Chemical and germanium isotopic compositions of sediments and sedimentary rocks from ODP Sites 129-801 and 185-1149

A new technique for the precise and accurate determination of Ge stable isotope compositions has been developed and applied to silicate rocks and biogenic opal. The analyses were performed using a continuous flow hydride generation system coupled to a MC-ICP-MS. Samples have been purified through anion- and cation-exchange resins to separate Ge from matrix elements and eliminate potential isobaric interferences. Variations of 74Ge/70Ge ratios are expressed as d74Ge values relative to our internal standard and the long-term external reproducibility of the data is better than 0.2? for sample size as low as 15 ng of Ge. Data are presented for igneous and sedimentary rocks, and the overall variation is 2.4? in d74Ge, representing 12 times the uncertainty of the measurements and demonstrating that the terrestrial isotopic composition of Ge is not unique. Co-variations of 74Ge/70Ge, 73Ge/70Ge and 72Ge/70Ge ratios follow a mass-dependent behaviour and imply natural isotopic fractionation of Ge by physicochemical processes. The range of d74Ge in igneous rocks is only 0.25? without systematic differences among continental crust, oceanic crust or mantle material. On this basis, a Bulk Silicate Earth reservoir with a d74Ge of 1.3+/-0.2? can be defined. In contrast, modern biogenic opal such as marine sponges and authigenic glauconite displayed higher d74Ge values between 2.0? and 3.0?. This suggests that biogenic opal may be significantly enriched in light isotopes with respect to seawater and places a lower bound on the d74Ge of the seawater to +3.0?.This suggests that seawater is isotopically heavy relative to Bulk Silicate Earth and that biogenic opal may be significantly fractionated with respect to seawater. Deep-sea sediments are within the range of the Bulk Silicate Earth while Mesozoic deep-sea cherts (opal and quartz) have d74Ge values ranging from 0.7? to 2.0?. The variable values of the cherts cannot be explained by binary mixing between a biogenic component and a detrital component and are suggestive of enrichment in the light isotope of diagenetic quartz. Further work is now required to determine Ge isotope fractionation by siliceous organisms and to investigate the effect of diagenetic processes during chert lithification.

Isotopic composition of diagenetic silica and associated pore waters of Japan Sea sediments

Over a broad region of the eastern Japan Sea, Neogene opaline diatomaceous sediments alter with depth to hard porcellanites and cherts composed of opal-CT and quartz. We examined the oxygen isotopic compositions of these diagenetic silica minerals at four widely spaced sites occupied during ODP Leg 127 in order to investigate the thermal history of the region. Formation temperatures computed from these isotopic data range from 22° to 68°C for opal-CT and from 44° to 92°C for diagenetic quartz, quite similar to temperature ranges estimated from the extrapolated modern gradients, 36°-43°C and 49°-64°C, respectively. At each site the isotopic temperature values cluster near the extrapolated ambient sediment temperatures. As a first approximation, the similarities suggest that the positions of the silica transformations in the basin are controlled by the present thermal regime. In detail, isotopic and ambient temperatures differ. If these differences are real, then they reflect variations in the thermal histories at these sites. At Sites 794 and 797 in the Yamato Basin, isotopic temperatures and gradients computed from these data are lower than or comparable to ambient temperatures and gradients. We suggest that the silica zones have roughly equilibrated with the modern gradients at these localities. At Site 795 in the Japan Basin, isotopic temperatures are also lower than ambient sediment temperatures at comparable depths, but the gradient computed from the isotopic temperatures is higher than the present measured gradient. For both scenarios to hold, the silica zones must have formed under initially high gradients during the early post-rift period at this locality. These zones were then rapidly buried and have yet to equilibrate with the modern lower gradient. At Site 796 on Okushiri Ridge, isotopic temperatures exceed present temperatures as expected for an area of recent uplift. The gradient computed from our isotopic data and the thickness of the opal-CT zone indicate a higher gradient than at present at this site, apparently reflecting higher heat fluxes during the early post-rift period or recent frictional heating from nearby reverse fault activity.