SUPPLEMENTARY INFORMATION

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1 DOI: 1.138/NGEO1825 Hydrogen generation from low temperature water-rock reactions L.E. Mayhew* 1, E.T. Ellison 1, T.M. McCollom 2, T.P. Trainor 3, and A.S. Templeton 1 *Corresponding author tel: (33) ; fax (33) ; mayhewl@colorado.edu 1 Department of Geological Sciences, UCB 399, University of Colorado - Boulder, Boulder, Colorado Laboratory for Atmospheric and Space Physics, UCB 392, University of Colorado - Boulder, Boulder, Colorado Department of Chemistry and Biochemistry, PO Box 75616, University of Alaska - Fairbanks, Fairbanks, Alaska pages (including cover page) 5 Figures 2 Tables NATURE GEOSCIENCE Macmillan Publishers Limited. All rights reserved.

2 DOI: 1.138/NGEO1825 Table S1. Major mineral constituents of the starting geologic substrates as identified by electron microprobe and/or XRD analyses. Chemical formulas were calculated from average normalized weight percent oxides of each phase as measured by electron microprobe. Starting material/phases Calculated mineral formula Forsythe mine fayalite fayalite fraction fayalite Fe 1.84 Mg.14 SiO 4 - Fa 88 magnetite Fe 3 O 4 clinopyroxene (Ca.92 Na.4 )(Mg 4 Fe.78 Al.4 )(Si 1.94 Al.6 )O 6 magnetite fraction magnetite Fe 3 O 4 fayalite Fe 1.84 Mg.14 SiO 4 clinopyroxene (Ca.92 Na.4 )(Mg 4 Fe.78 Al.4 )(Si 1.94 Al.6 )O 6 San Carlos olivine Mg 1.8 Fe SiO 4 - Fo 9 Hedenbergite CaFe Mn.1 Mg.1 Si 2 O 6 Petedunnite Ca.9 Zn.3 Mn.3 Fe.3 Mg Si 2 O 6 gahnite NA* San Carlos peridotite olivine Mg 1.8 Fe SiO 4 - Fo 9 clinopyroxene (Ca Na.1 )(Mg Fe.1 Al )(Si 1.9 Al.1 )O 6 orthopyroxene Ca.2 Mg 5 Fe.8 Si.97 Al.7 O 3 * phase was not analyzed by microprobe theoretical formula: ZnAl 2 O 4 Table S2. Geochemical parameters at the time* of sampling for synchrotron and XRD analyses. Values are averages of replicate vials. Experiment ph log fh 2 CO 2(aq) log fco 2 Aqueous species (µm) um Si Fe Mg Ca Fayalite fraction Magnetite fraction San Carlos olivine BDL Hedenbergite BDL Petedunnite BDL San Carlos peridotite BDL Media-only * San Carlos peridotite, fayalite, San Carlos olivine, and petedunnite were sampled at ~12 hours. Hedenbergite was sampled at ~23 hours. BDL below detection limit 2 NATURE GEOSCIENCE Macmillan Publishers Limited. All rights reserved.

3 DOI: 1.138/NGEO1825 SUPPLEMENTARY INFORMATION a. b. c. d. e. Figure S1. Mineral distribution maps of the unreacted starting substrates. (a.) San Carlos peridotite (red = pyroxene, green = olivine, blue = olivine + brucite). Scale bar = 1 um (b.) Petedunnite (red = Fe(III)-oxides, green = pyroxene, blue = gahnite). Scale bar = 1 um. (c.) Fayalite fraction (red = magnetite, green = fayalite, blue = pyroxene). Scale bar = 1 um. (d.) San Carlos olivine (red = San Carlos olivine > brucite, green = San Carlos olivine, blue = brucite > San Carlos olivine). Scale bar = 2 um. (e.) Hedenbergite (red = Fe(III)-(hydr)oxides, green = pyroxene, blue = altered pyroxene). Scale bar = 1 um. NATURE GEOSCIENCE Macmillan Publishers Limited. All rights reserved.

