2005 Annual Science Report
University of Hawaii, Manoa Reporting | JUL 2004 – JUN 2005
Serpentinization, Abiogenic Methane, and Extremophilic Archaea Within the Seafloor
We have made significant progress in understanding the origin of methane and extreme high pH (12.5) during serpentinization in the Mariana forearc. Low-chlorinity springs sampled from ten sites on nine serpentinite mud volcanoes show systematic chemical gradients across the outer Mariana forearc that result from progressive devolatilization of the subducting Pacific plate. Sites range from 50 to 90 km from the trench axis corresponding to depths to the top of the plate of ~15 to 29 km. Dissolved sulfate, Na/Cl, K, Rb, Cs, and B in the springs all increase regularly with distance from the trench, leached from the subducting sediment and altered basalt in response to increasing temperature at depth from ~100-300°C. Sites nearer the trench have high Ca (up to 75 mmol/kg) and Sr, low alkalinity, and pH 10.7, whereas sites farther from the trench have almost no Ca and Sr, alkalinity (some carbonate but mostly hydroxyl) as high as 69 meq/kg, and pH 12.5. Springs with high alkalinity also have high methane (>44 mmol/kg) that feeds sulfate-reducing microbial communities in the shallow subsurface and macrofauna at the seafloor. These distal springs form chimneys and crusts of CaCO3, whereas the proximal springs form chimneys of brucite. High alkalinity at the distal sites apparently results from decarbonation at the top of the subducting plate; because serpentinization during ascent generates both high pH and H2, the resulting dissolved carbonate is reduced to methane such that carbonate alkalinity is replaced by hydroxyl alkalinity: 4H2 + CO3= = CH4 + H2O + 2OH-. This reaction can account for the much higher pH of the distal springs. Chlorinity of the springs varies from 234-546 mmol/kg and is related more to latitude N-S than to distance from the trench. Distal springs have otherwise similar compositions over this entire range of chlorinity, implying that chloride derives from depth rather than from mixing with seawater within the seamounts themselves. The range in chlorinity can readily be explained by serpentinization at reasonable water/rock mass ratios of 0.2-1.0 if 30-40% of the spring water originates as residual pore water in subducted sediment and basalt rather than as H2O and 2% residual pore water, plus from altered basalt 2% H2O: residual pore water. Corresponding vertical fluxes of sulfate, C, Na, K, Rb, Cs, B, Ca, and Sr in the forearc springs represent 0.05-3% of the amounts subducted, consistent with continued supply at greater depths.