S1 Supporting Information 1 Mutual interactions between reduced Fe-bearing clay minerals and humic 2 acids under dark, oxygenated condition: hydroxyl radical generation and humic 3 acid transformation 4 Qiang Zeng 1,2 , Xi Wang 1,2 , Xiaolei Liu 1,3 , Liuqin Huang 4,5 , Jinglong Hu 1,2 , Rosalie 5 Chu 5 , Nikola Tolic 5 and Hailiang Dong* 1,2 6 1. Center for Geomicrobiology and Biogeochemistry Research, State Key Laboratory 7 of Biogeology and Environmental Geology, China University of Geosciences, Beijing 8 100083, China. 9 2. School of Earth Sciences and Resources, China University of Geosciences, Beijing 10 100083, China 11 3. School of Water Resources and Environment, China University of Geosciences, 12 Beijing 100083, China 13 4. State Key Laboratory of Biogeology and Environmental Geology, China University 14 of Geosciences, Wuhan 430074, China 15 5. Environmental Molecular Sciences Laboratory, Pacific Northwest National 16 Laboratory, Richland, Washington 99352, UnitedStates 17 * Corresponding author at: State Key Laboratory of Biogeology and Environmental 18 Geology, China University of Geosciences, Beijing 100083, China. Tel.: 19 +86-10-82320969; Email: [email protected]20 21 22 23 Total number of pages: 28 24 Total number of tables: 1 25 Total number of figures: 17 26 27 28
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S1
Supporting Information 1
Mutual interactions between reduced Fe-bearing clay minerals and humic 2
acids under dark, oxygenated condition: hydroxyl radical generation and humic 3
1. Center for Geomicrobiology and Biogeochemistry Research, State Key Laboratory 7 of Biogeology and Environmental Geology, China University of Geosciences, Beijing 8
100083, China. 9
2. School of Earth Sciences and Resources, China University of Geosciences, Beijing 10 100083, China 11
3. School of Water Resources and Environment, China University of Geosciences, 12 Beijing 100083, China 13
4. State Key Laboratory of Biogeology and Environmental Geology, China University 14 of Geosciences, Wuhan 430074, China 15
5. Environmental Molecular Sciences Laboratory, Pacific Northwest National 16 Laboratory, Richland, Washington 99352, UnitedStates 17
* Corresponding author at: State Key Laboratory of Biogeology and Environmental 18 Geology, China University of Geosciences, Beijing 100083, China. Tel.: 19
188 Figure S1. Correlation between dosage of sodium benzoate and the cumulative •OH 189 production from rNAu-2 oxygenation in the presence of 500 ppm PPHA. The error 190 bars represent standard deviation from duplicate experiments. 191
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194 Figure S2. Sorption of hydroxybenzoic acids to rNAu-2 and rSWy-2 surfaces, where 195 ce represents aqueous concentration of hydroxybenzoic acid and qe represents the 196 sorbed concentration after equilibrium for 2 hours. Experiments were conducted 197 under anaerobic conditions to avoid •OH production. 198
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Figure S3. Oxidation kinetics of rSWy-2 [2.5 g/L, total 0.7 mM Fe(II)] in the absence 203
and presence of different concentrations of PPHA (A) and LHA (B), corresponding 204
time-course accumulation of •OH (C, D), and linear correlations between •OH yield 205
and the amount of oxidized Fe(II) (E, F). The slope k represents •OH yield 206
(micromole) per millimole of oxidized Fe(II). The correlation coefficients (R2) were 207
greater than 0.98 for all groups. The error bars represent standard deviation from 208
duplicate experiments. 209
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Figure S4. Modeling of Fe(II) oxidation kinetics of rNAu-2 in the absence and 211 presence of different concentrations of HA. The kinetic data were fitted with a second 212
order rate equation, 1𝐶𝐶− 1
𝐶𝐶0= 𝑘𝑘𝑘𝑘, where C represents the total Fe(II) concentration at 213
selected sampling points, and C0 represents the initial Fe(II) concentration. The 214 correlation coefficients (R2) were greater than 0.92 for all groups. The error bars 215 represent standard deviation from duplicate experiments. 216
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Figure S5. Production of three monohydroxybenzoic acids during oxygenation of 218 rNAu-2 in the absence and presence of HA (A-G), and their relative percentages after 219 24 h oxygenation (H). The numbers 100, 250 and 500 denotes the HA concentration 220 (ppm). 221 222
