.
1452 Herman, J.S. and White, W.B. (1985) Dissolution kinetics of dolomite: Effect of lithology and fluid
1453 flow velocity. Geochim. Cosmochim. Acta 49, 2017-2026.
1454 Lüttge, A., Winkler, U. and Lasaga, A.C. (2002) Interferometric study of the dolomite dissolution: A
1455 new conceptual model for mineral dissolution. Geochim. Cosmochim. Acta 67, 1099-1116.
1456 Orton, R. and Unwin, P.R. (1993) Dolomite dissolution at low pH: a channel-flow study. J. Chem. Soc.
1457 Faraday Trans. 89, 3947-3954.
1458 Pokrovsky, O.S., Schott, J. and Thomas, F. (1999) Dolomite surface speciation and reactivity in aquatic
1459 systems. Geochim. Cosmochim. Acta 63, 3133-3143.
1460 Pokrovsky, O.S. and Schott, J. (2001)
1461 Pokrovsky, O.S., Golubev, S.V. and Schott, J. (2005) Dissolution kinetics of calcite, dolomite and
1462 magnesite at 25 ºC and 0 to 50 atm pCO2. Chem. Geol. 217, 239-255.
1463
1464
79

1465 Table Do1: Summary of experimentally measured dolomite steady-state dissolution rates
Dolomite 5-65 1-10 Busenberg and Plummer (1982)
Dolomite 25 2.5-9.5 Chou et al. (1989)
Dolomite Deike (1990)
Dolomite 25 4 Herman and White (1985)
Dolomite 25-80 -0.4-4.2 Gautelier et al. (1999)
Dolomite 80 6.5-7.2 Gautelier et al. (2007)
Dolomite 25 3 Lüttge et al. (2002)
Dolomite 25 3-4 Orton and Unwin (1993)
Dolomite Pokrovsky et al. (2001)
Dolomite 25 Pokovsky et al. (2003)
1467
1468 Figure Do1: Summary of experimentally measured dolomite steady-state dissolution rates
1470 dashed line.
80

-6 Busenberg and Plummer

(1982)
-7 Chou et al. (1989)
Deike (1990)
-8
Herman and White (1985)
log r+ (mol/cm2/s)
-9
Gautelier et al. (1999), 25
C
-10 Gautelier et al. (1999), 80
C
-11 Gautelier et al. (2006), 80
C
Luttge et al. (2002)
-12
-13
-14 Model, 25 C
-1 1 3 5 7 9 11
Model, 80 C
pH
1471
1472
81

1473 Enstatite
1474
1475 Dissolution rates of enstatite (MgSiO3) at 25 ºC and various pH have been published
1476 by Luce et al., (1972), Schott et al., (1981), Ferruzzi (1993), Siegel and Pfannkuch (1984), and
1477 Halder and Walther (2011). The rates are presented as a function of pH in Figure E1, other
1478 than the pH 4.1 rate reported by Siegel and Pfannkuch (1984). This rate was removed from
1479 the dataset because stoichiometric metal release was not observed in this experiment.
1480 Steady-state enstatite dissolution rates were reported as function of aqueous

1481 magnesium and silica activity, pH from 1 to 11, and temperature from 28° to 168° C by
1482 Oelkers and Schott (2001). These authors fit their data to
1483 ( ) ( ) (E1)
1484 where r+ signifies the enstatite steady state dissolution rate, AA refers to a pre-exponential
1485 factor equal to 4.x10-6 mol/cm²/sec, EA designates an activation energy equal to 48.5 kJ/mol,
1487 this equation describes the dissolution rates reported in the literature can be assessed in
1488 Figure E1. Rates calculated using Equation E-1 described 12 of 14 reported 25 C rates within
1489 0.8 log units with an average uncertainty of 0.2 log units.
1490
1491 References
1492
1493 Halder S. and Walther, J.V. (2011) Far-from-equilibrium enstatite dissolution rates in alkaline
1494 solutions at earth surface conditions. Geochim. Cosmochim. Acta, 76, 7486-7493.
1495 Luce, R.W., Bartlett, W.B., and Parks, G.A. (1972) Dissolution kinetics of magnesium silicates.
1496 Geochim. Cosmochim. Acta, 36, 35-50.
1497 Oelkers, E. H. and Schott, J. (2001) An experimental study of enstatite dissolution rates as a function
1498 of pH, temperature, and aqueous Mg and Si concentration, and the mechanism of
1499 pyroxene/pyroxenoid dissolution. Geochim. Cosmochim. Acta, 65, 1219-1231.
82
1500 Schott, J., Berner, R.A. and Sjoberg, E.L. (1981) Mechanism of pyroxene and amphibole weathering -
1501 I. Experimental studies of iron-free minerals. Geochim. Cosmochim. Acta, 45, 2123-2135.

1502 Siegel, D.I. and Pfannkuch, H.O. (1984) Silicate mineral dissolution at pH 4 and near standard
1503 temperature and temperature, Geochim. Cosmochim. Acta, 48, 197-201.
1504
1505
1506 Table E1: Summary of experimentally measured enstatite steady-state dissolution rates
range
Enstatite 25 1,6 Luce et al. (1972)
Bramble Enstatite 25 1-6 Schott et al. (1981)
Enstatite 25 4,1 Siegel and Plannkuch (1984),
Enstatite 25 2-7 Ferruzzi (1993)
Bramble Enstatite 28-160 2-11 Oelkers and Schott (2001)
Enstatite 25 8-13 Halder and Walther (2011).
1508
1509 Figure E1: Summary of experimentally measured enstatite steady-state dissolution rates
-12
Feruzzi (1993)
-13 Halder and Walther (2011)

log r+ (mol/cm2/s)
Luce et al. (1972)
-14 Oelkers and Schott (2001), 28 C
Oelkers and Schott (2001), 70 C


-16
Model, 25 C
Model, 70 C
-17
83 0 2 4 6 8 10 12 14
pH
1512

1513 Epidote
1514
1515 The dissolution kinetics of epidote (Ca2FeAl2Si3O12OH) was investigated at high

1516 temperature (250-350 ºC) and high-pressure (0.5-12 kbar) conditions by several authors
1517 including Blanchard (1994) and Brandon et al. (1996). Experimental studies at ambient
1518 temperature and atmospheric pressure were conducted by Nickel (1973) at pH of 0.2 to
1519 10.6, Sverdrup (1990) at pH ranging from 3 to 10.5, Rose (1991) at pH of 1.3 to 5.5 and
1520 Kalinowski et al. (1998) a pH ranging from 1 to 6. The experimental conditions where those
1521 experiments were conducted are reported in Table Ep1 and the available experimental rates
1522 at 25 ºC are plotted in Fig. Ep1
1523 The variation of epidote dissolution rates on pH and the presence of substantial
1524 aluminum in the epidote structure suggests that its rates may depend on aqueous aluminum
1525 concentration in a manner similar to aluminosilicates, e.g. albite. Nevertheless owing to the
1526 dearth of direct measurements of the effect of aqueous aluminum on epidote dissolution
1527 rates the fit of Palandri and Kharaka (2004) has been adopted in this study. This fit is
1528 expressed by :
1529 ( )
1530 ( )
1531 ( )
1532
1533 where rH+, rH2O and rOH- signifies the almandine forward dissolution rate in acidic, neutral
1534 and basic solutions and r+ the total dissolution rate, AA, AB and AC refer to pre-exponential
1535 factors equal to 7.244x10-3, 2.51x10-4 and 3.38x10-8 mol/cm²/s respectively, EA, EB and EC
1536 designate activation energies equal to 71.1, 70.7, and 79.1 kJ/mol, R represents the gas
1537 constant, and T denotes absolute temperature. The degree to which this equation describes
1538
84 the dissolution rates reported in the literature can be assessed in Figure Ep1. Rates
1539 calculated using Equation Ep-1 described 37 of 40 reported rates within 0.8 log units.
1540

1541 References
1542
1543 Blanchard, I.G. (1994) Epidote dissolution kinetics: An experimental study at 250 ºC and 500 bars
1544 between pH 6.4 and pH 12. M. Sc. Thesis, University of Leeds, UK.
1545 Brandon, A.D., Creaser, R.A. and Chacko, T. (1996) Constraints on rates of granitic magma transport
1546 from epidote dissolution kinetics. Science 271, 1845-1848.
1547 Kalinowski, B.E., Faith-Ell, C., Schweda, P. (1998) Dissolution kinetics and alteration of epidote in
1548 acidic solutions at 25 ºC. Chem. Geol., 151, 181-197.
1551 Rose, N.M. (1991) Dissolution rate of phrenite, epidote and albite. Geochim. Cosmochim. Acta, 55,
1552 3273-3286.
1555
85

1556 Table Ep1: Summary of experimentally measured epidote steady-state dissolution rates
Epidote 250 6.4 - 12 Blanchard (1994)
Epidote 250-350 xxxxx Brandon et al. (1996)
Epidote 25 2-6.5 Kalinowski et al. (1998)
Epidote 25 0.2-10.6 Nickel (1973)
Epidote 25 1.3-5.5 Rose (1991),
Epidote 25 3-10.5 Sverdrup (1990).
1558
1559 Figure Ep1: Summary of experimentally measured epidote steady-state dissolution rates
-12
Kalinowski (1998)
Nickel (1973)
-13
Rose (1991), 25 C
log r+ (mol/cm2/s)
-14 Rose (1991), 70 C
Rose (1991), 90 C
-15
Sverdrup (1990)
-16 Model 25 C (Palandri

and Kharaka, 2004)
-17 and Kharaka, 2004)
0 2 4 6 8 10 12
pH
1562
86

1563 Fayalite and other non-forsteric olivines

1564
1565 Owing to their relative rarity, relatively few studies have characterized the dissolution
1566 rates of the non-forsteritic olivines. The most common of these is fayalite (Fe 2SiO4) the iron
1567 end member of this mineral family. The study of fayalite dissolution kinetics is confounded
1568 by the oxidation of aqueous divalent iron at neutral to basic conditions. Fayalite dissolution
1569 kinetics were studied by Siever and Woodford (1979), Schott and Berner (1983), Siegel and
1570 Pfannkuch (1984), and Westrich et al. (1993). Of these studies only Siever and Woodford
1571 (1979) and Westrich et al. (1993) reported rates and only at pH 2 and 4.5 at 25 ºC. This
1572 limited dataset precludes a quantitative fit of the rate data for this mineral.
1573 Westrich et al. (1993) also reported dissolution rates for a variety of other divalent
1574 metal olivines at acidic pH and temperatures ranging from 25 to 45 ºC. The dissolution rates
1575 of each of these minerals exhibit similar behaviors over the condition studied. Each had
1576 activation energy of 56± 6 kJ/mol and each had 25 ºC dissolution rates that decreased by
1577 ~0.5 orders of magnitude with each pH unit increase in acid conditions. These behaviors are
1578 identical within uncertainty to those of forsterite (see below). The observation of Westrich
1579 et al (1993), suggests that the dissolution rates of all olivines as a function of temperature
1580 and pH can, at least provisionally, be considered proportional to those of forsterite. This
1581 observation was thus adopted in this study to estimate the dissolution rates of the non
1582 forsteritic olivines.
1583 Non-forsteritic olivines dissolution rates were calculated from
1584 (Fay1)
1585 where ra and rH2O refer to rates of two distinct dissolution pathways, a pH dependent
1586 pathway that dominates at pH<9 and a pH independent pathway that dominates at higher
1587 pH. These two rate equations are given by
1588  
ra  Aa s exp  E A , a / RT a H0.5 (Fay2)
87
1589 and
1590 rH 2O  AH 2O s exp  E A ,H 2O / RT  (Fay3)

1591 where AA ,a and AA ,H 2O represent pre-exponential factors listed in Table Fay2, and E A ,a
1592 and E A ,H 2O designate activation energies equal to 55.38 and 71.20 kJ/mol, R represents the
1593 gas constant, and T denotes absolute temperature. These activation energies are those of
1594 generated by a fit of the forsterite rate data (see below), whereas the pre-exponential
1595 factors were calculated such that dissolution rates of each olivine were proportional to that
1596 of forsterite and consistent with the rates reported by Westrich et al (1993). Examples of the
1597 results of these fits are shown in Fig Fay1 and Fay2.
1598
1599 References
1600
1603 2004-1068.
1604 Schott, J. and Berner, R.A (1983). X-ray photoelectron studies of the mechanism of iron silicate
1605 dissolution during weathering. Geochim. Cosmochim. Acta 47, 2233-2240.
1608 Siever, R. and Woodford, N. (1979) Dissolution kinetics and the weathering of mafic minerals.
1610 Westrich, H.R., Cygan, R.T.,m Casey, W.H., Zemitis, C., and Arnold, G.W. (1993) The dissolution
1611 kinetics of mixed-cations orthosilicate minerals.
88

1612 Table Fay1: Summary of experimentally measured fayalite steady-state dissolution rates
1613 reported in the literature. N/R refers to not reported.
range
Fayalite 25 N/R Schott and Berner (1983)
Fayalite 22 N/R Siegel and Pfannkuch (1984)
Fayalite 25 4.5 Siever and Berner (1979)
1614
1615 Table Fay2: Summary of experimentally measured fayalite steady-state dissolution rates
Mineral Pre-exponential factor Pre-exponential factor Composition

AA (mol/cm2/s) AH2O (mol/cm2/s)
Calcio-olivine 3.51x10-2 1.01x105 Ca2SiO4
Co-olivine 1.11x10-6 3.19x102 Co2SiO4
Fayalite 4.42x10-4 1.27x103 Fe2SiO4
Kirschsteinite 1.40x10-2 4.02x104 CaFeSiO4
Liebenbergite 1.76x10-7 5.06x10-1 Ni2SiO4
Monticellite 4.42x10-4 1.27x103 CaMgSiO4
Phenacite 2.21x10-8 6.36x10-2 BeSiO4
Tephroite 1.73x10-3 3.7x103 Mn2SiO4
Willemite 1.11x10-6 3.19x102 ZnSiO4
1617
1618
1619
1620
89
1621
1622

1623 Figure Fay1: Summary of experimentally measured non forsteritic olivine steady-state
1624 dissolution rates reported in the literature at 25 ºC as a function of pH. The results of the
1625 model are plotted as the dotted line. All data were from Westrich et al. (1993) unless
1626 otherwise specified. The dissolution rate of Co-forsterite at pH 6, 25 C, shown in the Fig was
1627 taken from Fig 4 of Westrich et al. (1993) rather than from their table in annex 1. The later
1628 value is inconsistent with the trend of the data and appears to be a typographical error.
-8 Siever and Woodfort (1979)

Ca2SiO4
25 ºC
Model Ca2SiO4
-9
Co-Olivine
Model Co-Olivine
-10
Co1.5Mg0.5SiO4
log r+ (mol/cm2/s)
CoMnSiO4
-11 Kirschsteinite
Model Kirschsteinite
-12 Fayalite
Liebenbergite
-13 Model Liebenbergite
Monticellite
-14 Model Monticellite

Phenacite
Model Phenacite
-15
Tephroite
1 3 5 7 9
Model Tephroite
pH
1629 Willemite
1630
90

1631 Figure Fay2: Summary of experimentally measured non forsteritic olivine steady-state
1632 dissolution rates at 25 ºC and pH 2. The results of the models are plotted as various line,
1633 forsterite, the solid line is given as a reference.
-6 Ca2SiO4
Model Ca2SiO4
-7
Co-Olivine
-8
Model Co-Olivine
-9 Fayalite
log r+ (mol/cm2/s)
Model Fayalite
-10
Forsterite
-11 Model Forsterite
-12 Kirschsteinite
Model Kirschsteinite
-13
Liebenbergite
-14 Model Liebenbergite
Phenacite
-15
Model Phenacite
-16 Tephroite
1 1,5 2 2,5 3
Model Tephroite
pH
Willemite
1634
91

1635 Fluorite and other divalent metal fluorides.

1636
1637 The halide mineral fluorite (CaF2) dissolution has been studied by gardner and
1638 Nancollas (1976), Hamza et al. (1987), Christoffersen et al. (1988), Zang and Nancollas
1639 (1990), Hamza and Hamdona (1991), Bosbach et al. (1995), De Giudici et al. (2004), Zhang et
1640 al. (2005) and Cama et al. (2010). Zang and Nancollas (1990) reported rate parameters at 25
1641 ºC, including an activation energy, Hamza and Hamdona reported rates at 25 ºC in NaCl
1642 solutions and Bosbach et al. (1995) reported direct AFM observation of fluorite dissolution
1643 but did not report rates. De Giudici measured the fluorite dissolution kinetics at 25 ºC and
1644 from pH 2, Zhang et al. (2005) studied the dissolution rate of fluorite in flow through reactor
1645 at 25 ºC and pH from 3.2 to 3.6 and Cama et al. (2010) reported rates measured with flow
1646 through systems, VSI and AFM at 25 ºC and pH ranging from 1.1 to 3.0. The experimental
1647 conditions where those experiments were conducted are reported in Table Flu1 and the
1648 available experimental rates at 25 ºC are plotted in Fig. Flu1. The reported data was fitted to
1649 ( ) Flu1
1650 where r+ signifies the fluorite steady-state dissolution rate in acidic solutions, AA refers to
1651 pre-exponential factors equal to 1.51x103 mol/cm²/s, EA designates an activation energy
1653 An EA of 73.0 kJ/mol was reported by Zhang and Nancollas (1990) based on Gardner and
1654 Nancollas (1976) but we recalculated the EA to be 9.87 kJ/mol based on the data provided by
1655 Zhang et al. (2005). The degree to which this equation describes the dissolution rates
1656 reported in the literature can be assessed in Figure Flu1. Rates calculated using Equation Flu-
1657 1 described 20 of 26 reported rates within 0.8 log units.
1658
1659
92

1660 References
1661
1662 Abdul-Rahman, A. (1988) The Kinetics of Crystal Growth and Dissolution of Magnesium and
1663 Strontium Fluoride Salts. The Effect of Additives. Ph.D. Thesis, State University of New York at
1664 Buffalo.
1665 Cama, J., Zhang, L. Soler, J.M., De Giudici, G., Arvidson, R.S. and Lüttge, A. (2010) Fluorite dissolution
1666 at acidic pH: In situ AFM and ex situ VSI experiments and Monte Carlo simulations. Geochim.
1667 Cosmochim. Acta 74, 4298-4311.
1668 De Guidici, G., Biddau, R., D’inco, M., Leoni, M. and Scardi, P. (2005) Dissolution of nanocrystalline
1669 fluorite powders: An investigation by XRD and solution chemistry. Geochim. Cosmochim.
1670 Acta 69, 4073-4083.
1671 Gardner, G.L. and Nancollas, G.H. (1976) The kinetics of crystal growth and dissolution of calcium and
1672 magnesium fluoride. J. Dent. Res. 55, 342-352.
1675 2004-1068.
1676 Zhang J. W. and Nancollas G. H. (1990) Mechanisms of growth and dissolution of sparingly soluble
1677 salts. In Mineral-Water Interface Geochemistry (eds. M. F. Hochella, Jr. and A. F. White).
1678 Mineralogical Society of America, Washington, D.C. pp. 365-396.
1679 Zhang, R., Hu, S., and Zhang, X. (2006) Experimental study of dissolution rates of fluorite in HCl-H2O
1680 solutions. Aq. Geochem. 12, 123-159.
1681
1682 Table Flu1: Summary of experimentally measured fluorite steady-state dissolution rates
range
Fluorite 25 1-3 Cama et al. (2010)
Fluorite 25 2 De Giudici et al. (2004)
Fluorite 25 6.5 Hamzam and Hamdona (1991)
Fluorite 25 3.2-3.6 Zhang et al. (2005)
1684
93
1685

