Pore-water anomalies in gas hydrate-bearing sediments of the deeper continental margins: Facts and problems

Naturally occurring gas hydrates, discovered under the deeper parts of the continental margins (generally below 500 m water depth) during the Deep Sea Drilling Project and the Ocean Drilling Program, impregnate terrigenous sediments 0.5 to 1 km thick. They form from biogenic as well as thermogenic hydrocarbon gases and are associated with characteristic chemical and isotopic anomalies in the pore waters resulting from hydrate decomposition. Typical downward trends derived from water samples squeezed on board ship show decreasing chlorinity coupled with increases in the heavy oxygen and hydrogen isotopes resulting from the combined effects of sediment compaction and salt and isotope fractionation by hydrates. Carbon isotopes can be used to differentiate between biogenic ( ¹³C < –55) and thermogenic ( ¹³C > –559) gas hydrates except where acetate-derived methane is involved. Smooth downward trends in the chemical and isotopic anomalies suggest steady increases in the proportion of hydrates among the pore-filling substances. Spikes are attributed to high local hydrate concentrations (or massive hydrate layers or nodules). Problems encountered in delineating the detailed relationships between hydrate occurrence and pore-water anomalies concern (i) the roof-effect of a hydrate zone which should be marked by a positive Cl^– and a negative ¹⁸O anomaly (the opposite of the hydrate decomposition effect) (ii) the composition ofin-situ pore waters from within hydrate zones; (iii) the suppression of a positive ¹⁸O hydrate-decomposition anomaly due to superposition of other oxygen-isotope fractionation effects (such as volcanic glass alteration); and (iv) the non-linear correlation between Cl^– depletion and¹⁸O enrichment, and the magnitude of the¹⁸O enrichment. The hydrate-decomposition mechanism still provides the most successful explanation for the chemical and isotopic porewater anomalies observed in hydrate-bearing sediments, but the problems encountered underscore the urgency for future research through deep-sea drilling in hydrate zones.Dedicated to Dr D. W. Davidson in honor of his great contributions to the sciences of inclusion phenomena.