Supporting Information

McCollom 10.1073/pnas.1611843113

Fig. S1. Back-scattered electron images and energy-dispersive spectrometer (EDS) analyses showing apparent occurrences of native metals in experiment
OLIVOPX230. (A) Overview of reaction products in polished grain mount. (B) Expanded view from A, with EDS of the area centered on the bright particle
outlined by the red circle shown in C. The EDS is dominated by Ni and Fe with little O, indicating that the small bright particles are composed of an Ni-Fe alloy.
The Mg and Si in the EDS data are likely from serpentine surrounding the alloy. (E) EDS of area outlined by the red circle in D. The prominent Pt peak and lack
of significant peaks for S or O indicate that the bright particle in the red circle in D is native Pt. Brc, brucite; Mgt, magnetite; Ol, olivine; SRP, serpentine.

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Fig. S2. Isopleths of constant mole percentage of H2 in the H2-H2O system as a function of pressure and temperature. The red X denotes the P–T conditions of
experiment OLIV300_sat2. Extrapolation of the isopleths indicates that the experiment is within the two-phase field for systems containing about 0.3 mol % H2,
indicating that the fluid should become saturated and exsolve a separate H2-rich vapor phase at aqueous concentrations around 170 mmol kg−1. It should be noted,
however, that the isopleths in the P–T region of the experiment as portrayed by Seward and Franck (31) are defined by only a few measurements, and therefore,
there is substantial uncertainty in the position of the isopleths. Furthermore, the diagram is drawn for pure water and H2, and the presence of dissolved salts and
additional volatile species (CO2 and CH4) will cause the isopleths to deviate somewhat from the pure system. Modified from ref. 31.

Fig. S3. Calculated equilibrium CH4(aq)/CO2(aq) ratios (solid lines) as a function of the concentration of H2(aq) at the experimental temperatures and 35 MPa,
with measured fluid compositions at the end of the serpentinization experiments shown for comparison (symbols). With increasing temperature, the position
of the line shifts to the right, reflecting the increased thermodynamic stability of CO2 relative to CH4 at higher temperatures. In all cases except OLIV320,
equilibrium CH4(aq)/CO2(aq) ratios at the experimentally measured H2(aq) values are >103, indicating there is a strong thermodynamic drive for the conversion of
dissolved inorganic carbon to CH4 to approach thermodynamic equilibrium. Experiment OLIV320 is close to equilibrium, indicating little or no thermodynamic
drive for formation of CH4. Thermodynamic data for the equilibrium calculations were obtained using SUPCRT92 (38) with parameters for dissolved compounds
from Shock et al. (39) and Shock and Helgeson (40). For the purposes of the calculations, activity coefficients of all dissolved species were assumed to be equal
to one. The concentration of dissolved CO2(aq) for the experiments was calculated from the measured ΣCO2 values at the estimated in situ pH using speciation
calculations performed with the program EQ3 (29).

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 Table S1. Measured fluid compositions during serpentinization experiments
Time (h) Temperature (°C) H2 (m) ΣCO2 (m) CH4 (μ) pH (25 °C)

Experiment OLIV200_fine
50 200 0.0003 19.0 5.5 6.4
2,018 200 0.58 15.8 9.5 8.8
5,621 200 1.25 11.6 12.4 9.4
7,753 200 2.28 10.7 14.5 9.3
9,219 201 2.94 9.6 14.8 9.2
Experiment OLIV230
2 232 0 17.9 1.4 —
479 232 0.14 — — 8.3
1,031 232 0.19 — — 8.7
1,967 231 0.14 1.0 0.3 8.7
2,496 232 0.23 — — —
3,386 232 0.79 — — 8.4
4,010 232 1.05 — — 6.8
4,013 Additional fluid injected
4,034 232 0.45 13.4 3.7 7.0
4,559 232 1.08 — — 8.9
5,063 232 1.49 — — 8.8
5,735 232 2.43 — — 8.7
7,055 232 4.09 6.6 6.4 8.3
8,159 232 5.78 6.0 5.5 8.0
Experiment OLIV300
11 300 0.45 20.2 16 8.4
1,172 301 7.2 18.0 22 7.6
1,891 300 9.0 13.3 25 7.3
2,683 300 11.0 12.5 25 7.1
Experiment OLIV320
70 320 0.27 17.8 17 7.8
481 320 0.75 20.1 71 7.5
1,343 320 1.8 21.0 210 7.1
2,087 320 2.6 18.1 270 7.0
Experiment OLIV300_sat2
21 300 113 59.5 48 —
2,012 301 180* 17.4* 97* 6.5
3,885 300 194* 11.0* 98* 7.0
Experiment OLIVOPX230
2 232 0.001 19.2 5.6 —
169 232 0.023 — — 6.8
840 232 0.24 — — 7.4
1,344 232 0.39 — — 7.0
2,015 232 1.1 — — 7.4
3,359 232 3.3 12.0 15.7 8.1
4,488 232 13.8 8.5 17.6 10.7
4,020 Additional fluid injected
4,535 232 6.1 9.0 8.4 9.5
5,567 232 14.7 — 9.0 11.2
7,271 232 35.8 — 17.0 11.6
8,183 232 49.8 3.8 20.0 11.7
8,711 232 52.0 3.3 22.0 11.7
9,287 232 61.0 2.8 25.0 —

Concentrations are in millimoles kilogram−1 (m) or micromoles kilogram−1 (μ). —, Not measured.
*These measurements indicate aqueous concentrations and may not represent the total amount of these
compounds if there is a vapor phase present.

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