4 DOI: 1.138/NGEO1825 oxidized Fe a. b. pyroxene c. Fe(III) oxides Figure S2. (a.) Distribution of minerals in San Carlos olivine reacted at 1 C. (red = Fe(III)- (hydr)oxide, green = San Carlos olivine, blue = brucite > San Carlos olivine). (b.) Plane light photomicrograph of the mapped area. Scale bars = 2 um. (c.) Distribution of minerals in hedenbergite reacted at 1 C. (red = Fe(III)-(hydr)oxide, green = pyroxene, blue = Fe-bearing talc). Fe(III)-(hydr)oxides are not preferentially associated with any specific primary phase as seen in (d.) the plane light photomicrograph of the mapped area. d. 4 NATURE GEOSCIENCE Macmillan Publishers Limited. All rights reserved.

5 DOI: 1.138/NGEO1825 SUPPLEMENTARY INFORMATION XANES 1 XANES 11 XANES 16 XANES 12 XANES 6 XANES 1 XANES 24 XANES 9 fayalite unreacted fayalite reacted XANES 14 XANES XANES 24 XANES 16 XANES 13 XANES 3 XANES 7 XANES 6 XANES 2 XANES 3 San Carlos peridotite unreacted San Carlos peridotite reacted XANES 7 XANES 5 XANES 14 XANES 4 XANES 15 XANES 16 XANES 9 petedunnite unreacted petedunnite reacted Figure S3. Plots of representative XANES spectra from the geologic substrates both unreacted and reacted at 1ºC. NATURE GEOSCIENCE Macmillan Publishers Limited. All rights reserved.

6 DOI: 1.138/NGEO1825 XANES 3 XANES 1 XANES 9 San Carlos olivine unreacted XANES 26 XANES 24 XANES 3 XANES 1 San Carlos olivine reacted XANES 6 XANES 16 XANES 1 XANES 21 hedenbergite unreacted XANES 5 XANES 19 XANES 4 XANES 7 hedenbergite reacted Figure S3 continued. Plots of representative XANES spectra from the geologic substrates both unreacted and reacted at 1ºC. 6 NATURE GEOSCIENCE Macmillan Publishers Limited. All rights reserved.

7 DOI: 1.138/NGEO1825 SUPPLEMENTARY INFORMATION Fe-bearing brucite Fe-bearing talc ferrihydrite normalized intensity chromite magnetite hedenbergite San Carlos olivine Figure S4. Stack plot of spectra of key Fe-bearing model compunds. Vertical lines at 7127, 713, and 7133 ev show the peak position for models that are predominantely Fe(II)-bearing, mixed valent, and Fe(III)-bearing, respectively NATURE GEOSCIENCE Macmillan Publishers Limited. All rights reserved.

8 DOI: 1.138/NGEO1825 log a SiO 2 (aq) Fe ++ fayalite fraction magnetite fraction hedenbergite San Carlos peridotite Fe(II) bearing talc petedunnite San Carlos olivine Mg 2.7 Fe.3 Si 4 O 1 (OH) 2 1 C value at time of sampling for synchroton analysis for each substrate Fe(II) bearing pyroxene CaMg.95 Fe.5 Si 2 O ph Figure S5. Mineral stability diagram showing the thermodynamically stable Fe-bearing phases under average bulk aqueous and gaseous chemical conditions of the water-rock reaction systems at the time of sampling for synhcrotron analyses. The bulk aqueous chemistry at the time of sampling each experiment is plotted on the diagram. The uncertainity in the ph measurements was +/-.5. The model parameters were [Fe 2+ ]=1-7 M, [Ca 2+ ]=1-2.9 M, [Mg 2+ ]=1-2.4, log fh 2aq = and log fco 2 = NATURE GEOSCIENCE Macmillan Publishers Limited. All rights reserved.

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