1686 Table Flu2: Summary of activation energies and pre-exponential parameters for earth
1687 fluorides reported in the literature.
Mineral AA(mol/cm2/s) EA(kJ/mol) Reference
Sellaite (MgF2) 86.0 Abdul-Rahman (1988)
Fluorite (CaF2) 9.8 9.87 This study
SrF2 72.0 Abdul-Rahman (1988)
1688
1689 Figure Flu1: Summary of experimentally measured fluorite steady-state dissolution rates
1690 reported in the literature at 25 ºC as a function of pH. The results of the model are plotted as
1691 the dotted line.
-9,00 Cama et al. (2010), AFM
-9,50 Cama et al. (2010), VSI
-10,00 Cama et al. (2010), Flow

thru
log r+ (mol/cm2/s)
-10,50 De Giudici et al. (2004)
-11,00 Hamzam and Hamdona

(1991)
-11,50 Zhang et al. (2005), 25 C
-12,00 Zhang et al. (2005), 100 C
-12,50 Model, 25 C
-13,00 Model, 100 C

1 2 3 4 5 6 7
pH
1692
1693
94

1694 Forsterite
1695
1696 A larger number of studies have focused on characterizing the dissolution rates of
1697 forsterite (Mg2SiO4) – see table F1. The variation of 25 ºC forsterite dissolution rates are
1698 depicted as a function of pH in Fig F1. There is a general consistency of the rates reported in
1699 most of the published studies. The two notable exceptions are Grandstaff (1978, 1986)
1700 which are approximately two orders of magnitude lower than the corresponding values
1701 reported in more recent studies, and those of Blum and Lasaga (1988) which in contrast to
1702 all of the other studies suggest that forsterite dissolution rates increase with increasing pH at
1703 basic conditions. In contrast to numerous other divalent metal silicates, the dissolution rates
1704 of forsterite appear to be independent of aqueous Mg concentration at far-from-equilibrium
1705 conditions. This observation was attributed to the fact that there are no Si-O-Si linkages in its
1706 structure (Oelkers, 2001). Several different approaches have been proposed to fit forsterite
1707 dissolution rates as a function of temperature and solution composition. Pokrovsky and
1708 Schott (2000) proposed a surface speciation model to describe these rates. In contrast, Olsen
1709 and Rimstidt (2008) and Hänchen et al. (2006) used an empirical model assuming constant
1710 temperature rates are solely a function of pH in the absence of organic species. This later
1711 assumption was validated by Declercq et al. (2013) who observed little effect of the
1712 presence of 13 aqueous organic ligands on forsterite dissolution rates.
1713 The lack of parameters describing the surface speciation of forsterite surfaces at
1714 elevated temperatures precludes the general application of the Pokrovsky and Schott (2000)
1715 model to describe forsterite dissolution at present. As such an empirical approach has been
1716 adopted to describe these rates. Forsterite dissolution rates have been assumed to follow
1717 two parallel reaction paths in accord with
1718 (F1)
1719 where ra and rH2O refer to rates of two distinct forsterite dissolution pathways, a pH
1720 dependent pathway that dominates at pH<9 and a pH independent pathway that dominates
1721 at higher pH. These two rate equations are given by
95
1722  
ra  Aa s exp  E A , a / RT a H0.5 (F2)

1723 and
1724 rH 2O  AH 2O s exp  E A ,H 2O / RT 
1725 where AA ,a and AA ,H 2O represent to a pre-exponential factors equal to 1.11x10-5 and 31.88
1726 mol/cm²/s, respectively, and E A ,a and E A ,H 2O designate activation energies equal to 55.38
1727 and 71.20 kJ/mol, R represents the gas constant, and T denotes absolute temperature.
1728 These parameters were obtained using a least squares fit of the data illustrated in Fig. F1-3.
1729 The degree to which this equation describes the dissolution rates reported in the literature
1730 can be assessed in these figures. Rates calculated using Equation F-1 to F3 described 54 of 60
1731 reported rates within 0.8 log units.
1732
1733 References
1734
1735 Awad A., Van Groos, A.F.K., Guggenheim, S. (2000) Forsteritic olivine: Effect of crystallographic
1736 direction on dissolution kinetics. Geochim. Cosmochim. Acta 64, 4765-4772.
1737 Blum, A., and Lasaga, A. (1988) Role of surface speciation in the low temperature dissolution of
1738 minerals. Nature 331, 431-433
1739 Bailey, A. (1974) Effect of temperature on the reaction of silicates with aqueous solutions in the low
1740 temperature range. First International Symposium on Water-Rock interactions. 1976, Praha,
1741 375-380.
1742 Chen Y. and Brantley S. L. (2000) Forsterite dissolution at 65°C and 2< pH< 5. Chem. Geol. 165, 267–
1743 281.
1744 Declercq, J., Bosc, O., and Oelkers, E.H. (2013) Do organic ligands affect forsterite dissolution rates?
1745 Geochim. Cosmochim. Acta, accepted.
1746 Golubev, S.V., Pokovsky, O.S. and Schott, J. (2005) Experimental determination of the effect of
1747 dissolved CO2 on the dissolution kinetics of Mg and Ca silicates at 25 ºC. Chem. Geol. 217,
1748 227-238.
1749 Grandstaff, D.E. (1978) Changes in surface area and morphology and the mechanism of forsterite
1750 dissolution. Geochim. Cosmochim. Acta 42, 1898-1901.
1751
96 Grandstaff, D.E. (1986) The dissolution rate of forsteritic olivine from Hawaiia beach sand. In Rates of
1752 Chemical Weathering of Rocks and Minerals (eds. S.M. Colman and D.P. Dethier)); Academic
1753 Press.

1754 Hänchen, M., Prigiobbe, V., Storti, G., Seward, T.M., Mazzotti, M. (2006) Dissolution kinetics of
1755 forsteritic olivine at 90-150 ºC including effect of the presence of CO2. Geochim. Cosmochim.
1756 Acta 70, 4403-4416.
1757 Jonckbloedt, R.C.L. (1997) Olivine dissolution in sulphuric acid at elevated temperatures –
1758 implications for the olivine process, an alternative waste acid neutralizing process. J.
1759 Geochem. Exploration 62, 337-346.
1760 Luce, R.W., Barlett, R.W., and Parks, G.A. (1972). Dissolution kinetics of magnesium silicates.
1762 Oelkers, E.H. (2000) An experimental study of forsterite dissolution kinetics as a function of
1763 temperature and aqueous Mg and Si concentration. Chem. Geol. 175, 485-494.
1764 Olsen, A.A. (2007) Forsterite dissolution kinetics: Applications and implications for chemical
1765 weathering. Ph.D. Thesis, Blacksburg, Virginia.
1766 Olsen, A.A. and Rimstidt, J.D. (2008)Oxalate-promoted forsterite dissolution at low pH. Geochim.
1767 Cosmochim. Acta 72, 1758-1766.
1768 Pokrovsky O.S. and Schott, J. (2000) Kinetics and mechanism of forsterite dissolution at 25 ºC and pH
1769 from 1 to 12. Geochim. Cosmochim. Acta 64, 3313-3325.
1770 Prigiobbe, V., Costa, G., Baciocchi, R., Hänchen, M. and Mazzotti, M. (2009) The effect of CO2 and
1771 salinity on olivine dissolution kinetics at 120 ºC. Chem. Eng. Sci. 64, 3510-3515.
1772 Rosso and Rimstidt (1999) A high resolution study of forsterite dissolution rates. Geochim.
1773 Cosmochim. Acta 64, 797-811.
1774 Van Herk, J., Pietersen, H.S. and Schuiling, R.D. (1989) Neutralization of industrial waste acids with
1775 olivine – The dissolution of forsteritic olivine at 40-70 ºC. Chem. Geol. 76, 341-352.
1776 Westrich et al. (1993)
1777 Wogelius, R.A. and Walter, J.V. (1991) Forsterite dissolution at 25 ºC: Effects of pH, CO2, and organic
1778 acids. Geochim. Cosmochim. Acta 55, 943-954.
1779 Wogelius, R.A. and Walter, J.V. (1992) Forsterite dissolution kinetics at near surface conditions.
1780 Chem. Geol. 97, 101-112.
1781
1782
97

1783 Table F1: Summary of experimentally measured forsterite steady-state dissolution rates
Forsterite 25 2 Awad et al. (2000)
Forsterite 25-65 4 Bailey (1974)
Forsterite 25 1.8-11.35 Blum and Lasaga (1988)
Forsterite 65 2-5 Chen and Brantley (2000)
Forsterite 25 1.95-11.85 Golubev et al. (2005)
Forsterite 1-46 3-5 Grandstaff (1978)
Forsterite 25 2 Grandstaff (1986)
Forsterite 90-150 2-10.59 Hänchen et al. (2006)
Forsterite 25 2 Jonckbloedt et al. (1997)
Forsterite 25 1.66-9.58 Luce et al. (1972)
Forsterite 25-65 2 Oelkers et al. (2000)
Forsterite 25 0.6-6.5 Olsen and Rimstidt (2008)
Forsterite 120 Prigiobbe et al. (2009)
Forsterite 25 1.03-12.06 Pokrovsky and Schott (2000)
Forsterite 25-45 1.8-3.8 Rosso and Rimstidt (2000)
Dunnite 25 4 Siegel and Pfannkuch (1984)
Forsterite 40-70 1-3 Van Herk et al. (1989)
Forsterite 25 1.9-6 Westrich et al. (1993)
Forsterite 25-65 1.8-9.8 Wogelius and Walther (1991)
1785
1786
98

1787 Figure F1: Summary of experimentally measured forsterite steady-state dissolution rates
1789 the dashed line.
-10,00 Awad et al. (1999)
25 ºC Bailey (1976)
Blum and Lasaga (1988)
-11,00
Golubev et al. (2005)
Grandstaff (1978)
-12,00 Grandstaff (1986)
log r+ (mol/cm2/s)
Jonckbloedt (1997)
-13,00 Luce et al. (1972a)

Oelkers (2000)
Olsen and Rimstidt (2008)
-14,00
Pokrovsky and Schott (2000)
-15,00 Rosso and Rimstidt (2000)
Westrich et al. (1993)
-16,00
Wogelius and Walter (1991)
Wogelius and Walter (1991)
-17,00 Wogelius and Walther (1991b)
1 3 5 7 9 11 Wogelius KHP
pH Model Declercq
1790
1791 Figure F2: Summary of experimentally measured forsterite steady-state dissolution rates
1793 the dashed line.
-9
Chen and Brantley
65 ºC (2000)
-10
Wogelius and
log r+ (mol/cm2/s)
Walther (1992)
-11
Van Herk (1989)
-12
Bailey (1976)
-13
Model Declercq
-14
99 1 3 5 7 9
pH
1794
1795

1796 Figure F3: Arrhenius plot of the data reported at pH 2 and used to calculate EA and AA.
-8
Chen and Brantley (2000)
pH 2
Hänchen et al. (2006)
-9
log r+ (mol/cm2/s)
-10 Rosso and Rimstidt (2000)
Awad et al. (1999)
-11 Blum and Lasaga (1988)
Jonckbloedt (1997)
-12
y = -3718,6x + 0,5035
Linear (fit)
-13
0,002 0,0025 0,003 0,0035 0,004
1/T (K)
1797
1798
100

1799 Glauconite
1800
1801 Glauconite (K0.6Na0.05Fe1.3Mg0.4Fe0.2Si3.8O10(OH)2) is an hydrated iron-rich micaceous

1802 clay mineral of the mica group. Glauconite dissolution was studied by Cloos et al. (1960). A summary
1803 of the published measurements conditions are presented in Table Gla1 and the existing rates
1804 are depicted in Fig. Gla1.
1805 Assuming a similar dissolution mechanism for micas the dissolution rate data
1806 obtained were fitted to :
1807 ( )( )
(Gla-1)
1808 where r+ signifies the biotite steady state dissolution rate, AA refers to a pre-exponential
1809 factor equal to 1x10-7 mol/cm²/s, EA designates an activation energy equal to 49.0±2 kJ/mol,
1810 R represents the gas constant, and T denotes absolute temperature and n signifies a
1811 stoichiometric coefficient equal to 0.125. In the absence of enough available data the
1812 different parameters of Eqn. Gla-1 were taken from the glauconite equation Gla-1. The
1814 be assessed in Figure Gla1. Rates calculated using Equation Gla-1 described xx of xx reported
1815 rates within 0.8 log unit.
1816
1817 References
1818
1819 Cloos, P., Gastuche, M.C., and Croegart, M. (1960) Cinétique de la destruction de la glauconite par
1820 l’acide chlorhydrique, étude préliminaire. International Geological Congress XXI 24, 35-50.
1821
1822 Table Gl1: Summary of experimental conditions for the various glauconite steady-state
101 range
Glauconite 25 Cloos et al. (1960)

1824
1825 Figure Gla1: Summary of experimentally measured glauconite steady-state dissolution rates
1827 dashed line.
-10
-11 25 ºC
-12
log r+ (mol/cm2/s)
-13
-14
-15
-16
-17 Model
-18
-19
-20
1 3 5 7 9
pH
1828
102

1829 Glaucophane
1830
1831 Sverdrup (1990) reported the dissolution rates of glaucophane

1832 (Na2Mg3Al2Si8O22(OH)2) , a Na bearing amphibole at 25 ºC and pH ranging from 3.1 to 6.8.
1833 These experiments are summarized in Table Gl1 and plotted on Fig. Gl1.
1834 In the absence of extensive rate data, the dissolution rates of glaucophane were
1835 assumed to follow a similar behavior to that of hornblende, in accord with:
1836 ( )( ) Gl-1
1837 where r+ signifies the glaucophane steady state dissolution rate, AA refers to a pre-
1838 exponential factor equal to 9.8x10-2 mol/cm²/s, EA designates an activation energy equal to
1839 55.8 kJ/mol, R represents the gas constant, T denotes absolute temperature, n signifies a
1840 stoichiometric coefficient equal to 0.3. By structural analogy, the EA was set to be equal to
1841 that of anthophyllite, the only amphibole for which there is sufficient temperature
1842 dependent data to constrain an Arrhenius plot. Owing to the dearth of rate data for
1843 glaucophane this rate equation is preliminary at best, and should be only used with caution.
1844 AA was recalculated to fit the Sverdrup (1990) glaucophane data. The degree to which this
1845 equation describes these dissolution rates can be assessed in Figure Gl1. Rates calculated
1846 using Equation Gl-1 described 3 of 4 reported rates to within 0.2 log units.
1847
1848 References
1849
103

1852 Table Gl1: Summary of experimentally measured glaucophane steady-state dissolution rates
Glaucophane 25 3 – 6.8 Sverdrup (1990)
1854
1855 Figure Gl1: Summary of experimentally measured glaucophane steady-state dissolution rates
1857 dotted line.
-10
25 ºC
-11
log r+ (mol/cm2/s)
-12
-13
-14 Sverdrup (1990)

Model
-15
-16
0 2 4 6 8 10
pH
1858
104

1859 Gibbsite
1860
1861 Gibbsite is one of the mineral forms of aluminum hydroxide and one of the three
1862 minerals making up the rock bauxite. Due to its importance for the industry as one of the
1863 main aluminum ore the dissolution kinetics of gibbsite have been investigated by many
1864 authors since the 1930s. Early dissolution experiments carried were carried out by Clay and
1865 Thomas (1938) showed that the dissolution rate of hydrous alumina in 0.2 M HCl is strongly
1866 increased in moderate concentration of some anions (i.e. fluoride, phosphate, phosphite,
1867 oxalate and sulphate). They recognized that those effects are due to the formation of a rate-
1868 determining complex on the surface of the mineral. Experimental studies by Scoford and
1869 Glastonbury (1971, 1972), Packter and Dhillon (1973) and Peric’ et al. (1985) demonstrated
1870 that the dissolution kinetics of gibbsite has a first order dependence on NaOH concentration
1871 in the strongly alkaline solutions (pH>13.25) relevant to the Al-mining industry.
1872 Packter and Dhillon (1969) also carried out dissolution experiments in acidic solutions
1873 at constant molar concentrations and showed that the dissolution rates depends on the type
1874 of acid, with faster rates in H2SO4, intermediate rates in HCl and slower rates un HClO4.
1875 Bloom (1983) measured the dissolution rate of two synthetic gibbsite samples at 25 ºC in
1876 HNO3 solutions with pH varying from 1.5 to 3.2. This work was then updated by Bloom and
1877 Erich (1987) measuring the dissolution kinetics at 25 ºC in the pH interval 1.7-3.9. Nagy and
1878 Lasaga (1992) studied dissolution and precipitation rates of gibbsite at 80 ºC and pH 3 as a
1879 function of chemical affinity. More recently Mogollón et al. (1996) measured the dissolution
1880 rate of natural gibbsitic bauxite in HClO4 solutions at 25 ºC using column reactors in the pH
1881 range 3.3 to 3.9. Mogollón et al. (1999) build upon their previous study by analyzing the
1882 dissolution kinetics of gibbsite at 25 ºC and 3.5 < pH < 4.5. Ridley et al. (1997) carried out far-
1883 from-equilibrium dissolution experiments of gibbsite at 5 ºC and near constant pH (=2). They
1884 showed that the dissolution kinetic of gibbsite in H2SO4-NaCl solutions are nearly 10 times
1885 faster than in HCl-NaCl solutions. Ganor et al. (1999) performed far from equilibrium
1886 dissolution experiments of synthetic gibbsite both in a stirred flow through reactor and in a
1887 column reactor at 25 ºC and outlet pH values from 2.5 to 4.1. Dietzel and Böhme (2005)
1888 measured the gibbsite dissolution rates at 20 ºC under both far-from-equilibrium and close-
1889 to-equilibrium conditions, by using both batch and flow-through reactors from pH 2 to 6.
1890 The data was fitted to the following equation:

1/ 3
 a2 
1891 r  AA exp  E A / RT   H  Gl-1
 a 2 
 Mg 
105
1892 where r signifies the glaucophane steady state dissolution rate, AA refers to a pre-
1893 exponential factor equal to 3.9x10-3 mol/cm²/sec, EA designates an activation energy equal
1894 to 56 kJ/mol, R represents the gas constant, and T denotes absolute temperature. AA and

1895 EA were estimated from the value of other amphibole. The degree to which this equation
1896 describes the dissolution rates reported in the literature can be assessed in Figure Ep1.
1897 Rates calculated using Equation Gl-1 described 4 of 4 reported rates within 0.1 log units with
1898 an average uncertainty of 0.1 log units.
1899 References
1900
106

1903 Goethite
1904
1905 The iron bearing oxide goethite (FeO(OH)) dissolution rate has been studied by
1906 Cornell et al. (1976) who reported rate at 20 ºC and pH 0.4, by Sidhu et al. (1981) at 25 ºC
1907 and pH 0.4, by Suter et al. (1991) at 25 ºC in the presence of 10-3 M oxalate. Ruan and Gilke
1908 (1995) reported rates as a function of temperature (30-50 ºC) and at pH 0.1 and Nowack and
1909 Sigg (1997) reported rates at 25 ºC in the presence of 1.2x10-5 M EDTA from pH 3.5 to 10. It
1910 can be noted that the values reported by Nowack and Sigg (1997) are inconsistent with the
1911 rest of the data, and thus was not included in the model. This inconsistency might stem from
1912 the use of EDTA in the experiment. The available data was fitted to:
1913 ( ) (Goe-1)
1914 where r+ the total dissolution rate, AA refers to a pre-exponential factors equal to 1.95x10-6
1915 and 3.02x10-9 mol/cm²/s respectively, EA designates an activation energy equal to 85.0
1916 kJ/mol, R represents the gas constant, and T denotes absolute temperature. EA was
1917 calculated by Palandri and Kharaka (2004) based on the values of Ruan and Gilke (1995). The
1919 be assessed in Figure Goe1. Rates calculated using Equation Goe-1 described 12 of 16
1920 reported rates within 0.8 log.
1921
1922 References
1923
1924 Cornell, R.M., Posner, A.M. and Quirk, J.P. (1976) Kinetics and mechanisms of the acid dissolution of
1925 goethite (et-FeOOH). J. Inorg. Nucl. Chem. 38, 563-567.
1926 Nowack, B. and Sigg, L. (1997) Dissolution of Fe(III) (hydr)oxydes by metal-EDTA complexes. Geochim.
1927 Cosmochim. Acta
1930
107 Ruan, H. D. and Gilkes, R. J. (1995) Acid dissolution of synthetic aluminous goethite before and after
1931 transformation to hematite by heating. Clay Minerals 30, 55-65.
1932 Sidhu, P.S., Gilkes, R.J., Cornell, R.M., Posner, A.M and Quirk, J.P. (1981) Dissolution of iron oxides
1933 and oxyhydroxides in hydrochloric and perchloric acids. Clays Clay Miner. 29, 269-276.

