(Table 1) Stable carbon isotope ratios of methane and carbon dioxide from ODP Leg 169S holes

Sites 1033 and 1034 of ODP Leg 169S in Saanich Inlet have an unusual diagenetic system, that has the appearance of being depth reversed, i.e. a bacterial methane accumulation zone underlain by a sulphate reduction zone. During the late Pleistocene grey, undifferentiated, glacio-marine clays were deposited with low Corg contents (<0.4 wt.%), and interstitial fluids replete in SO4 (ca. 27 mM), devoid of CH4 and low in nutrients. This indicates oxic conditions are present, reflecting the open exchange of waters with Haro Strait during the Pleistocene before the Saanich Peninsula emerged. In the earliest Holocene (ca. 11,000 years BP) the inlet was formed, severely restricting water circulation, and leading to the presence of anoxic bottom waters. The sediments are laminated and show a dramatic rise to high Corg, Norg and Stot contents (up to 2.5, 0.4, 1.4 wt.%, respectively) over a period of ca. 1000 years. The nutrient concentrations are especially high (TA, NH4, PO4 up to 115 meq/l, 20 mM and 400 µM, respectively), SO4 is exhausted and CH4 is prolific. Stable carbon isotope ratio measurements of CH4 and co-existing CO2 indicate that methanogenesis is via carbonate reduction (delta13C-CH4 ca. -60 to - 70 per mil, delta13C-CO2 ca. +10 per mil). At the sulphate-methane interfaces, both at the near-surface and at 50 mbsf (Site 1033) and 80 mbsf (Site 1034) methane consumption by sulphate reducing bacteria is intensive.

Geochemistry of marine sediments of the world's major subduction zones

This paper presents new major and trace-element data and Lu-Hf and Sm-Nd isotopic compositions for representative suites of marine sediment samples from 14 drill sites outboard of the world's major subduction zones. These suites and samples were chosen to represent the global range in lithology, Lu/Hf ratios, and sediment flux in subducting sediments worldwide. The data reported here represent the most comprehensive data set on subducting sediments and define the Hf-Nd isotopic variations that occur in oceanic sediments and constrain the processes that caused them. Using new marine sediment data presented here, in conjunction with published data, we derive a new Terrestrial Array given by the equation, epsilon-Hf = 1.55 * epsiolon-Nd + 1.21. This array was calculated using >3400 present-day Hf and Nd isotope values. The steeper slope and smaller y-intercept of this array, compared to the original expression (epsilon-Hf = 1.36 * epsilonNd + 2.89; Vervoort et al., 1999, doi:10.1016/S0012-821X(99)00047-3) reflects the use of present day values and the unradiogenic Hf of old continental samples included in the array. In order to examine the Hf-Nd isotopic variations in marine sediments, we have classified our samples into 5 groups based on lithology and major and trace-element geochemical compositions: turbidites, terrigenous clays, and volcaniclastic, hydrothermal and hydrogenetic sediments. Compositions along the Terrestrial Array are largely controlled by terrigenous material derived from the continents and delivered to the ocean basins via turbidites, volcaniclastic sediments, and volcanic inputs from magmatic arcs. Compositions below the Terrestrial Array derive from unradiogenic Hf in zircon-rich turbidites. The anomalous compositions above the Terrestrial Array largely reflect the decoupled behavior of Hf and Nd during continental weathering and delivery to the ocean. Both terrigenous and hydrogenetic clays possess anomalously radiogenic Hf, reflecting terrestrial sedimentary and weathering processes on the one hand and marine inheritance on the other. This probably occurs during complementary processes involving preferential retention of unradiogenic Hf on the continents in the form of zircon and release of radiogenic Hf from the breakdown of easily weathered, high Lu-Hf phases such as apatite.

Ge/Si ratios in marine siliceous microfossils

A procedure is presented to separate diatoms and radiolaria from marine sediments and from each other, to purify them of elements associated with other phases, and to dissolve them to determine their elemental composition. The cleaning procedure eliminates artifacts due to the presence of detrital clays and the high sorption capacity of hydrated silica. The concentration of trace elements (Al, Fe, Mg, and Ba) that we find in alkaline dissolutions of clean diatoms are at least an order of magnitude lower than previously reported. The overall long-term precision in the determination of Ge/Si in a sub-standard of clean diatoms is ±0.024 * 10**-6 (1 sigma). Ge/Si measured in diatoms and radiolaria from core tops indicates that high-latitude Holocene diatoms accurately record the present-day oceanic Ge/Si, while radiolarian ratios are systematically lower and display more scatter. Evaluation of Ge/Si in diatoms and radiolaria from Hole DSDP 265 (Plio-Pleistocene) suggests that post-depositional alteration of the ratio does not occur at this site, but the average ratio carried by diatoms over this time interval was lower than that in the present ocean.