(Table 1) Elemental composition, pyrite-Fe and degree of pyritisation in Upper Pliensbachian and Lower Toarcian sediments from the costal section of Yorkshire

Profiles of Mo/total organic carbon (TOC) through the Lower Toarcian black shales of the Cleveland Basin, Yorkshire, United Kingdom, and the Posidonia shale of Germany and Switzerland reveal water mass restriction during the interval from late tenuicostatum Zone times to early bifrons Zone times, times which include that of the putative Early Toarcian oceanic anoxic event. The degree of restriction is revealed by crossplots of Mo and TOC concentrations for the Cleveland Basin, which define two linear arrays with regression slopes (ppm/%) of 0.5 and 17. The slope of 0.5 applies to sediment from the upper semicelatum and exaratum Subzones. This value, which is one tenth of that for modern sediments from the Black Sea (Mo/TOC regression slope 4.5), reveals that water mass restriction during this interval was around 10 times more severe than in the modern Black Sea; the renewal frequency of the water mass was between 4 and 40 ka. The Mo/TOC regression slope of 17 applies to the overlying falciferum and commune subzones: the value shows that restriction in this interval was less severe and that the renewal frequency of the water mass was between 10 and 130 years. The more restricted of the two intervals has been termed the Early Toarcian oceanic anoxic event but is shown to be an event caused by basin restriction local to NW Europe. Crossplots of Re, Os, and Mo against TOC show similar trends of increasing element concentration with increase in TOC but with differing slopes. Together with modeling of 187Os/188Os and d98Mo, the element/TOC trends show that drawdown of Re, Os, and Mo was essentially complete during upper semicelatum and exaratum Subzone times (Mo/TOC regression slope of 0.5). Drawdown sensitized the restricted water mass to isotopic change forced by freshwater mixing so that continental inputs of Re, Os, and Mo, via a low-salinity surface layer, created isotopic excursions of up to 1.3 per mil in d98Mo and up to 0.6 per mil for 187Os/188Os. Restriction thereby compromises attempts to date Toarcian black shales, and possibly all black shales, using Re-Os chronology and introduces a confounding influence in the attempts to use d98Mo and initial 187Os/188Os for palaeo-oceanographic interpretation.

(Table 1) Sulfur isotopes, total sulfur, and degree of oxidation of basalt samples from DSDP Hole 69-504B and 70-504B

About 150 basalt samples from Hole 504B, near the Costa Rica Rift were analyzed for sulfur content and sulfur-isotope composition. The basement in Hole 504B can be divided into an upper part, which has oxidative alteration (274.5-550 m below sea floor), and a lower part, which has nonoxidative alteration (550-835 m below sea floor) (the interval from 540 to 585 meters actually is transitional). This division is reflected in both the sulfur content and the sulfurisotope composition. Oxidative alteration of basalts by sea water at low temperatures has resulted in a depletion in sulfur in the upper part of the hole (mostly less than 600 ppm S) as compared to fresh sulfur-saturated oceanic tholeiites (900-1200 ppm S). High amounts of sulfur in the lower part of the hole are a result of precipitation of secondary pyrite under non-oxidative or weakly oxidative conditions from solutions which dissolved igneous sulfides. The average sulfur-isotope composition of the primary igneous sulfides is d34S = -0.01 per mil, which is close to the assumed mantle sulfur composition (d34S = 0 per mil. Pyrite and sulfate sulfur extracted together in a separate preparation step (as "pyrite-sulfate" sulfur) indicate addition of sea-water sulfate to the upper part of the basalts. The d34S of secondary pyrite isolated by hand-picking varies between -8.0 and +5.8 per mil; the "pyrite-sulfate" sulfur (d34S = -4.8 to +10.5 per mil), as well as that of the isolated pyrite, may have originated in the precipitation of pyrite from solutions containing sulfur from the dissolution of igneous sulfides, but addition of sulfur transported by hydrothermal solutions cannot be excluded.