1934 Suter, D., Banwart, S. and Stumm, W. (1991) Dissolution of hydrous iron(III) oxydes by reductives
1935 mechanisms. Langmuir 7, 809-813.
1936
1937 Table Goe1: Summary of experimental conditions occurring during goethite steady-state
Goethite 20 0.4 Cornell et al. (1976)
Goethite 25 2.5-10 Nowack and Sigg (1997)
Goethite 30-50 0.1 Ruan and Gilkes (1995)
Goethite 25 0.4 Sidhu et al. (1981)
Goethite 25 2.2-5.8 Suter et al. (1991)
1939
1940 Figure Goe1: Summary of experimentally measured goethite steady-state dissolution rates
-10,00
Cornell et al. (1976)
-11,00
Nowack and Sigg

log r+ (mol/cm2/s)
-12,00
(1997)
-13,00 Ruan and Gilkes
(1995), 30
-14,00
Ruan and Gilkes
(1995), 50
-15,00
Sidhu et al. (1981)
-16,00
-17,00 Suter et al. (1991)

0 2 4 6 8 10
pH Model
1943
108

1944 Gypsum
1945
1946 Similar anhydrous analog, anhydrite, there is little quantitative dissolution rate data
1947 available for the hydrated calcium sulphate gypsum (CaSO4.2H2O). Also as was the case for
1948 anhydrite data are available for only a single pH at any given temperature. Dissolution rates
1949 were reported by Barton and Wilde (1971) at 25 ºC and pH 6, by Raines and Dewers (1997) at
1950 25 ºC and pH 6, Jeschke and Dreybrodt (2001) at 20 ºC and pH 6 and Colombani and Bert at
1951 20 ºC and pH 5.7. These rates are presented as a function of pH in Figure Gyp1. Owing to the
1952 scatter evident in these data any fit would be ambiguous, as such we have adopted the
1953 simple Arrhenius fit of anhydrite to describe gypsum dissolution (see above). Although this
1954 approach is preliminary at best, the rapid rates of gypsum dissolution likely lead this mineral
1955 to be close to equilibrium in most geologic systems of interest. As such the uncertainties
1956 associated with this preliminary fit will likely not impact significantly most geological
1957 calculations.
1959 literature can be assessed in Figure Gyp1. Rates calculated using Equation Gyp-1 described 9
1960 of 10 reported rates within 0.8 log units.
1961
1962 References
1963
1964 Barton A. F. M. and Wilde N. M. (1971) Dissolution rates of polycrystalline samples of gypsum and
1965 orthorhombic forms of calcium sulphate by the rotating disc method. Transactions of the
1966 Faraday Society 67, 3590-3597.
1967 Colombani, J., and Bert, J. (2007) Holographic interferometry study of the dissolution and diffusion of
1968 gypsum in water. Geochim. Cosmochim. Acta 71, 1913-1920.
1969 Jeschke, A.A., Vosbeck, K., and Dreybrodt, W. (2001) Surface controlled dissolution rates of gypsum
1970 in aqueous solutions exhibit nonlinear dissolution kinetics. Geochim. Cosmochim. Acta 65,
1971 27– 34.
109
1974 2004-1068.

1975 Raines, M. A. and Dewers, T. A. (1997) Mixed transport/reaction control of gypsum dissolution
1976 kinetics in aqueous solution and initiation of gypsum karst. Chem. Geol. 140, 29–48.
1977 Table Gyp1: Summary of experimentally measured gypsum steady-state dissolution rates
Gypsum 25 6 Barton and Wilde (1971)
Gypsum 20 5.7 Colombani and Bert (2007)
Gypsum 20 6 Jeschke and Dreybrodt (2002)
Gypsum 25 6 Raines and Dewers (1997)
1979
1980 Figure Gyp1: Summary of experimentally measured gypsum steady-state dissolution rates
-6
-7 Barton and Wilde

log r+ (mol/cm2/s)
(1971), 25 C
-8
Colombani and Bert
(2007), 20 C
-9
Jesche et al. (2001),
-10 20 C
Raines and Dewers
-11 (1997), 25 C
Model, 25 C
-12
0 2 4 6 8 10 12
pH
1983
110

1984 Hematite
1985
1986 The mechanism and rates of the dissolution of hydroxydes of trivalent ions and
1987 oxides of trivalent iron or partly containing it (e.g. magnetite and hematite) have been the
1988 subject of several studies. Cornell et al. (1976) reports hematite dissolution rates at 20 ºC
1989 and pH 0.4, Sidhu et al. (1981) reports rates at 25 ºC and pH 4. Banwart et al. (1989) report
1990 the results of an investigation of the effect of oxalate, acting as complex-former, and L-
1991 ascorbic acid, acting as reductant on the dissolution of hematite at pH 3, 25 ºC and ionic
1992 strength of 0.01 M, in a NaNO3-(HNO3) aqueous medium. The slowest dissolution
1993 mechanism was the proton promoted dissolution. The reductive dissolution, assisted by 10
1994 µM ascorbates proceeded faster than previous runs. The fastest dissolution mechanism was
1995 achieved by adding 100 µM ascorbate along with 50 µM oxalate. Suter et al. (1991)
1996 investigated the reductive dissolution of hematite assisted by ascorbate (10-4 M) in the pH
1997 range 2.5-6. Bruno et al. (1992) reported dissolution rates at 25 ºC in bicarbonate solutions.
1998 The dissolution of Fe(III) hydroxide in 4.8 x 10-2 M ascorbate was also investigated by Deng
1999 (1997) as a function of both pH, from 4.3 to 7.6, and temperature, from 20 to 60 ºC. He
2000 found that at 20 C the reductive dissolution rates are pH independent from pH 4.3 to 6. In
2001 contrast the rates decrease substantially with increasing pH in the pH interval 6-7.6. In
2002 agreement with what was observed by Suter et al. (1991). As shown by Deng (1997) these
2003 pH effects are consistent with the pH dependence of ascorbate adsorption onto Fe(III)
2004 hydroxide. The apparent activation energy resulted to be 27 kJ/mol at pH 6 and 47 kJ/mol at
2005 pH 7.5. Dos Santos and Stumm (1992) studied the reductive dissolution of hematite
2006 governed by H2S under constant PH2S of 10-4, 10-3 and 10-2 atm at 25 ºC and pH 3-7, below
2007 saturation with iron sulfide. Hematite dissolution proceeds very fast under these conditions.
2008 A study by Larsen and Postma (2001) reported rates at 25 C and pH 3.
2009 These experimental conditions are reported in Table Hem1 and the data points
2010 plotted on Fig. Hem1. The data was fitted by Palandri and Kharaka (2004) to the following
2011 equation:
111
2012 ( )
2013 ( )

2014
2015 where rH+ and rH2O signifies the hematite steady-state dissolution rate in acidic, neutral and
2016 basic solutions and rtt the total dissolution rate, AA and AB refer to pre-exponential factors
2018 equal to 37.9 kJ/mol, R represents the gas constant, and T denotes absolute temperature. In
2019 the absence of additional and more extensive data the Palandri and Kharaka fit has been
2020 adopted in this study. The degree to which this equation describes the dissolution rates
2021 reported in the literature can be assessed in Figure Hem1. Rates calculated using Equation
2022 Hem-1 described 4 of 36 reported rates within 0.8 log units.
2023 References
2024
2025 Banwart, S., Davies, S. and Stumm, W. (1989) The role of oxalate in accelerating the relative
2026 dissolution of hematite (α-Fe2O3) by ascorbate. Colloid Surf., 39, 303-309.
2027 Bruno, J., Stumm, W., Wersin, P., and Brandberg, F. (1992) On the influence of carbonate in mineral
2028 dissolution: I. The thermodynamics and kinetics of hematite dissolution in bicarbonate
2029 solutions at T = 25°C. Geochim. Cosmochim. Acta 56, 1139–1147.
2030 Bruno and Duro (2000) Reply to W. Hummel’s comment on and correction to “On the influence of
2031 carbonate in mineral dissolution: 1. The thermodynamics and kinetics of hematite dissolution
2032 in bicarbonate solutions at T 5 25°C”. Geochim. Cosmochim. Acta 64, 2173-2176.
2033 Cornell, R.M., Posner, A.M. and Quirk, J.P. (1976) Kinetics and mechanisms of the acid dissolution of
2034 goethite (et-FeOOH). J. Inorg. Nucl. Chem. 38, 563-567.
2035 Deng, Y. (1997) Effect of pH on the reductive dissolution rates of iron (III) hydroxide by ascorbate.
2036 Langmuir, 13, 1835-1839.
2037 Dos Santos, M. and Stumm, W. (1992) Reductive dissolution of iron (III) (hydr)oxides by hydrogen
2038 sulphide. Langmuir, 8, 1671-1675.
2039 Larsen, O and Postma, D. (2001) Kinetics of reductive bulk dissolution of lepidocrocite , ferrihydrate,
2040 and goethite. Geochim. Cosmochim. Acta, 65, 1367-1379.
2041 Petrie, L.M. (1995) Molecular interpretation for SO2 dissolution kinetics of pyrolusite, manganite and
2042 hematite. Geochim. Cosmochim. Acta 10, 253-267.
2043 Ruan, H. D. and Gilkes, R. J. (1995) Acid dissolution of synthetic aluminous goethite before and after
112
2044 transformation to hematite by heating. Clay Minerals 30, 55-65.
2045 Sidhu, P.S., Gilkes, R.J., Cornell, R.M., Posner, A.M and Quirk, J.P. (1981) Dissolution of iron oxides
2046 and oxyhydroxides in hydrochloric and perchloric acids. Clays Clay Miner. 29, 269-276.

2047 Suter, D., Banwart, S. and Stumm, W. (1991) Dissolution of hydrous iron(III) oxydes by reductives
2048 mechanisms. Langmuir 7, 809-813.
2049 Table He1: Summary of experimental conditions for the various hornblende steady-state
Hematite 25 3 Banwart (1989)
Hematite 20 0.4 Cornell et al. (1976)
Hematite 25 4.5 – 7.5 Deng (1997)
Hematite 25 3 - 11.5 Dos Santos and Stumm (1992)
Hematite 25 3 Larsen and Postma (2001)
Hematite 25-50 0.1 Ruan and Gilke (1995)
Hematite 25 0.4 Sidhu et al. (1981)
Hematite 25 2.5 - 6 Sutter et al (1991)
2051
2052 Figure He1: Summary of experimentally measured hematite steady-state dissolution rates
2054 dashed line.
-10 Banwart (1989)
-11 Cornell et al. (1976)
-12 Deng (1997)

log r+ (mol/cm2/s)
-13 Dos Santos and Stumm (1992)
pH2S 10-3 bar

-14
pH2S 10-4 bar
-15
Larsen and Postma (2001)
-16
Ruan and Gilkes (1995), 30
-17
Ruan and Gilkes (1995), 50
-18
Sidhu et al. (1981)
-19
113 Sutter et al. (1991)
0 2 4 6 8 10
pH Model (Palandri and Kharaka,

2055 2004)
2056

2057 Grossular
2058
2059 The dissolution rates of the calcium-aluminum garnet grossular (Ca3Al2(SiO4)3) were
2060 studied by Sverdrup (1990) at 25 ºC from pH 2.5 to 6.4. The data was fitted by Palandri and
2061 Kharaka (2004) to the following equation:
2062 ( )
2063 ( )
2064
2065 where rH+ and rH2O signifies the grossular steady-state dissolution rate in acidic and neutral
2066 solutions and rtt the total dissolution rate, AA and AB refer to pre-exponential factors equal
2067 to 6.17x105 and 3.02x103 mol/cm²/s respectively, EA and EB designates an activation energy
2068 equal to 85.0 and 103.8 kJ/mol, R represents the gas constant, and T denotes absolute
2069 temperature. As was the case for the garnets andradite and almandine, these activation
2070 energies are based on the fit of rates obtained at 8 and 25 ºC, and the rate data at 8 ºC were
2071 never directly reported. As such the degree to which these activation energies provide
2072 accurate rate estimates at substantially higher temperatures is questionable. The degree to
2074 in Figure Gro1. Rates calculated using Equation Gro-1 described 6 of 6 reported rates within
2075 0.8 log units.
2076
2077 References
2078
2081 2004-1068.
114
2084
2085

2086 Table Gro1: Summary of experimentally measured grossular steady-state dissolution rates
Grossular 25 2.5-6.4 Sverdrup (1990)
2088
2089 Figure Gro1: Summary of experimentally measured grossular steady-state dissolution rates
2091 model.
-8
log r+ (mol/cm2/s)
-10
-12 Sverdrup (1990)
Model (Palandri and

-14 Kharaka, 2004)
-16
0 2 4 6 8
pH
2092
115

2093 Halite
2094
2095 The mineral form of NaCl, halite (NaCl) or rock salt has been studied by Alkattan et al.
2096 (1997a, 1997b) in rotating disk reactors at temperature ranging from 25 to 80 ºC as a
2097 function of rotation speed and trace metal concentration. The available data is plotted on
2098 fig. Hal1 and fit to :
2099 ( ) (Hal1)
2100 where r+ signifies the halite forward dissolution rate, AA refers to pre-exponential factors
2101 equal to 3.11x10-8 mol/cm²/s, EA designates an activation energy equal to -22.5kJ/mol, R
2102 represents the gas constant, and T denotes absolute temperature. This fit differs from that
2103 reported by Palandri and Kharaka (2004), these authors apparently mistakenly fit NaCl
2104 diffusion rates reported by Alkattan et al. (1997a, b) rather than dissolution rates. Note, the
2105 activation energy calculated from the Alkattan et al (1997b) data is negative suggesting
2106 halite dissolution rates decrease somewhat with increasing temperature. Furthermore there
2107 is no pH dependence implied by our fit, the degree to which halite dissolution rates depend
2108 on pH cannot be assessed at present due to the lack of relevant data. The ability of equation
2109 Hal-1 equation to describe the dissolution rates reported in the literature can be assessed in
2110 Figure Hal1. Rates calculated using Equation Hal-1 described all of the reported rates within
2111 0.1 log units.
2112 References
2113
2114 Alkattan M., Oelkers E. H., Dandurand J.-L., and Schott J. (1997a) Experimental studies of halite
2115 dissolution kinetics: I. The effect of saturation state and the presence of trace metals. Chem.
2116 Geol. 137, 201-219.
2117 Alkattan M., Oelkers E. H., Dandurand J.-L., and Schott J. (1997b) Experimental studies of halite
2118 dissolution kinetics: II. The effect of the presence of aqueous trace anions and K3Fe(CN)6.
2119 Chem. Geol. 143, 17-26.
116
2122 2004-1068.
2123

2124 Table Hal1: Summary of experimentally measured halite steady-state dissolution rates
range
Halite 25 - 80 7 Alkattan et al. (1997a)
Halite 25 7 Alkattan et al. (1997b)
2126
2127 Figure Hal1: Summary of experimentally measured halite steady-state dissolution rates
2128 reported in the literature at 50 ºC as a function of pH and at pH 5.7 as a function of
2129 temperature. The results of the model are plotted as the dotted line.
-2,00 -3,00
-2,50
25 C
log r+ (mol/cm2/s)
-3,50
log r+ (mol/cm2/s)
-3,00
-4,00
-3,50 Alkattan et
Alkattan et al. (1997a) al. (1997a)
-4,00 -4,50
Alkattan et al. (1997b) model
-4,50 Model
-5,00
-5,00 0 25 50 75 100
2 4 6 8 10 T (C)
pH
2130
117

2131 Hornblende
2132
2133 Hornblende (Ca2Mg4Al1.75Fe0.25Si7O22(OH)2) is an amphibole variable composition

2134 typical of igneous rocks. It commonly has a chemical formula similar to that of tremolite,
2135 with substantial Fe and Al substituted for Mg and Si in its structure. There have been several
2136 studies of the dissolution rates of the amphibole hornblende. Nickel (1973) reported
2137 hornblende dissolution rates at 25 ºC as a function of pH from 1 to 5, and Cygan et al. (1989)
2138 reported rates at pH 4 and 25 ºC. Sverdrup (1990) reported hornblende dissolution at 25 ºC
2139 and pH from 1.6 to 7. Zhang et al. (1993) and Swoboda-Colberg and Drever (1993) reported
2140 rates at 25 ºC and pH from 3.6 to 4 and 4, 4.5 respectively. Frogner and Schweda (1998)
2141 reported rates at 25 ºC and pH 1 to 5, Golubev et al (2005) experimentally determined the
2142 rates at 25 ºC as a function of pH (2.1 – 11.1) and experiment duration. Brantley (2008)
2143 reported rates attributed to Givens and Brantley at 25 ºC and pH from 1.1 to 6.0. These
2144 experimental conditions are reviewed in Table Ho1 and the data points plotted on Fig. Ho1.
2145 Large inconsistencies are evident amongst these rates; at pH of ~3 there is nearly 4 orders of
2146 magnitude difference between the fastest and slowest rates, some of this large discrepancy
2147 may be attributable to the extensive amount of time required to achieve steady state
2148 hornblende dissolution. Golubev et al. (2005) observed that dissolution rates obtained from
2149 flow-reactor experiments running 1000 hours were approximately one order of magnitude
2150 slower than those ran for 100 hours. Moreover, of the earlier studies, only Frogner and
2151 Schweda (1998) conducted experiments which were demonstrated to exhibit stoichiometric
2152 metal release. An additional source of scatter may be the result of differences in the
2153 compositions of the hornblendes used in the various studies.
2154 The attempts to accurately fit hornblende forward dissolution rates are greatly
2155 confounded by the scatter of the data. This scatter also obscures the choice of rate equation.
2156 In the absence of definitive data, it is assumed that the hornblende dissolution is similar in
2157 rate behavior to tremolite. As such we have described hornblende rates using the tremolite
2158 rate equation:
118
2159 ( )( ) Ho-1
2160 together with values of EA and n deduced from the fit of tremolite dissolution rate data (

2161 55.8 kJ/mol, and 0.125, respectively). To best describe the scattered hornblende rate data,
2162 AA was set to be 0.5 log units higher than that determined for tremolite. The degree to
2164 in Figure Ho1. Rates calculated using Equation Ho-1 described 18 of 42 reported rates within
2165 0.9 log units.
2166 References
2167
2168 Brantley, S.L. (2008) Kinetics of mineral dissolution. Kinetics of water rock interactions
2169 Cygan, R.H., Casey, W.H, Roslough, M.B., Westricht,, H.R., Carr, M.J. and Holdren, G.R. (1989)
2170 Dissolution kinetics of experimentally shocked silicate minerals. Chem. Geol. 78, 229-244.
2171 Frogner, P. and Schweda, P. (1998) Hornblende dissolution kinetics at 25 ºC. Chem. Geol. 151, 169-
2172 179.
2174 CO2 on the dissolution kinetics of Mg and Ca silicates at 25 ºC. Chem. Geol. 217, 227-2538
2179 Swobodan-Colberg, N.G. and Drever, J.I. (1993) Mineral dissolution rates in plot-scale field ans
2181 Zhang, H, Bloom, P.R. and Nater, E.A. (1993) Change in surface area and dissolution rates during
2182 hornblende dissolution at pH 4.0. Geochim Cosmochim. Acta 57, 1681-1689.
2183
119

