(Table 1) Lithium contents and isotopic composition in sediments from DSDP Holes 64-477 and 64-477A

Lithium isotopic compositions of hydrothermally altered sediments of Deep Sea Drilling Project (DSDP) site 477/477A, as well as high temperature vent fluids of the Guaymas Basin, have been determined to gain an understanding of lithium exchange during fluid-sediment interaction at this sediment-covered spreading center. Unaltered turbidite of the basin has a d6Li value of -10%, 5-7% heavier than fresh oceanic basalts. Contact metamorphism induced by a shallow sill intrusion results in a decrease of the lithium content of the adjacent sediments and a lighter isotopic value (-8%). Below the sill, sediments altered by a deep-seated hydrothermal system show strong depletions in lithium, while lithium isotopic compositions vary greatly, ranging from -11 to +1%. The shift to lighter composition is the result of preferential retention of the lighter isotope in recrystallized phases after destruction of the primary minerals. The complexity of the isotope profile is attributed to inhomogeneity in mineral composition, the tortuous pathway of fluids and the temperature effect on isotopic fractionation. The range of lithium concentration and d6Li values for the vent fluids sampled in 1982 and 1985 overlaps with that of the sediment-free mid-ocean ridge systems. The lack of a distinct expression of sediment input is explained in terms of a flow-through system with continuous water recharge. The observations on the natural system agree well with the results of laboratory hydrothermal experiments. The experimental study demonstrates the importance of temperature, pressure, water/rock ratio, substrate composition and reaction time on the lithium isotopic composition of the reacted fluid. High temperature authigenic phases do not seem to constitute an important sink for lithium and sediments of a hydrothermal system such as Guaymas are a source of lithium to the ocean. The ready mobility of lithium in the sediment under elevated temperature and pressure conditions also has important implications for lithium cycling in subduction zones.

Degradation rates and productivity signals of organic-walled dinoflagellate cyst species in surface sediment samples

To understand the role of the ocean within the global carbon cycle, detailed information is required on key-processes within the marine carbon cycle; bio-production in the upper ocean, export of the produced material to the deep ocean and the storage of carbon in oceanic sediments. Quantification of these processes requires the separation of signals of net primary production and the rate of organic matter decay as reflected in fossil sediments. This study examines the large differences in degradation rates of organic-walled dinoflagellate cyst species to separate these degradation and productivity signals. For this, accumulation rates of cyst species known to be resistant (R-cysts) or sensitive (S-cysts) to aerobic degradation of 62 sites are compared to mean annual chlorophyll-a, sea-surface temperature, sea-surface salinity, nitrate and phosphate concentrations of the upper waters and deep-water oxygen concentrations. Furthermore, the degradation of sensitive cysts, as expressed by the degradation constant k and reaction time t, has been related to bottom water [O2]. The studied sediments were taken from the Arabian Sea, north-western African Margin (North Atlantic), western-equatorial Atlantic Ocean/Caraibic, south-western African margin (South Atlantic) and Southern Ocean (Atlantic sector). Significant relationships are observed between (a) accumulation rates of R-cysts and upper water chlorophyll-a concentrations, (b) accumulation rates of S-cysts and bottom water [O2] and (c) degradation rates of S-cysts (kt) and bottom water [O2]. Relationships that are extremely weak or are clearly insignificant on all confidence intervals are between (1) S-cyst accumulation rates and chlorophyll-a concentrations, sea-surface temperature (SST), sea-surface salinity (SSS), phosphate concentrations (P) and nitrate concentrations (N), (2) between R-cyst accumulation rates and bottom water [O2], SST, SSS, P and N, and between (3) kt and water depth. Co-variance is present between the parameters N and P, N, P and chlorophyll-a, oxygen and water depth. Correcting for this co-variance does not influence the significance of the relationship given above. The possible applicability of dinoflagellate cyst degradation to estimate past net primary production and deep ocean ventilation is discussed.

Osmium concentrations and isotope ratios of ODP Hole 207-1260B and the Furlo section

Oceanic anoxic events (OAEs) were episodes of widespread marine anoxia during which large amounts of organic carbon were buried on the ocean floor under oxygen-deficient bottom waters (Schlanger and Jenkyns, 1976; Schlanger et al., 1987). OAE2, occurring at the Cenomanian/Turonian boundary (about 93.5 Myr ago) (Gradstein et al., 2004), is the most widespread and best defined OAE of the mid-Cretaceous. Although the enhanced burial of organic matter can be explained either through increased primary productivity or enhanced preservation scenarios (Schlanger and Jenkyns, 1976; Schlanger et al., 1987). the actual trigger mechanism, corresponding closely to the onset of these episodes of increased carbon sequestration, has not been clearly identified. It has been postulated that large-scale magmatic activity initially triggered OAE2 (Sinton and Duncan, 1997; Kerr, 1998, doi:10.1144/gsjgs.155.4.0619), but a direct proxy of magmatism preserved in the sedimentary record coinciding closely with the onset of OAE2 has not yet been found. Here we report seawater osmium isotope ratios in organic-rich sediments from two distant sites. We find that at both study sites the marine osmium isotope record changes abruptly just at or before the onset of OAE2. Using a simple two-component mixing equation, we calculate that over 97 per cent of the total osmium content in contemporaneous seawater at both sites is magmatic in origin, a ~30-50-fold increase relative to pre-OAE conditions. Furthermore, the magmatic osmium isotope signal appears slightly before the OAE2 -as indicated by carbon isotope ratios- suggesting a time-lag of up to ~23 kyr between magmatism and the onset of significant organic carbon burial, which may reflect the reaction time of the global ocean system. Our marine osmium isotope data are indicative of a widespread magmatic pulse at the onset of OAE2, which may have triggered the subsequent deposition of large amounts of organic matter.