Geochemistry of gas hydrates of DSDP Hole 84-570

During Deep Sea Drilling Project (DSDP) Leg 84 a core 1 m long and 6 cm in diameter of massive gas hydrate was unexpectedly recovered at Site 570 in upper slope sediment of the Middle America Trench offshore of Guatemala. This core contained only 5-7% sediment, the remainder being the solid hydrate composed of gas and water. Samples of the gas hydrate were decomposed under controlled conditions in a closed container maintained at 4°C. Gas pressure increased and asymptotically approached the equilibrium decomposition pressure for an ideal methane hydrate, CH4.5-3/4H2O, of 3930 kPa and approached to this pressure after each time gas was released, until the gas hydrate was completely decomposed. The gas evolved during hydrate decomposition was 99.4% methane, ~0.2% ethane, and ~0.4% CO2. Hydrocarbons from propane to heptane were also present, but in concentrations of less than 100 p.p.m. The carbon-isotopic composition of methane was -41 to -44 per mil, relative to PDB standard. The observed volumetric methane/water ratio was 64 or 67, which indicates that before it was stored and analyzed, the gas hydrate probably had lost methane. The sample material used in the experiments was likely a mixture of methane hydrate and water ice. Formation of this massive gas hydrate probably involved the following processes: (i) upward migration of gas and its accumulation in a zone where conditions favored the growth of gas hydrates, (ii) continued, unusually rapid biological generation of methane, and (iii) release of gas from water solution as pressure decreased due to sea level lowering and tectonic uplift.

Geochemistry at DSDP Hole 84-567A

Dismembered ophiolitic rocks including abundant sheared, serpentinized peridotite (mostly harzburgite) and minor basalts, dolerites, gabbros, and altered metabasites (mainly altered amphibolite) were drilled at most of the sites on the upper to lower Middle America Trench landward slope off Guatemala during Leg 84 of the Deep Sea Drilling Project. These rocks show characteristic Cataclastic deformation with zeolite facies metamorphism and alteration after amphibolite and greenschist facies metamorphism. These features indicate that the rocks originated in mid-oceanic ridge, offridge, and possibly other areas including island arc areas and were metamorphosed under a high geothermal gradient at low pressure. They were then structurally deformed and mixed within a serpentinite melange. Such ophiolite melanges may have been emplaced onto the Trench landward slope area during the initiation of subduction of the Cocos Plate. The emplacement seems to be connected to that of the Nicoya Complex in Costa Rica. The slope cover from early Eocene to Recent shows no history of these metamorphic and deformational events, therefore the emplacement of the dismembered ophiolitic rocks occurred at least before the early Eocene. The dismembered ophiolite-based Trench landward slope off Guatemala is a newly documented style of subduction, which has also recently been found at the easternmost edge of the Philippine Sea Plate along the Izu-Mariana-Yap Trench landward slope.

Geochemistry of serpentenites from DSDP Hole 84-566C

We studied a unique chrysotile-antigorite serpentinite, drilled on Deep Sea Drilling Project Leg 84 (Site 566) in the Guatemala forearc. Our in situ major and trace element data provide new constraints on possible reactions and associated trace element mobilisation during shallow serpentinite subduction. Chrysotile of the studied serpentinite, formed by the hydration of an upper mantle peridotite precursor, is partially replaced by antigorite (alone) which also occurs in 0.5 mm wide unoriented veins crosscutting the rock. Based on textural relationships and the P-T-X stability of the rock forming phases, the replacement of chrysotile by antigorite occurred at T < 300 °C, due to interaction between the chrysotile-serpentinite and an aqueous fluid. A comparison of the chemical compositions of reactant and product phases reveals that about 90% of the Cl, more than 80% of the B and about 50% of the Sr hosted originally by chrysotile was lost during fluid-assisted chrysotile-to-antigorite transformation and accompanying partial dehydration, and documents the much lower affinity of antigorite for trace element uptake than that of chrysotile. The fluid-assisted chrysotile-to-antigorite transformation and associated trace element loss documented here can occur in the shallow (< 30 km) region of subduction zones. This transformation decreases notably the Cl and B inventory of subducting serpentinites, which are regarded as one of the most important carriers of these elements into subduction zones. The evolution of serpentinites during initial subduction stages thus appears to be critical in the recycling of specific trace elements such as B or Cl from forearc to subarc depths.