2184 Table Ho1: Summary of experimental conditions for the various hornblende steady-state
Hornblende 25 4 Cygan et al. (1989)
Hornblende 25 1-5 Frogner and Schweda (1998)
Hornblende 25 1.15-5.67 Givens and Brantley
Hornblende 25 2.1 – 11.1 Golubev et al. (2005)
Hornblende 25 3.6 – 10.6 Nickel (1973)
Hornblende 25 1.6 - 7 Sverdrup (1990)
Hornblende 25 4, 4.5 Swobodan-Colberg and Drever (1993)
Hornblende 25 3.6 - 4 Zhang (1993)
2186
2187 Figure Ho1: Summary of experimentally measured hornblende steady-state dissolution rates
2189 dotted line.
-11
Swoboda-Colberg and
25 ºC Drever (1993)
-12
Cygan et al. (1989)
-13 Frogner and Schweda

log r+ (mol/cm2/s)
(1998)
-14 Givens and Brantley in
Brantley et al.(2008)
-15 Golubev et al. (2005)
-16 Nickel (1973)
-17 Sverdrup (1990)
-18 Zhang et al. (1993)

0 2 4 6 8 10 12
Model, 25 C
pH
2190
120
2191

2192 Illite
2193
2194 Relatively few studies have been performed to determine the rates of illite
2195 (K0.6Mg0.25Al1.8Al0.5Si3.5O10(OH)2) dissolution. Early studies were carried out by Heydeman
2196 (1966) and Feigenbaum and Shainberg (1975) while more recent work was carried out by
2197 Köhler et al. (2003). Heydemann (1966) measured illite dissolution rates in batch reactors at
2198 pH 2.5 to 10 and 25 ºC. Feigenbaum and Shainberg (1975) determined dissolution rates of
2199 the same illite as Heydemann (1966) at 5 and 25 ºC and a pH close to 2.9 and 7.5. Nagy
2200 (1995) recalculated both the rates of Heydemann (1966) and Feigenbaum and Shainberg
2201 (1975) based on Si release. Holmqvist et al. (2001) reported dissolution rate from 6 to 23 ºC
2202 and pH ranging from 1 to 6. Köhler et al. (2003) investigated the dissolution rates of illite in
2203 batch reactors as a function of both pH, from 1.4 to 12.4, and temperature from 5 to 50 ºC.
2204 Köhler et al. (2003) provided the following empirical equation describing illite
2205 dissolution as a function of pH and temperature:
2206 Il-1
2207 where r+ signifies the illite steady state dissolution rate, EA , EB and EC designates activation
2208 energies, R represents the gas constant, and T denotes absolute temperature. The rate
2209 constants and activation energies were calculated by Köhler et al. (2003) with EA , EB and EC
2210 equal to 46, 14 and 67 kJ/mol respectively. The degree to which this equation describes the
2211 dissolution rates reported in the literature can be assessed in Figure Il1. Rates calculated
2212 using Equation Il-1 described 26 of 28 reported rates within 0.8 log. It should be kept in mind
2213 that the structure and formula of illite approximates that of muscovite. As such it might be
2214 anticipated that illite far-from-equilibrium dissolution rates depend on the aqueous
2215 aluminum and to some extent the aqueous silica concentration in the reactive fluid. Such a
2216 dependence of illite dissolution rates on these species is precluded at present by the dearth
2217 of relevant rate data.
2218
121

2219 References
2220
2221 Feigenbaum, S. and Shainberg, I. (1975) Dissolution of illite – A possible mechanism of potassium
2222 release. Soil. Sci. Soc. Am. Proc. 39, 985-990.
2223 Heydeman, A. (1966) Über die chemische Verwitterung von Tonmineralen (Experimentelle
2224 Utersuchungen). Geochim. Cosmochim. Acta 30, 995-1035.
2225 Köhler, S.J., Dufaud, F. and Oelkers, E.H. (2003) An experimental study of illite dissolution kinetics as
2226 a function of pH from 1.4 to 12.4 and temperature from 5 to 50ºC. Geochim. Cosmochim.
2227 Acta 67, 3583-3594.
2228 Nagy, K.L. (1995) Dissolution and precipitation kinetics of sheet silicate. In : White, A.F. and Brantley,
2229 S.L. (eds.), Chemical Weathering Rates of Silicate Minerals, Reviews in Mineralogy,
2230 Mineralogical Society of America 31, 173-233.
2231
122

2232 Table Il1: Summary of experimental conditions for the various illite steady-state dissolution
Illite 5-25 2.9-7.5 Feigenbaum and Shainberg (1975)
Illite 25 2.5-10 Heydeman (1966)
Kungsängen illite 6-23 1-6 Holmqvist et al. (2001)
Illite du Puy 5-50 1.4-12.4 Köhler et al. (2003)
2234
2235 Figure Il1: Summary of experimentally measured illite steady-state dissolution rates reported
2236 in the literature as a function of pH. The results of the model at 5, 25 and 50 ºC are plotted in
2237 dotted, dashed and dotted-dashed lines respectively.
2238
-15 5 ºC Köhler et al.(2003)
25 ºC Köhler et al.(2003)
-16
50 ºC Köhler et al.(2003)
log r+ (mol/cm2/s)
-17 Feigenbaum and Shainberg

(1975) in Nagy (1995)
Heynemann (1966) in Nagy
-18 (1995)
5 ºC Model
-19 25 ºC Model
50 ºC Model
-20
0 2 4 6 8 10 12 14
pH
2239
2240
123

2241 Ilmenite
2242
2243 The weakly magnetic titanium oxide mineral ilmenite dissolution has been studied by
2244 White et al. (1994) who reported rates at 25 C and pH 1 to 6. The available rate data was
2245 fitted by Palandri and Kharaka (2004) to:
2246 ( )
2247 ( )
2248
2249 where rH+ and rH2O signifies the ilmenite steady-state dissolution rate in acidic, neutral and
2250 basic solutions and rtt the total dissolution rate, AA and AB refer to pre-exponential factors
2252 equal to 37.9 kJ/mol, R represents the gas constant, and T denotes absolute temperature. In
2253 the absence of additional and more extensive data the Palandri and Kharaka fit has been
2254 adopted in this study. The degree to which this equation describes the dissolution rates
2255 reported in the literature can be assessed in Figure Ilm1. Rates calculated using Equation
2256 Ilm-1 described all reported rates within 0.8 log.
2257
2258 References
2259
2262 White, A. F., Peterson M. L., and Hochella M. F., Jr. (1994) Electrochemistry and dissolution kinetics of
2263 magnetite and ilmenite. Geochim. Cosmochim. Acta 58, 1859-1875.
2264
2265
124

2266 Table Ilm1: Summary of experimental conditions occurring during ilmenite steady-state
Ilmenite 25 1.1-6.0 White et al. (1993)
2268
2269 Figure Ilm1: Summary of experimentally measured ilmenite steady-state dissolution rates
-10
25 C
-12
log r+ (mol/cm2/s)
-14 White et al. (1994)
Model (Palandri and

Kharaka, 2004)
-16
-18
1 2 3 4 5 6 7
pH
2272
2273
125

2274 Quartz
2275
2276 The quartz is one of the most studied mineral of all time. The pH dependence of the
2277 dissolution rates of silicates has been the subject of numerous studies, cf. Dove (1995).
2278 Knauss and Wolery (1988) studied the dissolution of quartz at pH from 1.4 to 11.8 at 70 ºC.
2279 Tester et al. (1994) investigated the dissolution kinetics of quartz in pure water and also
2280 reported the rates obtained by 10 previous studies by Kitahara (1960), Van Lier et al. (1960),
2281 Siebert et al (1963), Weil and Fyfe (1964), Rimstidt and Barnes (1980), Blum et al. (1990),
2282 Brady and Walter (1990), Dove and Crerar (1990), Bennet (1991) and Berger et al. (1994a).
2283 Tester obtained two series of dissolution data on temperature ranging from 25 to 625 ºC.
2284 Dove and Elston (1992) described the kinetics of quartz at 25 ºC, pH 2 to 12 and NaCl
2285 concentration from 0 to 0.5 M. Dove (1994) extended those results to include temperature
2286 up to 300 ºC. Dove and Crerar (1990) investigated the dissolution of quartz at circumneutral
2287 pH in the temperature interval 100-300 C. Gislason et al. (1997) also measured at pH 3.5,
2288 temperature of 25 to 200 ºC and far from equilibrium conditions the dissolution of quartz.
2289
2290 References
2291
2292 Bennett, P.C. (1991) Quartz dissolution in organic-rich aqueous systems. Geochim. Cosmochim. Acta,
2293 55, 1781-1797.
2294 Brady, P.V. and Walther, J.V. (1990) Kinetics of Quartz dissolution rates at low temperature. Chem.
2295 Geol., 82, 253-264.
2296 Casey
2297 Dove, P.M. (1994) The dissolution of quartz in sodium chloride solutions at 25 ºC to 300 ºC. Am. J. Sci.,
2298 294, 665-712.
2299 Dove, P.M. (1999) The dissolution kinetics of quartz in aqueous mixed cation solutions. Geochim.
2300 Cosmochim. Acta, 63, 3715-3727.
2301 Dove, P.M. and Crerar, D.A. (1990) Kinetics of quartz dissolution in electrolytes solutions using
2302 hydrothermal mixed flow reactor. Geochim. Cosmochim. Acta, 54, 955-969.
2303 House, W.A. and Orr, D.R. (1992) Investigation of the pH dependence of the kinetics of quartz
2304 dissolution at 25 ºC. J. Chem. Soc., Faraday Trans., 88, 233-241.
2305 Knauss, K.G. and Copenhaver, S.A. (1995) The effect of malonate on the dissolution kinetics of albite,
2306
126 quartz and microcline as a function of pH at 70ºC. Appl. Geochem., 10, 17-33.
2307 Tester, J.W., Worley, W.G., Robinson, B.A., Grisgsby, C.O. and Feerer, J.L. (1994) Correlating quartz
2308 dissolution kinetics in pure water from 25 to 625 ºC. Geochim. Cosmochim. Acta, 58, 2407-
2309 2420.

2310 Wollast, R. and Chou, L. (1988) Rate control of weathering of silicate minerals at 25 C and pressure.
2311 Physical and Chemical Weathering in Geochemical Cycles
2312 Table Qu1: Summary of experimental conditions for the various quartz steady-state
Quartz 25 4 Bennet et al. (1988)
Quartz 25 1-5 Bennet (1991)
Quartz 25 2.1 – 11.1 Berger et al. (1994)
Quartz 25 3.6 – 10.6 Brady and Walther (1990)
Quartz 25 1.6 - 7 Casey et al. (1990)
Dove and Crerar (1990)
Quartz 25 4, 4.5 Dove (1994)
Dove (1999)
Quartz House and Orr (1992)
Quartz 70 Knauss and Copenhaver (1995)
Quartz Tester et al. (1994)
Quartz 25 3.6 - 4 Wollast and Chou (1988)
2314
2315
127

-14
25 C
-15
Dove (1994)
log r+ (mol/cm2/s)
Brady and Walther (1990)

-16
Bennett et al. (1988)e
Bennet (1991)
-17
Berger et al. (1994)
House and Orr (1992)
-18 Wollast and Chou (1988)
Model Bandtra et al 2005
-19
0 2 4 6 8 10 12
pH
2316
2317
128

2318 Jadeite
2319
2320 Jadeite is an inosilicate with a clinopyroxene structure, where Si-O chains are held
2321 together with Na and Al bridges. Its dissolution kinetics were only reported by Sverdrup
2322 (1990) at 25 ºC and pH ranging from 3 to 6. These 3 data points are plotted on Fig. Ja1 and
2323 listed in Table Ja1.
2324 Owing to its structure, and by analogy with Al-silicate minerals it seems reasonable to
2325 assume that its dissolution mechanism consists of the sequential removal of Na then Al via
2326 proton exchange reactions prior to the final removal of Si-O tetrahedra from the mineral. In
2327 such cases dissolution rates are commonly consistent with:
2328 ( ) ( ) Ja-1
2329 where r+ signifies the jadeite steady state dissolution rate, AA refers to a pre-exponential
2330 factor equal to 1.5x10-3 mol/cm²/sec, EA designates an activation energy equal to 48 kJ/mol,
2331 n refers to a constant equal to 0.25, R represents the gas constant, and T denotes absolute
2332 temperature. In the absence of any measured dependence of rates of temperature, EA was
2333 set to be equal to 48 kJ/mol by analogy with the amphiboles (reference), chain silicates also
2334 held together by bridging Al-octahedrals. The degree to which this equation describes the
2335 dissolution rates reported in the literature can be assessed in Figure Ja1. Rates calculated
2336 using Equation Ja-1 described 3 of 3 reported rates within 0.1 log units with an average
2337 uncertainty of 0.1 log units.
2338
2339 References
2340
2343
2344
129

2345 Table Ja1: Summary of experimentally measured jadeite steady-state dissolution rates
Jadeite 25 3, 4.5, 6 Sverdrup (1990)
2347
2348 Figure Ja1: Summary of experimentally measured jadeite steady-state dissolution rates
2350 dotted line.
2351
-10
25 ºC
-11
log r+ (mol/cm2/s)
-12
-13
Sverdrup 1990
Model
-14
-15
2 4 6 8 10
pH
2352
2353
130

2354 Kaolinite
2355
2356 The dissolution rate of kaolinite under controlled temperature and pH conditions has
2357 been the subject of many investigations. Kaolinite dissolution kinetics was studied by Turner
2358 (1964) at 25 C and pH ranging from -1 to 7. Polzer and Hem (1965) reported rate data at 25 C
2359 and pH 4 and Jörgensen and Mitchell (1970) reported rates at 25 C and pH of 3.6 and 6. The
2360 dissolution kinetics was investigated at pH 1 to 12 by Caroll and Walther (1990) at
2361 temperatures of 25 to 80 ºC. Wieland and Stumm (1992) measured kaolinite dissolution
2362 between pH 2 and 6.5 at 25 ºC while Ganor et al. (1994) reported rates measured at pH 3 to
2363 4.2 and temperature ranging from 25 to 80 ºC. Devidal et al. (1997) observed kaolinite
2364 dissolution rates at 150 ºC, 40 bars of CO2 and at pH from 2 to 7.8. Kaolinite dissolution
2365 kinetics were investigated in 0.1-4 M KOH solutions at 35 and 80 ºC by Bauer and Berger
2366 (1998). Metz and Ganor (2001) reported rates from 25 to 80 C and pH ranging from 3.0 to
2367 4.2, Huertas et al. (1999) studied kaolinite dissolution at 25 ºC and at pH from 1 to 13 and
2368 Cama et al. (2002) reported rates taken from pH 1 to 5 and temperature ranging from 25 to
2369 70 ºC. Yang and Steefel (2008) reported kaolinite dissolution rates at 22 C and pH of 4. The
2370 different conditions where the data was acquired are summarized in table Ka1. The rates are
2371 presented for the different temperatures as a function of pH in Figure Ka1, except for the
2372 rates obtained at 150 ºC by Devidal et al. (1997).
2373 The published data behavior presented in Fig. Ka1 was obtained by summing the
2374 contributions of the acidic, neutral and basic mechanisms reported by Palandri and Kharaka
2375 (2004):
2376  
rH   AA . exp  E A / RT  aHn 
Ka-1
2377 rW  AB . exp  E B / RT 
Ka-2
2378 
rOH   AC . exp  EC / RT  aOH
0.55
 
Ka-3
131
2379 r  rH   rW  rOH 
Ka-4

2380 where ri signifies the kaolinite forward dissolution rate, AA , AB and AC refer to pre-
2381 exponential factors equal to respectively 6.45x10-9, 4.36x10-17 and 1.94x10-4 mol/cm²/sec, EA
2382 , EB and EC designate the activation energies of their respective mechanisms equal to 46, 14
2383 and 67 kJ/mol, R represents the gas constant, and T denotes absolute temperature. The
2384 pre-exponential factors and activation energies were determined from an Arrhenius plot of
2385 the available data. The degree to which this equation describes the dissolution rates
2386 reported in the literature can be assessed in Figure Ka1. Rates calculated using Equation Ka-4
2387 described 50 of 205 reported rates within 0.8 log units.
2388
2389 References
2390
2391 Bauer, A. and Berger, G. (1998) Kaolinite and smectite dissolution rate in high molar KOH solutions at
2392 35º and 80ºC. Appl. Geochem. 13, 905-916.
2393 Cama, J., Metz, V. and Ganor, J. (2002) The effect of pH and temperature on kaolinite dissolution rate
2394 under acidic conditions. Geochim. Cosmochim. Acta 66, 3913-3926.
2395 Caroll, S.A. and Walter, J.V. (1990) Kaolinite dissolution at 25º, 60 º and 80 º C. Am. J. Sci. 290, 797-
2396 810.
2397 Devidal, J.L., Schott, J. and Dandurand, J.L. (1997) An experimental study of kaolinite dissolution and
2398 precipitation kinetics as a function of chemical affinity and solution composition at 150 ºC, 40
2399 bars CO2 and pH 2, 6.8 and 7.8. Geochim. Cosmochim. Acta 61, 5165-5186.
2400 Ganor, J., Mogollón, J.L. and Lasaga, A.C. (1995) The effect of pH on kaolinite dissolution rates and on
2401 activation energy. Geochim. Cosmochim. Acta 59, 1037-1052.
2402 Huertas, F.J., Chou, L. and Wollast, R. (1999) Mechanism of kaolinite dissolution at 25 C and pressure.
2403 Part II: Kinetic study. Geochim. Cosmochim. Acta 63, 3261-3275.
2404 Jörgensen, S.S. and Mitchell, B.D. (1970)
2405 Metz, V. and Ganor, J. (2001) Stirring effect on kaolinite dissolution rate. Geochim. Cosmochim. Acta
132
2406 65, 3475-3490.
2407 Polzer, W.L. and Hem, J.D. (1965) The dissolution of kaolinite. J. Phys. Res. 70, 6233-6240.

2410 2004-1068.
2411 Turner, R. (1964) Kinetic studies of acid dissolution of montmorillonite and kaolinite. Ph.-D thesis,
2412 university of California, Davis, California.
2413 Wieland, E. and Stumm, W. (1992) Dissolution kinetics of kaolinite in acidic solutions at 25 ºC.
2415 Yang, L., and Steefel, C.I. (2008) Kaolinite dissolution and precipitation kinetics at 22 ºC and pH 4.
2417
2418 Table Ka1: Summary of experimental conditions occurring during kaolinite steady-state
kaolinite 35, 80 11.5 – 13.9 Bauer and Berger (1998)
kaolinite 25 1-5 Cama et al. (2002)
kaolinite 25, 60, 80 1 - 12 Caroll and Walter (1990)
kaolinite 150 2, 6.8, 7.8 Devidal et al. (1997)
kaolinite 25, 50, 80 3 - 4.2 Ganor et al. (1995)
kaolinite 25 1 - 13 Huertas et al. (1999)
kaolinite 25 3.6, 6 Jörgensen and Mitchell (1970)
Kaolinite 25-70 2-3 Metz and Ganor (2001)
Kaolinite 25 4 Polzer and Hem (1965)
Kaolinite 25 -1-7 Turner (1964)
kaolinite 25 2 - 6.5 Wieland and Stumm (1992)
kaolinite 22 4 Yang and Steefel (2008)
2420
133
2421

2422 Figure Ka1: Summary of experimentally measured K-feldspar steady-state dissolution rates
2424 dotted line.
-12
Bauer and Berger (1998), 35 C
-13 Bauer and Berger (1998), 80 C
y= 0,058x2 - 0,7314x - 15,97 Cama et al. (2002), 25°C
-14
Cama et al. (2002), 50°C
log r+ (mol/cm2/s)
-15 Cama et al. (2002), 70°C
Caroll and Walter (1990), 25 C

-16
Caroll and Walter (1990), 60 C
-17 Caroll and Walter (1990), 80 C
Huertas (1999), 25 C
-18
Ganor et al. (1994), 25 C
-19 Ganor et al. (1994), 50 C
Ganor et al. (1994), 80º C

-20
Wieland and Stumm (1992), 25 C
0 2 4 6 8 10 12 14
2425 pH model
134

2426 K-Feldspar
2427 Dissolution rates of K-feldspar have been published by Bevan and Savage (1989) at
2428 temperature ranging from 25 to 95 C and pH of 1 to 9, Busenberg and Clemency (1976)
2429 studied the K-feldspar dissolution at pH 5 and 24 C while Gautier et al. (1994) measured the
2430 rates at pH 9 and 150 C as a function of ΔG. Knauss and Copenhaver (1994) reported
2431 dissolution rates at 70 C and between pH 4 and 10. Siegel and Pfannkuch (1984) published
2432 dissolution rates at 25 C and pH 4 while Stillings et al. (1996) studied the dissolution kinetics
2433 of K-feldspar at 25 C and pH ranging from 3 to 7. The different conditions where the data
2434 was acquired are summarized in table Kf1. The rates are presented for the different
2435 temperatures as a function of pH in Figure Kf1.
2436 The dissolution rates of K-feldspar were fitted by Gautier et al. (1994) to the following
2437 equation:
1/ 3
 a H3  
2438 r  AA .(1  exp  E A / 3.R.T )    (Kf-1)
 a 3 
 Al 
2439 where r signifies the K-feldspar steady state dissolution rate, AA refers to a pre-
2440 exponential factor equal to 2.77x10-13 mol/cm²/sec, EA designates an activation energy equal
2441 to 57.34 kJ/mol, R represents the gas constant, and T denotes absolute temperature. The
2443 be assessed in Figure Kf1. Rates calculated using Equation Kf-1 described 12 of 14 reported
2445
2446 References
2447 Bevan, J. and Savage, D. (1989) The effect of organic acids on the dissolution of K-feldspar under
2448 conditions relevant to burial diagenesis. Mineral. Mag., 53, 415-425.
2449 Busenberg, E. and Clemency, C.V. (1976) The dissolution kinetics of feldspar at 25ºC and 1 atm CO2
2450 partial pressure. Geochim. Cosmochim. Acta. 40, 41-49.
2451 Gautier J.-M., Oelkers E. H., and J. S. (1994) Experimental study of K-feldspar dissolution rates as a
135
2452 function of chemical affinity at 150°C and pH 9. Geochim. Cosmochim. Acta 58, 4549–4560.
2453 Knauss, K.G. and Copenhaver, S.A. (1995) The effect of malonate on the dissolution kinetics of albite,
2454 quartz and microcline as a function of pH at 70ºC. Appl. Geochem., 10, 17-33.