(Table 2) Distribution of alkenone unsaturation index UK37 of the eastern North Atlantic

This paper reports the concentrations and within-class distributions of long-chain alkenones and alkyl alkenoates in the surface waters (0-50 m) of the eastern North Atlantic, and correlates their abundance and distribution with those of source organisms and with water temperature and other environmental variables. We collected these samples of >0.8 µm particulate material from the euphotic zone along the JGOFS 20°W longitude transect, from 61°N to 24°N, during seven cruises of the UK-JGOFS Biogeochemical Ocean Flux Study (BOFS) in 1989-1991; the biogeographical range of our 53 samples extends from the cold (<10°C), nutrient-rich and highly productive subarctic waters of the Iceland Basin to the warm (>25°C) oligotrophic subtropical waters off Africa. Surface water concentrations of total alkenone and alkenoates ranged from <50 ng/l in oligotrophic waters below 40°N to 2000-4500 ng/l in high latitude E. huxleyi blooms, and were well correlated with E. huxleyi cell densities, supporting the assumption that E. huxleyi is the predominant source of these compounds in the present day North Atlantic. The within-class distribution of the C37 and C38 alkenones and C36 alkenoates varied strongly as a function of temperature, and was largely unaffected by nutrient concentration, bloom status and other surface water properties. The biosynthetic response of the source organisms to growth temperature differed between the cold (<16°C) waters above 47°N and the warmer waters to the south. In cold (<16°C) waters above 47°N, the relative amounts of alkenoates and C38 alkenones synthesized was a strong function of growth temperature, while the unsaturation ratio of the alkenones (C37 and C38) was uncorrelated with temperature. Conversely, in warm (>16°C) waters below 47°N, the relative proportions of alkenoates and alkenones synthesized remained constant with increasing temperature while the unsaturation ratios of the C37 and C38 methyl alkenones (Uk37 and Uk38Me, respectively) increased linearly. The fitted regressions of Uk37 and Uk38Me versus temperature for waters >16°C were both highly significant (r**2 > 0.96) and had identical slopes (0.057) that were 50% higher than the slope (0.034) of the temperature calibration of Uk37 reported by Prahl and Wakeham (1987; doi:10.1038/330367a0) over the same temperature range. These observations suggest either a physiological adjustment in biochemical response to growth temperature above a 16-17°C threshold and/or variation between different E. huxleyi strains and/or related species inhabiting the cold and warm water regions of the eastern North Atlantic. Using our North Atlantic data set, we have produced multivariate temperature calibrations incorporating all major features of the alkenone and alkenoate data set. Predicted temperatures using multivariate calibrations are largely unbiased, with a standard error of approximately ±1°C over the entire data range. In contrast, simpler calibration models cannot adequately incorporate regional diversity and nonlinear trends with temperature. Our results indicate that calibrations based upon single variables, such as Uk37, can be strongly biased by unknown systematic errors arising from natural variability in the biosynthetic response of the source organisms to growth temperature. Multivariate temperature calibration can be expected to give more precise estimates of Integrated Production Temperatures (IPT) in the sedimentary record over a wider range of paleoenvironmental conditions, when derived using a calibration data set incorporating a similar range of natural variability in biosynthetic response.

Geochemistry and degree of organic carbon preservation in non-bioturbated, shaly sediments

Based on 13 published porewater H2S and sulphate profiles the amount of H2S escaping from non-bioturbated shales varies between some few % to 45% of the amount of bacterially generated H2S. This finding permits calculation of the original organic carbon (TOCor) content of immature nonbioturbated shales using TOC and sulphur content data. In two immature non-bioturbated sequences from Hungary (Toarcian and Oligocene) the first-order correlation between HI and TOC/TOCor was found to be stronger than that between HI and TOC, indicating that sulphate reduction was the leading process both in decrease in TOC content and degradation of kerogen source potential.

(Table 1) Sulfur isotopes, total sulfur, and degree of oxidation of basalt samples from DSDP Holes 69-504B and 70-504B

Whole-rock basalt samples from the upper half of Deep Sea Drilling Project Hole 504B have oxygen-isotope compositions typical of mid-ocean-ridge basalts which have experienced a moderate degree of low-temperature alteration by sea water. By contrast, d18O values in the lower half of the hole correspond to basalts which have experienced almost no detectable oxygen-isotope alteration. These observations suggest that the overall water/rock ratio was lower in the lower half of the drilled crust. A correlation between d18O values and 87Sr/86Sr ratios suggests that the water/rock ratio, rather than temperature variation, was the main factor determining basalt d18O values. Hydrogen-isotope data appear to be consistent with a low water/rock ratio in the lower part of the crust.