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Figure S6. Time course changes of Fe(II)(aq) concentration (A, B), total Fe(aq) 223 concentration (C, D), and Fe(II)aq/total Fe ratio (E, F) during oxidation of rNAu-2 in 224 the presence of different concentrations of HA. The error bars represent standard 225 deviation from duplicate experiments. 226 227
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228
Figure S7. XRD pattern showing d(001) peak of rNAu-2 after oxygenation for 24 h in 229 the absence and presence of PPHA and LHA. 230
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232
Figure S8. Modeling of Fe(II)aq oxidation kinetics in the absence and presence of 500 233 ppm HA. An external supply of H2O2 (50 μmol/L) had no effect on Fe(II)aq oxidation. 234 The kinetic data were fitted with a second order rate equation. The correlation 235 coefficients were all higher than 0.98. 236 237
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Figure. S9. Time course production of H2O2 in aqueous phase during oxygenation of 239 rNAu-2. Unaltered NAu-2 produced a negligible amount of H2O2. 240
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Figure S10. Time course increase of Fe(II)(aq) after addition of either HA (100 ppm) or 242 Fe(III)(aq)-HA complex (100 μmol/L Fe(III) and 100 ppm HA) into a rNAu-2 243 suspension (1 g/L). In a separate experiment, rNAu-2 was pre-exposed in air for 12 h 244 to achieve a different Fe(II)/Fe(III) ratio. The first sampling point was measured 245 immediately after Fe(III)(aq)-HA addition. Different amounts of Fe(II) generation upon 246 addition of Fe(III)(aq)-PPHA and Fe(III)(aq)-LHA are likely due to different reduction 247 potential of these complexes. 248 249
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250 Figure S11. Plots of relative percentages of three monohydroxybenzoic acids as the 251 oxidation products of SB in rNAu-2-HA and Fe(II)(aq) -HA systems. For Fe(II)(aq) -HA 252 system, the Fe(II)(aq) concentration was 150 μmol/L with 500 ppm HA, and 90 μmol/L 253 with 250 ppm HA, respectively, simulating the Fe(II)(aq)-HA concentration in 254 rNAu-2-HA system (Figure S6A-B). Both PPHA and LHA were used. 255 256
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Figure S12. GPC elution profiles of HA before (A, B) and after (C, D) oxidation as 257 well as change in cumulative molecular mass distribution of the P1 peak after 258 oxidation (E, F). 259 260 261 262
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263
264 Figure S13. Time course changes of the HIX index of PPHA and LHA caused during 265 oxidation of rNAu-2. 266 267 268
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269 Figure S14. High resolution C1s XPS profiles of PPHA and LHA before (A, B) and 270 after (C, D) oxidation by •OH. The inset tables show the relative percentages of 271 carbon-related functional groups calculated from the corresponding peak areas. 272 273 274 275 276 277 278
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Figure S15. Progressive increase of the intensity of COOH group (1403 cm-1) in 279 PPHA and LHA samples with increasing oxygenation time. The sharp peak at 1384 280 cm-1 was caused by the presence of NO3- in natural OM.13,14 281 282
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283 Figure S16. Plots of KMD(COO) value against Kendrick nominal mass in CHO 284 formulas. The removed compounds were only present before oxygenation. The 285 produced compounds were only present after oxygenation. The conserved compounds 286 were present in both un-oxygenated and oxygenated samples. (A, C) showed plots of 287 conserved and produced compounds for PPHA and LHA samples, respectively. (B, D) 288 showed plots of removed and produced compounds for PPHA and LHA samples, 289 respectively. 290 291
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Figure S17. Plots of KMD(H2) value against Kendrick nominal mass in CHO 292 formulas. The removed compounds were only present before oxygenation. The 293 produced compounds were only present after oxygenation. The conserved compounds 294 were present in both un-oxygenated and oxygenated samples. (A, C) showed plots of 295 conserved and produced compounds for PPHA and LHA samples, respectively. (B, D) 296 showed plots of removed and produced compounds for PPHA and LHA samples, 297 respectively. 298 299 300 301
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