2455 Siegel,D.I. and Pfannkuch, H.O. (1984) Silicate mineral dissolution at pH 4 and near standard
2456 temperature and pressure. Geochim. Cosmochim. Acta, 48, 197-201.
2457 Stillings, L.L., Drever, J.I., Brantley, S.L., Sun, Y., Oxburgh, R. (1996) Rates of feldspar dissolution at pH
2458 3-7 with 0-8 mM oxalic acid. Chem. Geol., 132, 79-89.
2459
2460 Table Kf1: Summary of experimentally measured forsterite steady-state dissolution rates
2462
Orthoclase 70, 90 1, 4, 9 Bevan and Savage (1989)
Orthoclase, Microcline 25, 70 5 Busenberg and Clemency (1976)
K-feldspar 150 9 Gautier et al. (1994)
K-feldspar 70 4-10 Knauss and Copenhaver (1995)
K-Feldspar 25 3.82-5.65 Manley and Evans (1986)
K-Feldspar 25 3-11 Schweda (1989)
Microcline 25 4 Siegel and Pfannkuch (1984)
K-feldspar 25 3-7 Stillings et al. (1996)
K-feldspar 25 4, 4.5 Swoboda-Colberg and Drever (1993)
K-feldspar 25 7 Tan (1980)
K-feldspar 25 3.5-5 Van Hess (2002)
2463
2464 Figure Kf1: Summary of experimentally measured K-feldspar steady-state dissolution rates
2466 dotted line.
136

-10
Busenberg and Clemency (1976),
25 ºC
Bevan and Savage (1989), 25 ºC
-12
Bevan and Savage (1989), 70 ºC
log r+ (mol/cm2/s)
Gautier et al. (1994), 150 ºC
-14 Knauss and Copenhaver (1995),

70 ºC
Siegel and Pfannkuch (1984), 25
ºC
-16 Stillings et al. (1996), 25 ºC
Model (25 ºC)
-18 Model (70 ºC)

0 2 4 6 8 10
pH Model (150 ºC)
2467
137

2468 Kyanite
2469 Kyanite steady state dissolution rates were reported by Nickel (1973) at 25 ºC and pH
2470 from 0.2 to 11 and measured in mixed flow reactors as a function of aqueous aluminum and
2471 silica concentration at pH 1.6 to 2.2 and at temperatures from 108 to 194°C by Oelkers and
2472 Schott (1999). These experimental conditions are summarized in table Ky1. The rates
2473 obtained at pH 2 are presented as a function of the inverse of temperature in Figure Ky1.
2474 All measured rates, which were obtained at far from equilibrium conditions where
2475 the contribution of reverse reaction is negligible, are consistent with Oelkers and Schott
2476 (1999):
2477 ( )( ) (Ky-1)
2478 where r+ signifies the overall kyanite steady state dissolution rate normalized to a 1 cm 2
2479 surface, AA refers to a pre-exponential factor equal to 2x10-5 mol/cm2/sec, EA designates an
2480 apparent activation energy equal to 75 kJ/mol, R represents the gas constant, and T denotes
2481 absolute temperature. The degree to which this equation describes the dissolution rates
2482 reported in the literature can be assessed in Figure Ky1. Rates calculated using Equation Ky-
2483 1 described all of the reported rates by Oelkers and Schott (1999) within 0.8 log units.
2484
2485 References
2486 Oelkers, E.H. and Schott, J. (1999) Experimental study of kyanite dissolution rates as a function of
2487 chemical affinity and solution composition. Geochim. Cosmochim. Acta 63, 785-797.
2490
138

2491 Table Ky1: Summary of experimentally measured kyanite steady-state dissolution rates
Kyanite 108-194 1.6-2.2 Oelkers and Schott (1999)
Kyanite 25 0.2 - 11 Nickel (1973)
2493
2494 Figure Ky1: Summary of experimentally measured kyanite steady-state dissolution rates
2495 reported in the literature as a function of 1/T and pH. The results of the model are plotted as
-12
-10
pH 2 Oelkers and Schott
(1999), 150 C
-13 -11 Nickel (1973), 25 C
log r+ (mol/cm2/s)
log r+ (mol/cm2/s)
Model (Oelkers et
-12
-14 al. (1999)
-13
-15
-14
Oelkers and Schott
-16 (1999) -15
Model
-17 -16
0,002 0,00225 0,0025 0,00275 0,003 0 2 4 6 8 10
1/T (K) pH
2497
2498
2499
139

2500 Leucite
2501
2502 The potassium aluminum feldspathoid leucite (KAlSi2O6) dissolution has been studied
2503 by Krueger (1939) and reported by Sverdrup (1990) at 25 ºC and from pH 0 to 11. Although
2504 Sverdrup (1990) suggested that the dissolution mechanism of leucite would be similar to
2505 that of the pyroxene, especially jadeite, its structure most closely approaches that of the
2506 feldspathoid nepheline. In the absence of sufficient data to deduce a more comprehensive
2507 rate description and to be consistent with the rates adopted in this study for nepheline we
2508 fit the available leucite dissolution rate data to the equations reported by Palandri and
2509 Kharaka (2004) for :
2510 ( )
2511 ( )
2512 ( )
2513
2514 where rH+, rH2O and rOH- signify the leucite forward dissolution rate in acidic, neutral and
2515 basic solutions and r+ the total dissolution rate, AA, AB and AC refer to pre-exponential
2516 factors equal to 1.21x1013, 1.08 and 8.69x10-6 mol/cm²/s respectively, EA, EB and EC
2518 constant, and T denotes absolute temperature. The origin of these activation energies is,
2519 however, unclear as we have been unable to locate the source of leucite rate data at
2520 temperatures other then 25 ºC. The degree to which this equation describes the dissolution
2521 rates reported in the literature can be assessed in Figure Leu1. Rates calculated using
2522 Equation Leu-1 described all reported rates within 0.8 log units.
2523
2524
140

2525 References
2526
2527 Krueger, G. (1939) Verwitterungsverungsversuche am Leuzite. Chemie der Erde 12, 236-264.
2530 2004-1068.
2533
2534 Table Leu1: Summary of experimentally measured leucite steady-state dissolution rates
Leucite 25 0 - 11 Krueger (1939) in Sverdrup (1990)
2536
2537 Figure Leu1: Summary of experimentally measured leucite steady-state dissolution rates
2539 model.
-9
25 C
-10
log r+ (mol/cm2/s)
-11
-12
Krueger (1939)
-13 Model
-14
-15
0 2 4 6 8 10 12
pH
2540
141

2541 Magnesite
2542 Few kinetics studies have been carried out on magnesite (MgCO3), with respect to
2543 the work done on calcite dissolution. At 25 ºC Chou et al. (1989) reported a linear
2544 dependence of magnesite dissolution rate as a function of proton activity in the 2<pH<5
2545 range while Pokrovsky and Schott (1999) report nearly pH-independent rates in the range
2546 0<pH<3 and rates proportional to the proton activity in the range 3<pH<5. Higgins et al.
2547 (2002) reported dissolution rates measured with bulk techniques and AFM at 60 ºC and pH
2548 from 2 to 4.5., Pokrovsky et al. (2003) reported rates at 25 ºC and pH ~3.5 as a function of
2549 pCO2, Jordan et al. (2007) reported rates at 100 ºC at pH ranging from 5.55 to 9.7. The
2550 conditions where the data was acquired are summarized in table Mag1 and the available
2551 rate data are presented in Fig. Mag1.
2552 The available data was fitted to an equation from Busenberg and Plummer (1982)
2553 adapted by Chou et al. (1989):
( )
( ) ( )
( ) ( )
2554 where rH+, rH2CO3 and rH2O signifies the magnesite forward dissolution rate in acidic, neutral
2555 and basic solutions and rtt the total dissolution rate, AA, AB and AC refer to pre-exponential
2556 factors equal to 8.86, 1x10-3 and 2.2x10--8 mol/cm²/s respectively, EA, EB and EC designate
2557 activation energies equal to 34.0, 21.0 and 16.0 kJ/mol, R represents the gas constant, T
2558 denotes absolute temperature and n signifies a stoichiometric coefficient equal to 0.75. The
2560 be assessed in Figure Mag1. Rates calculated using Equation Mag-1 described xx of xx
142
2561 reported rates within 0.8 log units.
2562

2563 References
2566 Higgins, S.R., Jordan, G. and Eggleston, C. (2002) Dissolution kinetics of magnesite in acidic aqueous
2567 solutions: A hydrothermal atomic force microscopy study assessing step kinetics and
2568 dissolution flux. Geochim. Cosmochim. Acta 66, 3201-3210.
2569 Jordan, G., Pokrovsky, O.S., Guichet, X., and Schmahl, W.W. (2007) Organic and inorganic ligand
2570 effects on magnesite dissolution at 100 °C and pH=5 to 10. Chem. Geol. 242, 484-496.
2571 Pokrovsky, O.S. and Schott, J. (1999) Processes at the magnesium-bearing carbonates/solution
2572 Interface. II. Kinetics and mechanism of magnesite dissolution. Geochim. Cosmochim. Acta
2573 63, 881-897.
2574 Pokrovsky, O.S., Golubev, S.V. and Schott, J. (2003) Dissolution kinetics of calcite, dolomite and
2575 magnesite at 25 8C and 0 to 50 atm pCO2. Chem. Geol. 217, 239-255.
2576
2577 Table Mag1: Summary of experimentally measured magnesite steady-state dissolution rates
Magnesite 25 2.1 - 8 Chou et al. (1989)
Magnesite 60 2 - 4.5 Higgins et al. (2002)
Magnesite 100 5.55 – 9.7 Jordan et al. (2007)
Magnesite 25 0.2 – 11.4 Pokrovsky and Schott (1999)
Magnesite 25 3.2 – 4.5 Pokrovsky et al. (2003)
2579
2580
143

2581 Figure Mag1: Summary of experimentally measured magnesite steady-state dissolution rates
2583 dotted line.
-8
25 C
-9
-10
log r+ (mol/cm2/s)
Chou et al. (1989)

-11
-12 Pokrovsky and Schott

(1999)
-13 Pokrovsky et al. (2003)
-14 Model
-15
-16
0 2 4 6 8 10 12
pH
2584
2585
144

2586 Magnetite
2587
2588 The iron oxide mineral magnetite (Fe3O4) dissolution has been studied by White et al.
2589 (1994) who reported rates at 25 ºC and pH 1 to 6. The available rate data was fitted by
2590 Palandri and Kharaka (2004) to:
2591 ( )
2592 ( )
2593
2594 where rH+ and rH2O signifies the magnetite steady-state dissolution rate in acidic, neutral
2596 factors equal to 4.68x10-10 and 3.02x10-12 mol/cm²/s respectively, EA designates an activation
2597 energy equal to 18.6 kJ/mol (Palandri and Kharaka, 2004), R represents the gas constant, and
2598 T denotes absolute temperature. In the absence of additional and more extensive data the
2599 Palandri and Kharaka fit has been adopted in this study. The degree to which this equation
2600 describes the dissolution rates reported in the literature can be assessed in Figure Mag1.
2601 Rates calculated using Equation Ilm-1 described all reported rates within 0.8 log.
2602
2603 References
2604
2607 White, A. F., Peterson M. L., and Hochella M. F., Jr. (1994) Electrochemistry and dissolution kinetics of
2608 magnetite and ilmenite. Geochim. Cosmochim. Acta 58, 1859-1875.
2609
2610
145

2611 Table Mag1: Summary of experimental conditions occurring during magnetite steady-state
Magnetite 25 1.1-6.0 White et al. (1993)
2613
2614 Figure Mag1: Summary of experimentally measured magnetite steady-state dissolution rates
-12
25 C
log r+ (mol/cm2/s)
-13
White et al. (1994)
Model (Palandri and

-14 Kharaka, 2004)
-15
0 2 4 6 8 10
2617 pH
146

2618 Muscovite
2619 The mica muscovite (KAl3Si3O10(OH)2) dissolution rates were measured by Böhmeke
2620 (1946) at 25 ºC and pH ranging from 5 to 11. Nickel (1973) reported the dissolution rates at
2621 25 ºC and pH = 0.2 to 10 measured in stirred tank reactors. Cabrera and Talibudeen (1978)
2622 studied the muscovite dissolution kinetics at 25 ºC and pH 3, Hurd et al. (1979) reported
2623 kinetic data at 1 ºC and pH 8. Lin and Clemency (1981) measured the dissolution rates of
2624 muscovite at 25 ºC in a CO2 rich solution at pH 5 in closed system rectors. Knauss and Wolery
2625 (1989) reported muscovite dissolution rates at 70 ºC as a function of pH in flow-through
2626 reactors. Kalinowski and Schweda (1996) reported muscovite dissolution rates at 25 ºC and
2627 pH = 1.1, 2.0, 3.0 and 4.1 measured in dialysis-cell reactors.
2628 Oelkers et al. (2008) determined that the variation of rates with reactive solution
2629 composition depends on the solution pH. At pH 6, 7 rates were found to decrease
2630 significantly with increasing reactive fluid Al activity but be independent of aqueous SiO 2
2631 activity. pH < 7 rates measured from 60 to 175 ºC are consistent with:
2632 ( )( ) (Mu-1)
2633 where r+ refers to the far-from-equilibrium muscovite dissolution rate, R designates the gas
2634 constant, T signifies absolute temperature and ai represents the activity of the subscripted
2635 aqueous species and n signifies a stoichiometric coefficient equal to 0.2. EA depicting the
2636 activation energy of the reaction was determined from an Arrhenius plot of the data
2637 obtained at pH 2 by Oelkers et al. (2008) to be 46.03 kJ/mol and AA a pre-exponential factor
2638 was calculated to be 5.32x10-9 mol/cm2/s.
2640 literature can be assessed in Figure Mu1. Rates calculated using Equation Mu-1 described 63
2642
2643
147

2644 References
2645 Böhmeke, A. (1946) Undersuchungen ueber die Verwitterungen des Muskovit. PhD Thesis, University
2646 of Göttingen.
2647 Cabrera, F. And talibudeen, O. (1978) The release of aluminium from aluminosilicate minerals. Clay
2648 and Clay Minerals 26, 434-440.
2649 Hurd, D.C., Fraley, c. and Fugate, J.K. (1979) Silica apparent solubilities and rates of precipitation in
2650 E.A. Jeanne (Ed.), Chemical Modeling of Aqueous Systems. Am. Chem. Soc. Symp. Series 93,
2651 413-445.
2653 alteration at pH 1-4, 25 ºC. Geochim. Cosmochim. Acta 60, 367-385.
2654 Knauss, K.G. and Wolery, T.J. (1989) Muscovite dissolution kinetics as a function of pH and time at 70
2655 ºC. Geochim. Cosmochim. Acta 53, 1493-1502.
2656 Lin, F.-C. and Clemency, C.V. (1981) The kinetics of dissolution of muscovites at 25 and 1 atm CO2
2660 Oelkers, E.H., Schott, J., Gauthier, J.M. (2008) An experimental study of the dissolution mechanism
2661 and rates of muscovite. Geochim. Cosmochim. Acta 72, 4948-4961.
2662 Stumm, W., Furrer, G., Wieland, E. and Zinder, B. (1987) The effect of complex-forming ligands on the
2663 dissolution of oxides and aluminosilicates. In J.I. Drever, Ed., The chemistry of Weathering,
2664 55-74.
2667
148

2668 Table Mu1: Summary of experimentally measured forsterite steady-state dissolution rates
Muscovite 25 5-11 Böhmeke (1946)
Muscovite 25 3 Cabrera and Talibudeen (1978)
Muscovite 1 8 Hurd et al. (1979)
Muscovite 25 1-4 Kalinowski and Schweda (1996)
Muscovite 70 2-10 Knauss and Wolery (1989)
Muscovite 25 5 Lin and Clemency (1981)
Muscovite 25 0.2-10.6 Nickel (1973)
Muscovite 60-175 2 Oelkers et al. (2008)
Muscovite 25 3, 5 Stumm et al. (1987)
Muscovite 25 4, 4.5 Swoboda-Colberg and Drever (1993)
2670
2671
149

2672 Figure Mu1: Summary of experimentally measured muscovite steady-state dissolution rates
2673 reported in the literature at 25 Cº as a function of pH. The results of the model are plotted as
2675
-15 Böhmeke (1946), 25 C
25 ºC
Cabrera and Talibudeen
-15,5
(1978), 25 C
Hurd et al. (1979), 1 C
log r+ (mol/cm2/s)
-16
Kalinowski and Schweda
(1996)
-16,5 Knaus and Wolery (1989), 70
C
Lin and Clemency (1981b),
-17 25 C
Nickel (1973), 25 C
-17,5 Stumm et al. (1987), 25 C
Swoboda-Colberg and
-18 Drever (1993)
0 2 4 6 8 10 12 Model, 25 C
pH
2676
2677 Figure Mu2: Summary of experimentally measured muscovite steady-state dissolution rates
2678 reported by Oelkers et al. (2008) at 150 ºC as a function of pH. The results of the model are
2679 plotted as the dotted line.
-11
-11,5 150 ºC
-12
log r + (mol/cm2/s)
-12,5
-13
-13,5
-14 Model
-14,5
-15
150
1 3 5 7 9
pH
2680

2681 Nepheline
2682
2683 The dissolution rates of the feldspathoid nepheline (NaAlSiO4) were reported by Tole
2684 et al. (1986) at 25 to 80 ºC and pH ranging from 3 to 11, Brady and Walther (1989) reported
2685 values at 25 ºC and pH 8, Lasaga (1998) reported rate at 25 ºC and pH 5 and Hamilton et al.
2686 (2001) reported rates at 25 ºC and pH from 1.3 to 12.4. In the absence of additional data to
2687 improve existing data fits, these we have adopted the empirical pH power function fit of
2688 Palandri and Kharaka (2004) in accord with:
2689 ( )
2690 ( )
2691 ( )
2692
2693 where rH+, rH2O and rOH- signifies the nepheline forward dissolution rate in acidic, neutral
2695 factors equal to 1.95x104, 7.94x10-2 and 7.24x10-9 mol/cm²/s respectively, EA, EB and EC
2696 designate an activation energy equal to 62.9, 65.4 and 37.8 kJ/mol, R represents the gas
2697 constant, and T denotes absolute temperature. In the absence of additional and more
2698 extensive data the Palandri and Kharaka fit has been adopted in this study. The degree to
2700 in Figure Nep1. Rates calculated using Equation Nep-1 described all of the rates reported by
2701 Tole et al. (1986) within uncertainty. In contrast, it can be seen in this figure that the rates
2702 provided by Hamilton et al. (2001) are systematically ~1 order of magnitude lower than the
2703 corresponding Tole et al. (1986) values, and are thus approximately one order of magnitude
2704 lower than those calculated with the fit equation listed above.
2705
151
2706

