Methane Seepage at Hyperalkaline Springs in the Ronda Peridotite Massif (Spain)

Methane-rich, hyperalkaline spring waters and bubbling pools have been sampled in the Ronda peridotite massif in southern Spain. Water chemistry (T: 17.1-21.5 ºC; pH: 10.7-11.7; DO: <2 mg/L; Ca-OH facies) is characteristic of present-day serpentinization. Dissolved CH4 concentrations range from 0.1 to 3.2 mg/L. CH4 stable C and H isotope ratios suggest a dominant abiotic origin in two natural spring sites (delta13C: -13 to -29 ‰ VPDB; delta2H: -309 to -333 ‰ VSMOW) and a mixed biotic-abiotic origin in springs with artificial water delivery systems (i.e., pipes or fountains; delta13C: -44 to -69 ‰; delta2H: -180 to -319 ‰). At the natural springs, gas is mainly released through bubbles close to the water outlet (CH4 flux ~1 kg/day by individual bubble trains), and subordinately by microseepage from the ground, even at distances of ~100 m from the bubble-spring site (flux of 10's, up to 97, mg CH4 m-2day-1). Gas seepage is strictly controlled by faults. Under-saturation of CH4 in water, bubbling and seepage location suggest that CH4 is not exclusively transported to the surface by hyperalkaline water, but it follows autonomous migration pathways along faults. Similar 'dry' seepage of abiotic gas was observed in the Philippines, New Zealand, Turkey and Italy. Like other land-based serpentinization systems, the Ronda peridotite massif is characterized by low heat flow (<40 mW/m2), with temperatures <60°C at depths of 1.5 km. At these low T and high pH conditions, CO32- is the only available carbon source dissolved in the water, and unlikely contributes to catalysed Fischer-Tropsch Type reactions. Methane production from CO2 hydrogenation in a gas phase system (unsaturated fractured rocks) cannot be excluded. The presence of ruthenium-enriched chromitites in the Ronda peridotites may support the hypothesis that CH4 is produced by CO2 hydrogenation catalyzed by Ru minerals, even at temperatures below 100°C, as demonstrated in recent laboratory experiments (Etiope and Ionescu, 2014, Geofluids, in press).