2707 References
2708 Brady P. V. and Walther J. V. (1989) Controls on silicate dissolution rates in neutral and basic pH
2709 solutions at 25°C. Geochim. Cosmochim. Acta 53, 2823-2830.
2712 2004-1068.
2713 Lasaga A. C. (1998) Kinetic Theory In the Earth Sciences. Princeton University Press, Princeton.
2714 Tole M. P., Lasaga A. C., Pantano C., and White W. B. (1986) The kinetics of dissolution of nepheline
2715 (NaAlSiO4). Geochim. Cosmochim. Acta 50, 379-392.
2716 Table Nep1: Summary of experimentally measured nepheline steady-state dissolution rates
Nepheline 25 8 Brady and Walther (1989)
Nepheline 25 1.3 – 12.4 Hamilton et al. (2001)
Nepheline 25 5 Lasaga (1998)
Nepheline 25 - 80 3 - 11 Tole et al. (1986)
2718
2719 Figure Nep1: Summary of experimentally measured nepheline steady-state dissolution rates
2720 reported in the literature as a function of pH and temperature. The dotted and dashed lines
2721 represent the results of the model.
-8 Brady and Walther

(1989), 25 C
Hamilton et al. (2001),
-9
25 C
Lasaga (1998), 25 C
log r+ (mol/cm2/s)
-10
Tole at al. (1986), 25 C
-11 Tole at al. (1986), 60 C
Tole at al. (1986), 80 C

-12
Kharaka, 2004)
-13 Model 60 C (Palandri and
Kharaka, 2004)
152 Model 80 C (Palandri and
-14 Kharaka, 2004)
0 2 4 6 8 10 12
pH
2722

2723 Oligoclase
2724
2725
2726
-10
-11
25 ºC Casey et al. (1991)
Cygan et al. (1989)

-12
log r+ (mol/cm2/s)

-13
-14 Oxburgh et al. (1993)
-15 Stillings and Brantley (1995)
-16 Stillings et al. (1996)
-17
Swoboda-Colberg and
Drever (1993)
-18
0 2 4 6 8 10 Model
pH
2727
153

2728 Paragonite
2729
2730 The phyllosilicate of the mica group paragonite (NaAl3Si3O10(OH)2) was studied by Lin
2731 and Clemency (1981) at 25 C and pH of 5.5 and reported by Nagy (1995). The conditions
2732 where the data was acquired are summarized in table Par1 and the available rate data are
2733 presented in Fig. Par1.
2734 Paragonite is a mica with a structure similar to muscovite where the K is replaced by
2735 Na, therefore owing to this similarity the dissolution rate data were fitted to:
2736 ( )( ) (Par-1)
2740 activation energy of the reaction was assumed to be equal to muscovite at 46.03 kJ/mol and
2741 AA the pre-exponential factor was calculated to fit the data reported by Nagy (1995) at
2742 1.32x10-7 mol/cm2/s.
2744 literature can be assessed in Figure Par1. Rates calculated using Equation Par-1 described all
2745 the reported rates within 0.8 log units.
2746
2747 References
2748 Lin, F.-C., and Clemency, C. (1981) The kinetics of dissolution of muscovites at 25°C and 1 atm CO2
2752 Mineralogical Society of America, 31, 173-233.
154
2753

2754 Table Par1: Summary of experimental conditions occurring during paragonite steady-state
Paragonite 25 5.5 Lin and Clemency (1981)
2756
2757 Figure Par1: Summary of experimentally measured phlogopite steady-state dissolution rates
2759 dotted line.
-12,00
25 ºC
-13,00
-14,00
log r+ (mol/cm2/s)
-15,00
model
-16,00
Palandri and
-17,00 Kharaka (2004)
Lin and Clemency
-18,00 (1981)
0 2 4 6 8 10 12
pH
2760
155

2761 Pyrite
2762
2763 The dissolution kinetics of the iron sulfide pyrite (FeS2) have been investigated by
2764 Gibbs et al., 1997a; Gibbs et al., 1997b; Holmes and Crundwell, 2000; Kamei and Ohmoto,
2765 2000; Lennie and Vaughan, 1992; McKibben and Barnes, 1986; Moses and Herman, 1991;
2766 Moses et al., 1987; Nicholson et al., 1988; Nicholson et al., 1990; Rickard, 1997; Rickard and
2767 Luther, 1997; Rickard, 1975; Rimstidt and Vaughan, 2003; Schoonen and Barnes, 1991a;
2768 Schoonen and Barnes, 1991b; Schoonen and Barnes, 1991c; Wiersma and Rimstidt, 1984;
2769 Williamson and Rimstidt, 1994. The different conditions where the data was acquired are
2770 summarized in table Ph1. The rates are presented for the different temperatures as a
2771 function of pH in Figure Ph1.
2772
156

2773 Phlogopite
2774 The dissolution kinetics of phlogopite (KAlMg3Si3O10(OH)2), an iron free mica, was
2775 studied by Lin and Clemency (1981a,b) at pH 5.34 and 25 ºC, Clemency and Lin (1981)
2776 reported dissolution rates at pH 3.05 and 25 ºC, McClelland (1950), Pitault et al. (1981),
2777 Schnitzler and Kodama (1976), Rausell-Colom et al. (1965), Razzaghe and Robert (1979),
2778 Marshall (1962). Kuwahara and Aoki (1995) studied phlogopite dissolution at pH 2 from 50º
2779 to 120 ºC but did not generate dissolution rates. Kalinowski and Schweda (1996) reported
2780 phlogopite rates at pH ranging from 1.1 to 4.1 and 25 ºC, Rufe and Hochella (1999) and
2781 Taylor et al. (2000). The different conditions where the data was acquired are summarized in
2782 table Ph1. The rates are presented for the different temperatures as a function of pH in
2783 Figure Ph1.
2784 As phlogopite is a biotite the same equation was used:
2785 ( )( ) (Ph-1)
2786 where r+ refers to the far-from-equilibrium phlogopite dissolution rate, AA represents a rate
2787 constant, R designates the gas constant, T signifies absolute temperature and ai represents
2788 the activity of the subscripted aqueous species, EA defines the activation energy of the
2789 reaction and n designates a stoichiometric coefficient equal to 0.125. The EA, of 49kJ/mol
2790 calculated for biotite was used, and AA was recalculated to 6.21.10-8 mol/cm2/s to fit the
2791 data by Kalinowski and Schweda (1996). The estimated EA value used in Ph-1 is somewhat
2792 higher than the EA calculated by Kuwahara and Aoki (29-42 kJ/mol).
2794 literature can be assessed in Figure Ph1. Rates calculated using Equation Ph-1 described 14
2796 References
2797 Clemency, C.V. and Lin, F.-C. (1981) Dissolution kinetics of phlogopite. II. Open-system using an ion-
2798 exchange resin. Clays Clay Miner. 29, 107-112.
157
2800 alteration at pH 1-4, 25 C. Geochim. Cosmochim. Acta 60, 367-385.

2801 Kuwahara, Y. and Aoki, Y. (1995) Dissolution process of phlogopite in acidic solution. Clays Clay
2802 Miner. 43, 39-50.
2803 Lin, F.-C. and Clemency, C.V. (1981) Dissolution kinetics of phlogopite. I. open-system. Clays Clay
2804 Miner. 29, 101-106.
2805 Lin, F.-C. and Clemency, C.V. (1981) Dissolution kinetics of phlogopite. II. Closed-system. Clays Clay
2806 Miner. 29, 107-112.
2807 Marshall, C.E. (1962) Reactions of feldspar and micas with aqueous solutions. Econ. Geol. 57, 1219-
2808 1227.
2809 McClelland, J.E. (1950) The effect of time, temperature and particle size on the release of bases from
2810 common soil-forming minerals of different crystal structure. Proceedings of the soil science
2811 society, 301-307.
2815 Pitault, B., Belin, E., Boutouaba, D. and Senemaud, C. (1981) K x-ray emission spectra from natural
2816 silicates. Chem. Phys. Lett.1, 123-125.
2817 Razzaghe, M.K., and Robert, M. (1979) Geochimie des elements majeurs des micas en milieu
2818 organique: mechanism de l’alteration des silicates. Ann. Agron. 30, 493-512.
2819 Rausell-Colom, J.A., Sweatman, T.R., Wells, C.B. and Norrish, K. (1965) Studies in the artificial
2820 weathering of mica in Experimental Podology, Hallworth E.G. and Crawford, D.V. (Eds.),
2821 Butterworths, pp. 40-72.
2822 Rufe, E. and Hochella, M.F. Jr. (1999) Quantitative assessment of reactive surface area of phlogopite
2823 during acid dissolution. Science 285, 874-876.
2824 Schnitzler, M. and Kodama, H. (1976) The dissolution of micas by fulvic acids. Geoderma 15, 381-391.
2825 Taylor A.S., Blum J.D., Lasaga A.C. and MacInnis I.N. (2000a) Kinetics of dissolution and Sr release
158
2827
2828
2829

2830 Table Ph1: Summary of experimental conditions occurring during smectite steady-state
phlogopite 25 3.05 Clemency and Lin (1981)
phlogopite 25 1-4 Kalinowski and Schweda (1996)
phlogopite 50 - 120 2 Kuwahara and Aoki (1995)
phlogopite 25 5.34 Lin and Clemency (1981c)
phlogopite 25 3.35 – 5.34 Nagy (1995)
Phlogopite 25 2, 5.7 Rufe and Hochella (1999)
phlogopite 25 3.3 Taylor et al. (2000)
2832
2833 Figure Ph1: Summary of experimentally measured phlogopite steady-state dissolution rates
2835 dotted line.
-12,00
Clemency and Lin (1981)
25 ºC
-13,00 Lin and Clemency (1981c)
log r+ (mol/cm2/s)
-14,00 Kalinowski and Schweda

(1996)
Nagy (1995)
-15,00
Rufe and Hochella (1999)

-16,00
-17,00
Model
-18,00
0 2 4 6 8 Razzaghe and Robert
(1979)
pH
2836
2837
159

2838 Prehnite
2839
2840 The calcium and aluminum phyllosilicate prehnite (Ca2Al2Si3O10(OH)2) has been
2841 studied by Rose (1991) at temperatures of 25 to 90 ºC and pH from 1.4 to 10.8. In the
2842 absence of additional data to improve existing data fits, these we have adopted the
2843 empirical pH power function fit of Palandri and Kharaka (2004) in accord with:
2844 ( )
2845 ( )
2846 ( )
2847
2848 where rH+, rH2O and rOH- signifies the prehnite forward dissolution rate in acidic, neutral and
2849 basic solutions and rtt the total dissolution rate, AA, AB and AC refer to pre-exponential
2850 factors equal to 2.75x10-1, 1.58x10-1 and 3.16x10-3 mol/cm²/s respectively, EA, EB, EC
2852 constant, and T denotes the absolute temperature. The degree to which this equation
2853 describes the dissolution rates reported in the literature can be assessed in Figure Pre1.
2854 Rates calculated using Equation Pre-1 described all the reported rates within 0.8 log units.
2855
2856 References
2859 Rose, N.M. (1991) Dissolution rate of phrenite, epidote and albite. Geochim. Cosmochim. Acta, 55,
2860 3273-3286.
2861
2862
160

2863 Table Pre1: Summary of experimental conditions occurring during prehnite steady-state
Prehnite 25-90 1.4 – 10.8 Rose (1991)
2865
2866 Figure Pre1: Summary of experimentally measured prehnite steady-state dissolution rates
2868 dotted and dashed line for the 25 and 90 ºC models, respectively.
2869
-12
90 ºC
-13
Rose (1989), 25 C
log r+ (mol/cm2/s)
-14
Rose (1989), 90 C
-15
Model (Palandri
and Kharaka,
-16
2004), 25 C
Model (Palandri
and Kharaka,
-17 2004), 90 C
-18
0 2 4 6 8 10 12
pH
2870
161

2871 Pyrophyllite
2872
2873 The phyllosilicate of the mica group pyrophyllite (Al2Si4O10(OH)2) were reported by
2874 Kline and Fogler (1981) in Nagy (1995) and they reported dissolution rates at 25 ºC and 1M
2875 HF solution. Scheidegger et al. (1996) also reported rates of pyrophyllite dissolution at 25 ºC
2876 and pH 7.5 in batch reactors. The different conditions where the data was acquired are
2877 summarized in table Pyr1 and the available rate data are presented in Fig. Pyr1.
2878 Pyrophyllite is a phyllosilicate with mica sheets. The dissolution rate data were fitted
2879 to:
2880 ( )( ) (Pyr-1)
2884 activation energy of the reaction was assumed to be equal to muscovite at 46.03 kJ/mol and
2885 AA the pre-exponential factor was calculated to fit the data reported by Scheidegger et al.
2886 (1996) at 2.2x10-8 mol/cm2/s.
2888 literature can be assessed in Figure Pyr1. Rates calculated using Equation Pyr-1 described 1
2890
2891 References
2892 Kline, W.E., and Fogler, H.S. (1981) Dissolution of silicate minerals by hydrofluoric acid. Ind. Eng.
2893 Chem. Fundam. 20, 155-161.
162
2897 Scheidegger, A.M., Lamble, G.M., and Sparks, DL. (1996) Investigation of Ni sorption on pyrophyllite:
2898 An XAFS study. Environ. Sci. Technol. 30, 548-554.

2899
2900 Table Pyr1: Summary of experimental conditions occurring during pyrophyllite steady-state
Pyrophyllite 25 0 Kline and Fogler (1981)
Pyrophyllite 25 7.5 Scheidegger et al. (1996)
2902
2903 Figure Pyr1: Summary of experimentally measured pyrophyllite steady-state dissolution rates
2905 dotted line.
2906
-12
-13
log r+ (mol/cm2/s)
-14
Kline and Fogler
(1981)
-15
Scheidegger et al.
-16 (1996)
Model
-17
-18
0 2 4 6 8 10
pH
2907
163

2908 Rhodochrosite
2909
2910 The dissolution kinetics of rhodochrosite (MnCO3) were investigated by Jensen et al.
2911 (2002) who reported rates gathered in anaerobic aquatic environment a 25 ºC and pH 7.5.
2912 Duckworth and Martin (2003) reported rates at 25 ºC and pH from 1.5 to 11.
2914 followed the interpretative guidelines of Plummer et al. (1978) for calcite and added an
2915 activation energy term for each dissolution mechanism. The pre-exponential factors were
2916 recalculated to fit the data:
2917 [ ( )] ( ) ( ) (Rho-1)
2918 where r+ signifies the siderite steady state dissolution rate, AA, AB and AC refer to pre-
2919 exponential factor equal to 57.9, 1x10-2 and 2.2x10-2 mol/cm²/s respectively, EA, EB and EC
2920 designate an activation energy equal to 61.0, 45.0 and 44.0 kJ/mol respectively, R represents
2921 the gas constant, T denotes absolute temperature and n is a reaction order equal to 0.7. The
2922 activation energies were assumed to be similar to siderite and the pre-exponential factors
2923 recalculated to fit Duckworth and Martin (2003) data. The degree to which this equation
2924 describes the dissolution rates reported in the literature can be assessed in Figure Sid1.
2925 Rates calculated using Equation Rho-2 described 24 of 25 reported rates within 0.8 log units.
2926
2927
164

2928 References
2929
2930 Duckworth, O.W. and Martin, S.T. (2004) Role of molecular oxygen in the dissolution of siderite and
2931 rhodochrosite. Geochim. Cosmochim. Acta 68, 607-621.
2932 Jensen, D.L., Boddum, J.K., Tjell, J.C. and Christensen, T.H. (2002) The solubility of rhodochrosite
2933 (MnCO3) and siderite (FeCO3) in anaerobic aquatic environments. Appl. Geochem. 17, 503-
2934 511.
2935 Table Rho1: Summary of experimental conditions occurring during rhodochrosite steady-
2936 state dissolution rates reported in the literature.
Rhodochrosite 25 1.5-11 Duckworth and Martin (2004)
Rhodochrosite 25 7.5 Jensen et al. (2002)
2937
2938 Figure Rho1: Summary of experimentally measured rhodochrosite steady-state dissolution

2939 rates reported in the literature as a function of pH. The results of the model are plotted as
-9,00
25 ºC
-10,00
log r+ (mol/cm2/s)
-11,00
-12,00 Duckworth and Martin

(2003b)
Model
-13,00
-14,00
165
0 2 4 6 8 10 12
pH
2941
2942

2943 Serpentine minerals

2944
2945 The dissolution kinetics of serpentine minerals (chrysotile, antigorite and lizardite)
2946 has been the subject of a rather limited number of experimental investigation, i.e. Luce et al.
2947 (1972) carried out batch experiments on lizardite at 25 ºC from pH 1.5 to 9, Lin and
2948 Clemency (1981) measured the dissolution rate of antigorite at 25 ºC and constant 1 bar CO2
2949 pressure at pH 6 to 6.5, Bales and Morgan (1985) determined the kinetics of chrysotile
2950 dissolution in batch experiments at 25 C and in the pH range 7-10 and Hume and Rimstidt
2951 (1992) studied the dissolution rate of chrysotile in synthetic lung fluid at 37 ºC. Thomassin et
2952 al. (1977) determined the activation energy for chrysotile dissolution to be 70 kJ/mol. These
2953 datasets were reviewed in 2004 by Cipolli et al., considerations upon which we based our
2954 kinetic equation:
2955 Log r+ = -0,31xpH – 7.08
2956 where r refers to the far-from-equilibrium phlogopite dissolution rate, R designates

2957 the gas constant, T signifies absolute temperature and ai represents the activity of the
2958 subscripted aqueous species. EA depicting the activation energy of the reaction was
2959 determined to be 70 kJ/mol and AA a pre-exponential factor was calculated -0,31
2960 mol/cm2/s. The degree to which the Eqn. Serp1 defines the available data can be assessed
2961 with the help of Fig. Serp 1.
2962
2963 References
2964
2965 Bales, R.C. and Morgan, J.J. (1985). Dissolution kinetics of Chrysotile at pH 7 to 10. Geochim.
2966 Cosmochim. Acta 49, 2281-2288.
2967 Hume, L.A. and Rimstidt, J.D. (1992). The biodurability of chrysotile asbestos. Am. Miner. 77, 1125-
2968 1128.
2969 Lin, F.-C. and Clemency, C.V., (1981). The dissolution kinetics of brucite, antigorite, talc, and
166
2970 phlogopite at 25 C and pressure. Am. Mineral. 66, 801-806.
2971 Luce, R.W., Barlett, R.W., and Parks, G.A. (1972). Dissolution kinetics of magnesium silicates.

2973 Thomassin, J.H., Goni, J., Baillif, P., Touray, J.C. and Jaurand, M.C. (1977) An XPS study of the
2974 dissolution kinetics of chrysotile in 0.1 N oxalic acid at different temperatures. Phys. Chem.
2975 Miner. 1, 385-398.
167

2976 Siderite
2977
2978 The dissolution kinetics of siderite (FeCO3) were investigated by Greenberg and
2979 Tomson (1992), Duckworth and Martin (2003), Golubev et al. (2009) and Tang and Martin
2980 (2011). Greenberg and Tomson (1992) determined the dissolution kinetics at 26 and 60 ºC at
2981 pH 4.88. Jensen et al. (2002) reported rates gathered in anaerobic aquatic environment a 25
2982 C and pH 7.5. Duckworth and Martin (2003) reported rates at 25 ºC and pH from 1.5 to 11,
2983 Golubev et al. (2009) reported rates at 25 to 100 ºC in acidic conditions (1<pH<4.6) and Tang
2984 and Martin (2011) reported dissolution rates in the presence of chromate at 25 ºC and pH
2985 from 1 to 11.
2987 followed the interpretative guidelines of Plummer et al. (1978) for calcite and added an
2988 activation energy term for each dissolution mechanism. The pre-exponential factors were
2989 recalculated to fit the data:
2990 [ ( )] ( ) ( ) (Do-2)
2991 where r+ signifies the siderite steady state dissolution rate, AA, AB and AC refer to pre-
2992 exponential factor equal to 57.9, 1x10-2 and 2.2x10-7 mol/cm²/s respectively, EA, EB and EC
2993 designate an activation energy equal to 61.0, 45.0 and 45.0 kJ/mol respectively, R represents
2994 the gas constant, T denotes absolute temperature and n is a reaction order equal to 0.7. The
2995 activation energies were determined from an Arrhenius plot of the data reported by
2996 Golubev et al. (1999) in acidic condition and calculated by Marini (2004) for neutral and basic
2997 conditions. The degree to which this equation describes the dissolution rates reported in the
2998 literature can be assessed in Figure Sid1. Rates calculated using Equation Sid-2 described 85
3000
3001
168

3002 References
3003
3004 Duckworth, O.W. and Martin, S.T. (2004) Role of molecular oxygen in the dissolution of siderite and
3005 rhodochrosite. Geochim. Cosmochim. Acta 68, 607-621.
3006 Golubev, S.V., Bénézeth, Schott, J., Dandurand, J.L. and Castillo, A. (2009) Siderite dissolution kinetics
3007 in acidic aqueous solutions from 25 to 100 °C and 0 to 50 atm pCO2. Chem. Geol. 265, 13-19.
3008 Greenberg, J. and Tomson, M (1992) Precipitation and dissolution kinetics and equilibria of aqueous
3009 ferrous carbonate vs temperature. Appl. Geochem. 7, 185-190.
3010 Jensen, D.L., Boddum, J.K., Tjell, J.C. and Christensen, T.H. (2002) The solubility of rhodochrosite
3011 (MnCO3) and siderite (FeCO3) in anaerobic aquatic environments. Appl. Geochem. 17, 503-
3012 511.
3013 Tang, Y. and Martin, S.T. (2011) Siderite dissolution in the presence of chromate. Geochim.
3014 Cosmochim. Acta 75, 4951-4962.
3015
3016
169

3017 Table Sid1: Summary of experimental conditions occurring during siderite steady-state
Siderite 25 1.5-11 Duckworth and Martin (2004)
Siderite 25-100 1-4.6 Golubev et al. (2009)
Siderite 26-60 4.88 Greenberg and Tomson (1992)
Siderite 25 7.5 Jensen et al. (2002)
Siderite 25 1-11 Tang and Martin (2011)
3019
3020 Figure Sid1: Summary of experimentally measured siderite steady-state dissolution rates
3022 dotted line.
-7
Duckworth and
25 ºC Martin (2003)
-8
Golubev et al (2009),
25C
-9
log r+ (mol/cm2/s)
60C
-10
100C
-11 Greenberg and
Tomson (1992)
-12 Tang and Martin
(2011)
-13 Model, 25C
-14 Model, 100C

0 2 4 6 8 10 12
pH
3023
3024
170

3025 Smectite - Montmorillonite

3026
3027 This complex group of minerals has been the subject of comparatively limited studies
3028 aimed at determining their dissolution kinetics. Hayasi and Yamada (1990) reported rates for
3029 Wyoming montmorillonite at pH 11 and 80 ºC. Zysset and Schindler (1996) determined the
3030 dissolution rate of Crook Country Wyoming montmorillonite at 25 ºC and pH ranging from 1
3031 to 5. Bauers and Berger (1998) carried out dissolution experiments on two smectites, Ceca
3032 and Ibeco, at 35 and 80 ºC with pH ranging from 11.5 to 14. Huertas et al. (2001) reported
3033 smectite dissolution rates at pH ranging from 7.5 to 8.6 and temperatures of 20º, 40º and 60
3034 ºC, Cama et al. (2002) investigated the dissolution rate of smectite as a function of
3035 thermodynamic activity at 80 ºC and pH of 8.8 and Rozalen et l. (2008) measured the
3036 dissolution kinetics of smectite at 25 ºC with pHs ranging from 1.1 to 13.7. The different
3037 conditions where the data was acquired are summarized in table Sm1. The rates are
3038 presented for the different temperatures as a function of pH in Figure Sm1.
3039 The published data presented in Fig. Sm1 was fitted with the help of Eqn. Sm-1
3040 defined by Huertas et al. (2001):
0.1
 a3  
3041 r  AA . exp  E A / RT   H 
 a 3 
 Al  Sm-1
3042 where r+ signifies the kaolinite steady state dissolution rate, AA refers to a pre-exponential
3043 factor equal to 5.65x10-13 mol/cm²/s, EA designates an activation energy equal to 27 kJ/mol,
3044 R represents the gas constant, T denotes absolute temperature and n signifies a
3045 stoichiometric coefficient equal to 0.1. AA and EA were determined from an Arrhenius plot
3046 of the data obtained at pH 8 by Huertas et al. (2001). The degree to which this equation
3047 describes the dissolution rates reported in the literature can be assessed in Figure Sm1.
3048 Rates calculated using Equation Sm-1 described xx of xx reported rates within 0.8 log units.
3049 The data provided by Zisset and Schindler (1996) is out of range for the serie containing 1M
3050 KCl which is probably due to the effect of the high concentration of the salt and the data
171
3051 published by Bauer and Berger (1998), Cama et al. (2000) and Hayasi and Yamada (1990).
3052

3053 References
3054
3055 Amram, K., and Ganor, J. (2005) The combined effect of pH and temperature on smectite
3056 dissolution rate under acidic conditions. Geochim. Cosmochim. Acta 69, 2535-2546.
3057 Bauer, A. and Berger, G. (1998) Kaolinite and smectite dissolution rate in high molar KOH
3058 solutions at 35º and 80ºC. Appl. Geochem. 13, 905-916.
3059 Cama, J., Ganor, J., Ayora, C. and Lasaga, C (2000) Smectite dissolution kinetics at 80 ºC and
3060 pH 8.8. Geochim. Cosmochim. Acta 64, 2701-2717.
3061 Hayasi, H. and Yamada, M. (1990) Kinetics of dissolution of noncrystalline oxides and
3062 crystalline clay minerals in a basic Titron solution. Clays Clay Miner. 38, 308-314.
3063 Huertas, F.J., Caballero, E., Jiménez de Cisneros, C., Huertas, F. and Linares, J. (2001) Kinetics
3064 of montmorillonite dissolution in granitic solutions. Appl. Geochem. 16, 397-407.
3065 Metz, V., Amram, K., and Ganor, J. (2005) Stoichiometry of smectite dissolution reaction.
3067 Rozalén, M.L., Huertas, F.J., Brady, P.V., Cama, J., Garcia-Palma, S. and Linares, J. (2008)
3068 Experimental study of the effect of pH on the kinetics of montmorillonite dissolution
3069 at 25 ºC. Geochim. Cosmochim. Acta 72, 4224-4253.
3070 Zysset, M. and Schindler, P.W. (1996) The proton promoted dissolution kinetics of K-
3071 montmorillonite. Geochim. Cosmochim. Acta 60, 921-931.
3072
172

3073 Table Sm1: Summary of experimental conditions occurring during smectite steady-state
smectite 35, 80 11.5 – 13.9 Bauer and Berger (1998)
montmorillonite 25 1-5 Cama et al. (2002)
montmorillonite 25, 60, 80 1 - 12 Hayasi and Yamada (1990)
montmorillonite 150 2, 6.8, 7.8 Huertas et al. (2001)
montmorillonite 25, 50, 80 3 - 4.2 Rozalén et al. (2008)
K-montmorillonite 25 2 - 6.5 Zysset and Schindler (1996)
3075
3076 Figure Sm1: Summary of experimentally measured smectite steady-state dissolution rates
3078 dotted line.
-12 Amram and Ganor (2005) 25 C
Amram and Ganor (2005) 70 C

-13
Bauer and Berger (1998), Ibeco, 35 C
-14
log r+ (mol/cm2/s)
Bauer and Berger (1998), Ceca, 35 C
Bauer and Berger (1998), Ibeco, 80 C

-15
Bauer and Berger (1998), Ceca, 80 C
-16 Cama et al. (2000), 80 C
Hayasi and Yamada (1990), 80 ºC

-17
Huertas et al. (2001), 20 C
-18 Huertas et al. (2001), 60 C
Huertas et al. (2001), 40 C

-19
Metz et al. (2005), 50 C
0 2 4 6 8 10 12 14
3079 pH
3080
3081
173

3082 Sphalerite
3083
3084 The zinc sulfide sphalerite (Zn, Fe S) dissolution has been studied by Majima et al.
3085 (1981) at temperature from 25 to 55 C and pH of 0.5, Crundwell and Verbaan (1987) at 25 C
3086 and pH 1, Moses and Hernan (1990) at 25 C and pH 6 and 7, Rimstidt et al. (1994) at 40 C and
3087 pH 2, Domenech et al (2002) at 22 C and pH of 2.5 to 4.3, Weisener et al. (2003) at 25 to 85 C
3088 and pH of 1, Malmström and Collin (2004) at 22 C and pH 1, Acero et al. (2007) at
3089 temperature of 25-70 C and pH from 1 to 4.2 and Jordan et al (2011) at pH 2 and
3090 temperature ranging from 20 to 200 C.
3091
3092 References
3093
3094 Acero, P., Cama, J. and Ayora, C. (2007) Sphalerite dissolution kinetics in acidic environment. Appl.
3095 Geochem. 22, 1872-1883
3096 Crundwell, F., Verbaan, B., 1987. Kinetics and mechanisms of the nonoxidative dissolution of
3097 sphalerite (zinc-sulphide). Hydrometallurgy 17, 369–384.
3098 Domènech, C., de Pablo, J., Ayora, C., 2002. Oxidative dissolution of pyritic sludge from the
3099 Aznalcollar mine (SW Spain). Chem. Geol. 190, 339–353.
3100 Jordan, G., Pokrovsky, O., Bahlo, J., Guichet, X., and Schlueter, C. (2011) Sphalerite dissolution
3101 kinetics at low hydrothermal conditions. Chem. Geol. 286, 272-279.
3102 Majima, H., Awakura, Y., Misaki, N., 1981. A kinetic-study of non-oxidative dissolution of sphalerite in
3103 aqueous hydrochloric-acid solutions. Metall. Trans. B 12, 645–649.
3104 Malmström, M.E., Collin, C., 2004. Sphalerite weathering kinetics: effect of pH and particle size. In:
3105 Wanty, R.B., Seal II, R.R. (Eds.), Proc. 11th Symp. Water–Rock Interaction, vol. 1. pp. 849–852.
3106 Rimstidt, J.D., Chermak, J.A., Gagen, P.M., 1994. Rates of reaction of galena, sphalerite, chalcopyrite
3107 and arsenopyrite with Fe(III) in acidic solutions. In: Alpers, C.N., Blowes, D.W. (Eds.),
3108 Environmental Geochemistry of Sulphide Oxidation. Am. Chem. Soc. Symp. Series 550,
3109 Washington, DC, 2–13.
3110 Weisener, C., Smart, R., Gerson, A., 2003. Kinetics and mechanisms of the leaching of low Fe
3111 sphalerite. Geochim. Cosmochim. Acta 67, 823–830.
174
3112
3113

3114 Table Sph1: Summary of experimentally measured sphalerite steady-state dissolution rates
range
sphalerite 25 5 Acero et al. (2007)
sphalerite 37 2-8 Crundwell and Verbaan (1987)
Sphalerite Demènech et al. (2002)
Sphalerite Jordan et al. (2011)
Sphalerite Majima et al. 81981)
Sphalerite Malmström and Collin (2004)
sphalerite Moses and Herman (1990)
Sphalerite Rimstidt et al. (1994)
sphalerite 25-150 1.7-9 Weisener et al (2003)
3116
3117 Figure Sph1: Summary of experimentally measured sphalerite steady-state dissolution rates
3119 dotted line.
-10
Acero et al. (2007)

log r+ (mol/cm2/s)
-12 Crundwell and Verbaan (1987)

Demènech et al (2002)
Jordan et al. (2011)
-14 Majima et al. (1981)
Malmström and Collin (2004)
Moses and Herman (1990)
-16 Weisener et al. (2003)

0 2 4 6 8 10 12
pH
175
3120

3121 Spodumene
3122
3123 Spodumene like jadeite (NaAl(SiO3)2) is an inosilicate with a clinopyroxene structure,

3124 where Si-O chains are held together with a monovalent cation and Al bridges; for the case of
3125 spodumene the monovalent cation is Li. Its dissolution kinetics was only reported by
3126 Sverdrup (1990) at 25 ºC and pH ranging from 3 to 6.5. These data points are plotted on Fig.
3127 Sp1 and detailed in Table Sp1.
3128 By analogy with jadeite it seems reasonable to assume that its dissolution mechanism
3129 consists of the sequential removal of Li then Al via proton exchange reactions prior to the
3130 final removal of Si-O tetrahedra from the mineral. In such cases dissolution rates are
3131 commonly consistent with:
3132 ( ) ( ) Sp-1
3133 where r signifies the spodumene steady state dissolution rate, AA refers to a pre-exponential
3134 factor equal to 1.5x10-3 mol/cm²/sec, EA designates an activation energy equal to 48 kJ/mol,
3135 n refers to a constant equal to 0.25, R represents the gas constant, and T denotes absolute
3136 temperature. As was the case for jadeite, EA was set to be equal to 48 kJ/mol by analogy
3137 with the amphiboles, chain silicates also held together by bridging Al-octahedrals. The
3139 be assessed in Figure Sp1. Rates calculated using Equation Sp-1 described 3 of 3 reported
3141
3142 References
3143
3146
3147
3148
3149
176
3150

3151 Table Sp1: Summary of experimental conditions occurring during spodumene steady-state
Spodumene 25 3, 4.5, 6.5 Sverdrup (1990)
3153
3154 Figure Sp1: Summary of experimentally measured spodumene steady-state dissolution rates
3156 dashed line.
-8
-9
25 ºC
-10
log r+ (mol/cm2/s)
-11
-12
-13 Sverdrup (1990)

Model
-14
-15
-16
2 4 6 8 10
3157 pH
3158
3159
177

3160 Staurolite
3161
3162 The dissolution rates of the iron aluminum nesosilicate staurolite

3163 (Fe1.4Li0.1Mg0.1Al8.7Si3.9O21.7(OH)2.3) was reported by Nickel (1973) at 25 ºC and pH ranging
3164 from 0.2 to 11. These data were fit by Palandri and Kharaka (2004) using:
3165 ( )
3166 ( )
3167 ( )
3168
3169 where rH+, rH2O and rOH- signifies the staurolite forward dissolution rate in acidic, neutral
3170 and basic solutions and r+ the overall dissolution rate, AA, AB and AC refer to pre-exponential
3171 factors equal to 2.57x10-8, 5.25x10-5 and 2.34x10-11 mol/cm²/s respectively, EA, EB and EC
3172 designate an activation energies equal to 18.9, 56.6 and 47.2 kJ/mol, R represents the gas
3173 constant, and T denotes absolute temperature. As was the case for andradite in the absence
3174 of additional and more extensive data, the Palandri and Kharaka (2004) fit was adopted in
3175 this study. It should be noted that these activation energies are based on the fit of rates
3176 obtained at 8 and 25 ºC, and the rate data at 8 ºC were never directly reported. The degree
3177 to which this equation describes the dissolution rates reported in the literature can be
3178 assessed in Figure St1. Rates calculated using Equation St-1 described 8 of 9 reported rates
3179 within 0.8 log units.
3180
3181 References
178
3186 2004-1068.

3189 Table St1: Summary of experimentally measured staurolite steady-state dissolution rates
Staurolite 25 0.2-11 Nickel (1973)
3191
3192 Figure St1: Summary of experimentally measured staurolite steady-state dissolution rates
3194 model.
-10
-11
-12
log r+ (mol/cm2/s)
-13
-14 Nickel (1973)
-15 Model (Palandri et Kharaka,

2004)
-16
-17
-18
0 2 4 6 8 10 12
pH
3195
179

3196 Struvite
3197
3198 The magnesium ammonium phosphate struvite (NH4MgPO4-6H2O) dissolution has

3199 been studied by Roncal-Herrero and Oelkers (2011) at 25 ºC and pH 7.7 to 10.6.
3200
3201 References
3202
3203 Roncal-Herrero, T., and Oelkers, E.H. (2011) Experimental determination of struvite dissolution and
3204 precipitation rates as a function of pH. Appl. Geochem. 26, 921-928.
3205
3206 Table Str1: Summary of experimental conditions for the struvite steady-state dissolution
range
Tourmaline 25 0.2-10.5 Roncal-Herrero and Oelkers (2011)
3208
3209 Figure Str1: Summary of experimentally measured struvite steady-state dissolution rates
3211 dotted line.
3212
-12
25 ºC
-12,5
log r+ (mol/cm2/s)
-13
-13,5
Roncal-Herrero
and Oelkers (2011)
-14
Model
-14,5
180 0 2 4 6 8 10 12
pH
3213

3214 Talc
3215
3216 Dissolution rates of talc at 25 to 150 ºC and various pH have been studied by Lin and
3217 Clemency (1981), Jurinski and Rimstidt (2001) and Saldi et al., (2007). The rates are
3218 presented as a function of pH in Figure E1. Rates reported by Jurinski and Rimstidt (2001) at
3219 37 ºC exhibit a pH dependence inconsistent with those of Saldi et al. (2007); these former
3220 rates are mostly pH independent, whereas the later rates decrease continuously with
3221 increasing pH. This latter dependence is consistent with that of other Mg silicate minerals
3222 including enstatite and tremolite (e.g. Oelkers and Schott, 2001).
3223 Steady-state talc dissolution rates were fit to (Saldi et al., 2007)
  a2 
1/ 8

 
r  S  AA  H   AB  exp  EA / RT 

3224 (T-1)
  a Mg 2  
 
 
3225 where r signifies the talc steady-state dissolution rate, AA and AB refer to pre-exponential
3226 factors equal to 5x10-9 and 0.8x10-9 mol/cm²/sec4, EA designates an activation energy equal
3227 to 45 kJ/mol, R represents the gas constant, and T denotes absolute temperature.  stands
3228 for Temkin's average stoichiometric number equal to the ratio of the rate of destruction of
3229 the activated or precursor complex relative to the overall rate. For the case of talc,  is
3230 taken to be equal to 4, the number of Si in the talc chemical formula. This choice is
3231 consistent with the assumption that the activated species for talc dissolution contains one Si
3232 atom. The degree to which this equation describes the dissolution rates reported in the
3233 literature can be assessed in Figure T1. Rates calculated using Equation T-1 described 46 of
3234 50 reported rates within 0.8 log units with an average uncertainty of 0.3 log units.
3235 References
3236
3237 Jurinski J.B., Rimstidt, J.D. (2001). Biodurability of talc. Am. Min. 86, 392-399.
3238 Lin F.-C., Cemency, C.V. (1981) The dissolution kinetics of brucite, antigorite, talc and phlogopite at
3239 25 C and pressure. Am. Min., 66, 801-806.
181
4 -4
Note this value is corrected from that in the original Oelkers and Schott (2001) that was reported as 2.4x10
mol/cm²/sec.
3240 Saldi G.D., Köhler S.J., Marty N., Oelkers E.H., 2007. Dissolution rates of talc as a function of
3241 solution composition, pH and temperature. Geochim. Cosmochim. Acta 71, 3446-3457.
3242
3243 Table T1: Summary of experimentally measured talc steady-state dissolution rates reported
3244 in the literature.
range
Talc 25 5 Lin and Cemency (1981)
Talc 37 2-8 Jurinski and Rimstidt (2001)
Talc 25-150 1.7-9 Saldi et al. (2007)
3245
3246 Figure T1: Summary of experimentally measured talc steady-state dissolution rates reported
3247 in the literature as a function of pH. The results of the model at 25 ºC are plotted in dotted
3248 line.
-12
-13
log r (mol/cm2/s)
-14
-15
-16
-17
-18
0 2 4 6 8 10 12
pH
150 Jur 37C

135 80
182 25 Model 25
3249
3250

3251 Tourmaline
3252
3253 The dissolution rates of the boron containing cyclosilicate tourmaline were studied by
3254 Nickel (1973) and recalculated by Sverdrup (1990) and these data are plotted in fig. Tou1. In
3255 the absence of a mechanistic model Palandri and Kharaka (2004) fit these rates assuming
3256 they are controlled by two parallel reactions, one proton promoted, and one water
3257 promoted in accord with :
3258 ( )
3259 ( )
3260 which can be summed to yield the overall forward rate using
3261
3262 where rH+ and rH2O signifies the tourmaline steady-state dissolution rate in response to the
3263 proton and water promoted mechanisms, respectively, and r+ the total forward dissolution
3264 rate, AA and AB refer to pre-exponential factors equal to 5.37x102 and 4.9x10-1 mol/cm²/s
3265 respectively, EA designates an activation energy equal to 75.5 and 85.0 kJ/mol respectively, R
3266 represents the gas constant, and T denotes absolute temperature. The degree to which
3267 these equations describes the measured can be assessed in Figure Tou1. Rates calculated
3268 using Equation Tou-1 described all 3 of the reported rates within 0.8 log units.
3269
3270 References
3271
3274 2004-1068.
183
3279

3280 Table Tou1: Summary of experimental conditions for the various tourmaline steady-state
range
Tourmaline 25 0.2-10.5 Nickel (1973)
3282
3283 Figure Tou1: Summary of experimentally measured tourmaline steady-state dissolution rates
3285 dotted line.
-12
-13
log r+ (mol/cm2/s)
-14
Nickel (1973) in
Sverdrup (1990)
-15
Model (Palandri and
Karakha, 2004)
-16
-17
0 2 4 6 8 10 12
pH
3286
3287
184

3288 Tremolite
3289
3290 The Ca bearing amphibole tremolite (Mg7Si8O22(OH)2) dissolution was studied by

3291 Tunn (1939) at 25 ºC and pH ranging from 0.2 to 11; these data were recalculated and
3292 reported by Sverdrup (1990). Schott et al. (1981) reported dissolution rates at 20 ºC and pH 1
3293 and 6 at 25 ºC. Recently Dietrich et al. (2012) reported tremolite rate data at temperatures
3294 from 25 to 150 ºC and pH ranging from 1.9 to 6.9. These experimental conditions are
3295 reported in Table Tre1 and plotted on Fig. Tre1.
3296 The data was fitted to:
3297 ( )( ) Tre-1
3298 where r+ signifies the tremolite steady state dissolution rate, AA refers to a pre-exponential
3299 factor equal to 1.54x10-6 mol/cm²/s, EA designates an activation energy equal to 55.8 kJ/mol,
3300 R represents the gas constant, T denotes absolute temperature and n signifies a
3301 stoichiometric coefficient equal to 0.125. In the absence of extensive data for tremolite
3302 dissolution rates as a function of the temperature EA was set equal to that of anthophyllite
3303 (55.8 kJ/mol). AA was calculated to fit the data shown in Fig Tre1. As such tremolite forward
3304 dissolution rates are equal to 0.9 times that of anthophyllite rates for all temperature and
3305 solution composition. The faster rates of tremolite dissolution can be attributed to the
3306 presence of rapidly removed Ca from its structure. The degree to which equation Tre-1
3307 describes the dissolution rates reported in the literature can be assessed in Figure Tre1.
3308 Rates calculated using Equation Tre-1 described 30 of 35 reported rates within 0.8 log units.
3309
3310 References
3311
3312 Diedrich, T.R., Oelkers, E.H. and Schott, J. (2011) Quantifying tremolite, serpentine and talc
3313 dissolution rates: implication for the biodurability of Mg-silicate dust. 2011 GSA Annual
3314 Meeting.
3315
185 Mast, M.A. and Drever, J.I (1987) The effect of oxalate on the dissolution rates of oligoclase and
3316 tremolite. Geochim. Cosmochim. Acta 51, 2559-2568.
3317 Schott, J., Berner, R.A., Sjöberg, E.L. (1981) Mechanism of pyroxene and amphibole weathering - I.
3318 Experimental studies of iron-free minerals. Geochim. Cosmochim. Acta 45, 2123-2135.

3321 Tunn, W. (1939) Untersuchungen ueber die Verwitterung des Tremolit. Chemie der Erde 12, 275-303.
3322
3323 Table Tre1: Summary of experimentally measured tremolite steady-state dissolution rates
Tremolite 25-150 1.9-6.8 Dietrich et al. (2012)
Tremolite 22 2-9 Mast and Drever (1987)
Tremolite 20 1, 6 Schott et al. (2001)
Tremolite 25 3 – 6.8 Sverdrup (1990)
Tremolite 25 0.2-11 Tunn (1939)
3325
3326 Figure Tre1: Summary of experimentally measured tremolite steady-state dissolution rates
3328 dotted line.
-14
25 ºC Dietrich et al.
(2012), 25 C
-15 Dietrich et al.

(2012), 35 ºC
log r+ (mol/cm2/s)
Mast and Drever

(1987), 22 ºC
-16
Schott et al. (1981),
20 C
-17 Tunn (1939)
Model, 25 C
-18
0 2 4 6 8 10
186 pH
3329

3330 Uraninite
3331
3332 The oxide uraninite (UO2) dissolution kinetics have been studied by Grandstaff
3333 (1976) and lately by Ivanov and Popov (2011) at 25 C from 5 to 8.5. The available data was
3334 fitted by Palandri and Kharaka (2004) to:
3335 ( ) Ur1
3336 where r+ signifies the uraninite total forward dissolution rate, AA refers to a pre-exponential
3337 factor equal to 2.26x10-9 mol/cm²/s, EA designates an activation energy equal to 75.5 kJ/mol,
3339 this equation describes the measured can be assessed in Figure Ur1. Rates calculated using
3340 Equation Ur-1 described all the reported rates within 0.8 log units.
3341
3342 References
3343
3344 Grandstaff D. E. (1976) A kinetic study of the dissolution of uraninite. Econ. Geol. 71, 1493-1506.
3345 Ivanov, V.V. and Popov, I.B. (2011) Kinetics of Dissolution of Stoichiometric Uraninite. Radiochem. 53,
3346 160-163.
3347
3348
187

3349 Table Ur1: Summary of experimental conditions occurring during variscite steady-state
Uraninite 25 - Granstaff (1976)
Uraninite 25 5-8.5 Ivanov and Popov (2011)
3351
3352 Figure Ur1: Summary of experimentally measured variscite steady-state dissolution rates
3355
-11
-12
log r+ (mol/cm2/s)
-13
Ivanov and Popov
(2011)
-14
Model (Palandri and
Kharaka (2004)
-15
-16
2 4 6 8 10
pH
3356
188

3357 Variscite
3358
3359 The hydrated aluminum phosphate variscite (AlPO4:2H2O) dissolution has been studied
3360 by Roncal-Herrero and Oelkers (2011) in mixed flow and batch reactors at 25 C and pH ranging from
3361 1.51 to 8.99. The different conditions where the data was acquired are summarized in table
3362 Wit1. The rates are presented for the different temperatures as a function of pH in Fig. Wit1.
3363 Variscite dissolution rates were described by Roncal-Herrero and Oelkers (2011) by:
3364 Var1
3365 Where r+ represent the forward variscite dissolution rates.
3366
3367 References
3368
3369 Roncal-Herrero, T., and Oelkers, E.H. (2011) Does variscite control phosphate availability in acidic
3370 natural waters? An experimental study of variscite dissolution rates. Geochim. Cosmochim.
3371 Acta 75, 416-426.
3372
3373 Table Var1: Summary of experimental conditions occurring during variscite steady-state
Variscite 25 1.5 - 9 Roncal-Herrero and Oelkers (2011)
3375
3376 Figure Var1: Summary of experimentally measured variscite steady-state dissolution rates
3379
3380
189

-13
log r+ (mol/cm2/s)
-14
Roncal-Herrero and
Oelkers (2011)
-15
Roncal-Herrero and
Oelkers (2011)
-16 Model
-17
1 3 5 7 9
pH
3381
190

3382 Witherite
3383
3384 The barium carbonate mineral witherite (BaCO3) has been studied by Chou et al.
3385 (1989) at 25 ºC and pH ranging from 4.5 to 9.8. The different conditions where the data was
3386 acquired are summarized in table Wit1. The rates are presented for the different
3387 temperatures as a function of pH in Fig. Wit1.
3388 The available data was fitted to an equation from Chou et al. (1989) with the
3389 inclusion of activation energies to:
( )
( ) ( )
( ) ( )
3390 where rH+, rH2CO3 and rH2O signifies the witherite forward dissolution rate in acidic, neutral
3392 factors equal to 8.86, 10 and 2.2x10--5 mol/cm²/s respectively, EA, EB and EC designate
3393 activation energies equal to 34.0, 21.0 and 16.0 kJ/mol, R represents the gas constant, T
3394 denotes absolute temperature and n signifies a stoichiometric coefficient equal to 0.75. The
3396 be assessed in Figure Wit1. Rates calculated using Equation Wit-1 described all of the
3397 reported rates at 25 ºC within 0.8 log units.
3398
3399 References
3400
191
3403

3404 Table Wit1: Summary of experimental conditions occurring during witherite steady-state
Witherite 25 4.5-9.8 Chou et al. (1989)
3406
3407 Figure Wit1: Summary of experimentally measured witherite steady-state dissolution rates
3410
-6
-7
25 ºC
log r+ (mol/cm2/s)
-8
-9
-10
Chou et al.
-11 (1989)
Model
-12
2 4 6 8 10
pH
3411
192

3412 Wollastonite
3413
3414 Wollastonite dissolution rates were reported by Rimstidt and Dove (1986) at 23.5 ºC
3415 and pH ranging from 4.5 to 7, Sverdrup (1990) at 25 ºC and pH 3, 4 and 7, Feruzzi (1994) at
3416 25 ºC at 25 C and pH from 2 to 9.6, Xie (1994), Xie and Walther (1994), Weissbart and
3417 Rimstidt (2000) at 23.5 ºC and pH 1.9 to 6.2, Golubev et al. (2005) at 25 C and pH ranging
3418 from 3.1 to 12.2, Pokrovsky et al. (2009), also at 25 ºC and with pH from 6.9 to 11.0, and
3419 Schott et al. (2012) at 25 ºC and pH ranging from 0.26 to 12.
3420 The different conditions where the data was acquired are summarized in table Wo1.
3421 The rates are presented for the different temperatures as a function of pH in Figure Wo1.
3422 The published data presented in Fig. Wo1 was fitted using (c.f. Oelkers and Schott, 2001)
3423 ( ) ( ) Wo-1
3424 where r+ signifies the wollastonite steady state dissolution rate, AA refers to a pre-
3425 exponential factor equal to 2x10-4 mol/cm²/s, EA designates an activation energy equal to 45
3426 kJ/mol, R represents the gas constant, and T denotes absolute temperature. EA was taken
3427 from Palandri and Kharaka (2004). The degree to which this equation describes the
3428 dissolution rates reported in the literature can be assessed in Figure Wo1. Rates calculated
3429 using Equation Wo-1 described 95 of 108 reported rates at 25 ºC within 0.8 log units.
3430
3431
193

3432 References
3433
3434 Feruzzi, G.G. (1994) The character and rates of dissolution of pyroxenes and pyroxenoid. M. Sc.
3435 Thesis, University of California, Davis.
3437 CO2 on the dissolution kinetics of Mg and Ca silicates at 25 ºC. Chem. Geol. 217, 227-238.
3440 Pokrovsky, O.S., Shirikova, L.S., Benezeth, P., Schott, J. and Golubev, S.V. (2009) Effect of organic
3441 lignads and heterotrophic bacteria on wollastonite dissolution kinetics. Am. J. Sci. 309, 731-
3442 772.
3443 Rimstidt, J.D. and Dove, P.M. (1986) Mineral/solution reaction rates in a mixed-flow reactor:
3444 Wollastonite hydrolysis. Geochim. Cosmochim. Acta 50, 2509-2516.
3445 Schott, J., Pokrovsky, O., Spalla, O., Devreux, F., Gloter, A. and Mielczarski, A. (2012) Formation,
3446 growth and transformation of leached layers during silicate minerals dissolution: The
3447 exemple of wollastonite. Geochim. Cosmochim. Acta 98, 259-281.
3450 Weissbart, E.J. and Rimstidt, J.D. (2000) Wollastonite: Incongruent dissolution and leached layer
3451 formation. Geochim. Cosmochim. Acta 64, 4007-4016.
3452 Xie, Z. (1994) Surface properties of silicates, their solubilities and dissolution kinetics. PhD Thesis,
3453 Northwestern University, Evanston, IL.
3454 Xie, Z. and Walther, J.V. (1994) Dissolution stoichiometry and adsorption of alkali and
3455 alkaline earth elements to the acid-reacted wollastonite surface at 25 ºC. Geochim.
3456 Cosmochim. Acta 58, 2587-2598.
3457
3458
194

3459 Table Wo1: Summary of experimental conditions occurring during smectite steady-state
Wollastonite 25 2 – 9.6 Feruzzi (1994)
Wollastonite 25 3.1 – 12.2 Golubev et al. (2005)
Wollastonite 25 6.9 - 11 Pokrovsky et al. (2009)
Wollastonite 23.5 4.5 - 7 Rimstidt and Dove (1986)
Wollastonite 25 0.9 - 12 Schott et al. (2012)
Wollastonite 25 2, 4, 7 Sverdrup (1990)
Wollastonite 25 1.9 - 6.2 Weissbart and Rimstidt (2000)
Wollastonite 25 - 80 1.6 – 12.4 Xie (1994)
Wollastonite 25 - Xie and Walther (1994)
3461
3462 Figure Wo1: Summary of experimentally measured smectite steady-state dissolution rates
-10 Feruzzi (1994)
Golubev et al. (2005)

-11
log r+ (mol/cm2/s)
Rimstidt and Dove (1986)

-12
Schott et al. (2012)
-13 Sverdrup (1990)
Weissbart and Rimstidt

(2000)
-14
Xie (1994)
25 ºC
Model
-15
195 0 2 4 6 8 10 12
pH
3465

3466 Zoisite
3467
3468 Zoisite (Ca2Al3(SiO4)3OH) is a Ca endmember of the epidote group of minerals. To

3469 date, only a single study has reported zoisite dissolution rates (Sverdup, 1990). The
3470 dissolution rates of zoisite reported by Sverdrup (1990) match closely corresponding values
3471 reported by the same author on epidote. As can be seen in Fig Ep1 the dissolution rates of
3472 epidote reported by Sverdrup (1990) have a pH variation inconsistent with rates reported in
3473 the majority of other studies. As such we have adopted the epidote fit to describe the
3474 dissolution rates of zoisite in this study. This approach contrast to that of Palandri and
3475 Kharaka (2004) who fit these Sverdrup (1990) rates to a distinct equation. As such, rate
3476 calculations performed using the Palandri and Kharaka (2004) equations would yield 25 C
3477 dissolution rates of zoisite that differ by as much as 3 orders of magnitude from those of
3478 epidote depending on pH; which is likely unrealistic considering the similarity of their
3479 respective structures and compositions.
3480
3481
196

3482 References
3483
3488
3489 Table Z1: Summary of experimentally measured zoisite steady-state dissolution rates
Zoisite 25 3-10.5 Sverdrup (1990).
3491
3492 Figure Z1: Summary of experimentally measured zoisite steady-state dissolution rates
3494 dotted line.
-12
-13
log r+ (mol/cm2/s)
-14
Sverdrup (1990)
-15
Model (Palandri and
Kharaka, 2004)
-16
-17
0 2 4 6 8 10 12
pH
3495
197

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CarbFix Project no.

281348 WP5 – PHREEQC Database

18 Authors: Julien Declercq, Eric H. Oelkers

Geoscience Environement Toulouse | 14. Av. E. Belin 31400 Toulouse

Geoscience Environement Toulouse | 14. Av. E. Belin 31400 Toulouse

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Geoscience Environement Toulouse | 14. Av. E. Belin 31400 Toulouse

122 Kaolinite........................................................................................................................................... 131

Geoscience Environement Toulouse | 14. Av. E. Belin 31400 Toulouse

156 References ................................................................................................................................... 189

Geoscience Environement Toulouse | 14. Av. E. Belin 31400 Toulouse

167 THIS IS A PRELIMINARY VERSION OF THIS DATABASE; PROOFREADING AND CORRECTIONS BY

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Geoscience Environement Toulouse | 14. Av. E. Belin 31400 Toulouse

203 Mineral Description

Geoscience Environement Toulouse | 14. Av. E. Belin 31400 Toulouse

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Geoscience Environement Toulouse | 14. Av. E. Belin 31400 Toulouse

Geoscience Environement Toulouse | 14. Av. E. Belin 31400 Toulouse

Mineral T, °C pH range Reference

Cleavelandite 80 3, 8.8 Burch et al. (1991)

Cleavelandite 80 8.8 Burch et al. (1993)

Albite 25 2 Casey (1991)

Cleavelandite 25 1.2–7.11 Chou and Wollast (1984)

Cleavelandite 25 1-12.5 Chou and Wollast (1985)

Albite An2 5-90 1, 4.5 Chen and Brantley (1997)

Albite 225 0.8-8 Hellmann et al. (1990)

Albite 100-300 2-10 Hellmann (1994)

Albite 150 8.8 Hellmann and Tisserand (2006)

Albite, Ab 99.07 n.c. n.c. Holdren and Berner (1978)

Cleavelandite n.c. 3 Holdren and Speyer (1987)

Albite, Ab 99.07 25, 70 1.39-11.75 Knauss and Wolery (1986)

Albite 200 7,27 Lagache (1965), recalculated by Helgeson

Albite 25 1.4 Rose (1991)

Albite An2 25 3.32 Stillings et al. (1996)

Albite 22 Welch and Ullman (1996)

Albite 25 1-12 Wollast and Chou (1985)

Geoscience Environement Toulouse | 14. Av. E. Belin 31400 Toulouse

25 ºC Chou and Wollast (1985)

Geoscience Environement Toulouse | 14. Av. E. Belin 31400 Toulouse

Geoscience Environement Toulouse | 14. Av. E. Belin 31400 Toulouse

Mineral T, °C pH range Reference

Almandine 25 0.2-11 Nickel (1973)

Almandine 25 3-7 Schott and Petit (1987)

329 Andesine / Labradorite

331 Andesine (Na0.7Ca0.Al1.3Si2.7O8) and labradorite are two feldspars of the

Geoscience Environement Toulouse | 14. Av. E. Belin 31400 Toulouse

Geoscience Environement Toulouse | 14. Av. E. Belin 31400 Toulouse

Mineral T, °C pH range Reference

Andesine 25 3, 8.8 Casey et al. (1991)

Andesine 25 3 Holdren and Speyer (1987)

Andesine, An46 25 3.1 – 7.3 Oxburgh et al. (1994)

Labradorite 25 4 Siegel and Pfannkuch (1984)

Labradorite 25 3 – 3.12 Stillings and Brantley (1995)

Andesine, An43, An47 25 2.96 – 7.65 Stillings et al. (1996)

Andesine, An30 25 Swoboda-Colberg and Drever (1993)

Labradorite 25 3.08 Taylor et al. (2000)

Andesine 230 - 245 0.4 – 1.7 Tzuzuki and Suzuki (1980)

Andesine, An49 22 3.1 – 9 Welch and Ullman (1996)

-13 Busenberg and Clemency

Casey et al. (1991)

Oxburgh et al. (1994)

Holdren and Spayer (1987)

Stillings and Brantley (1995)