Zircons, isotope ratios and element analyses from tonalite and oxide gabbro of the mid-ocean ridge from ODP Hole 176-735B

A limiting factor in the accuracy and precision of U/Pb zircon dates is accurate correction for initial disequilibrium in the 238U and 235U decay chains. The longest-lived-and therefore most abundant-intermediate daughter product in the 235U isotopic decay chain is 231Pa (T1/2 = 32.71 ka), and the partitioning behavior of Pa in zircon is not well constrained. Here we report high-precision thermal ionization mass spectrometry (TIMS) U-Pb zircon data from two samples from Ocean Drilling Program (ODP) Hole 735B, which show evidence for incorporation of excess 231Pa during zircon crystallization. The most precise analyses from the two samples have consistent Th-corrected 206Pb/238U dates with weighted means of 11.9325 ± 0.0039 Ma (n = 9) and 11.920 ± 0.011 Ma (n = 4), but distinctly older 207Pb/235U dates that vary from 12.330 ± 0.048 Ma to 12.140 ± 0.044 Ma and 12.03 ± 0.24 to 12.40 ± 0.27 Ma, respectively. If the excess 207Pb is due to variable initial excess 231Pa, calculated initial (231Pa)/(235U) activity ratios for the two samples range from 5.6 ± 1.0 to 9.6 ± 1.1 and 3.5 ± 5.2 to 11.4 ± 5.8. The data from the more precisely dated sample yields estimated DPazircon/DUzircon from 2.2-3.8 and 5.6-9.6, assuming (231Pa)/(235U) of the melt equal to the global average of recently erupted mid-ocean ridge basaltic glasses or secular equilibrium, respectively. High precision ID-TIMS analyses from nine additional samples from Hole 735B and nearby Hole 1105A suggest similar partitioning. The lower range of DPazircon/DUzircon is consistent with ion microprobe measurements of 231Pa in zircons from Holocene and Pleistocene rhyolitic eruptions (Schmitt (2007; doi:10.2138/am.2007.2449) and Schmitt (2011; doi:10.1146/annurev-earth-040610-133330)). The data suggest that 231Pa is preferentially incorporated during zircon crystallization over a range of magmatic compositions, and excess initial 231Pa may be more common in zircons than acknowledged. The degree of initial disequilibrium in the 235U decay chain suggested by the data from this study, and other recent high precision datasets, leads to resolvable discordance in high precision dates of Cenozoic to Mesozoic zircons. Minor discordance in zircons of this age may therefore reflect initial excess 231Pa and does not require either inheritance or Pb loss.

Geochemical and nannofossil analyses of Cenomanian/Turonian sediments of DSDP Hole 75-530A

One of the key objectives of Deep Sea Drilling Project (DSDP) Leg 75 was to shed light on the underlying causes of Cretaceous oceanic anoxia in the South Atlantic by addressing two major hypotheses: productivity productivity-driven anoxia vs. enhanced ocean stratification leading to preservation of organic matter and black shale deposition. Here we present a detailed geochemical dataset from sediments deposited during the Cenomanian/Turonian (C/T) transition and the global oceanic anoxic event 2 (OAE 2) at DSDP Site 530A, located off-shore Namibia (southeast Angola Basin, north of Walvis Ridge). To characterise the succession of alternating black and green shales at this site and to reconstruct the evolution of their paleoenvironmental setting, we have combined data derived from investigations on bulk organic matter, biomarkers and the inorganic fraction. The location of the C/T boundary itself is biostratigraphically not well constrained due to the carbonate-poor (but organic matter-rich) facies of these sediments. The bulk d13Corg record and compound-specific d13C data, in combination with published as well as new biostratigraphic data, enabled us to locate more precisely the C/T boundary at DSDP Site 530A. The compound-specific d13C record is the first of this kind reported from C/T black shales in the South Atlantic. It is employed for paleoenvironmental reconstructions and chemostratigraphic correlation to other C/T sections in order to discuss the paleoceanographic aspects and implications of the observations at DSDP Site 530A in a broader context, e.g., with regard to the potential trigger mechanisms of OAE 2, global changes in black shale deposition and climate. On a stratigraphic level, an approximation and monitoring of the syndepositional degree of oxygen depletion within the sediments/bottom waters in comparison to the upper water column is achieved by comparing normalised concentrations of redox-sensitive trace elements with the abundance of highly source specific molecular compounds. These biomarkers are derived from photoautotrophic and simultaneously anoxygenic green sulphur bacteria (Chlorobiacea) and are interpreted as paleoindicators for events of photic zone euxinia. In contrast to a number of other OAE 2 sections that are characterised by continuous black shale sequences, DSDP Site 530A represents a highly dynamic setting where newly deposited black shales were repeatedly exposed to conditions of subtle bottom water re-oxidation, presumably leading to their progressive alteration into green shales. The frequent alternation between both facies and the related anoxic to slight oxygenated conditions can be best explained by variations in vertical extent of an oxygen minimum zone in response to changes in a highly productive western continental margin setting driven by upwelling.

(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.

Geochemistry of boninite and harzburgite of ODP Leg 125 basement samples

Holes drilled into the volcanic and ultrabasic basement of the Izu-Ogasawara and Mariana forearc terranes during Leg 125 provide data on some of the earliest lithosphere created after the start of Eocene subduction in the Western Pacific. The volcanic basement contains three boninite series and one tholeiite series. (1) Eocene low-Ca boninite and low-Ca bronzite andesite pillow lavas and dikes dominate the lowermost part of the deep crustal section through the outer-arc high at Site 786. (2) Eocene intermediate-Ca boninite and its fractionation products (bronzite andesite, andesite, dacite, and rhyolite) make up the main part of the boninitic edifice at Site 786. (3) Early Oligocene intermediate-Ca to high-Ca boninite sills or dikes intrude the edifice and perhaps feed an uppermost breccia unit at Site 786. (4) Eocene or Early Oligocene tholeiitic andesite, dacite, and rhyolite form the uppermost part of the outer-arc high at Site 782. All four groups can be explained by remelting above a subduction zone of oceanic mantle lithosphere that has been depleted by its previous episode of partial melting at an ocean ridge. We estimate that the average boninite source had lost 10-15 wt% of melt at the ridge before undergoing further melting (5-10%) shortly after subduction started. The composition of the harzburgite (<2% clinopyroxene, Fo content of about 92%) indicates that it underwent a total of about 25% melting with respect to a fertile MORB mantle. The low concentration of Nb in the boninite indicates that the oceanic lithosphere prior to subduction was not enriched by any asthenospheric (OIB) component. The subduction component is characterized by (1) high Zr and Hf contents relative to Sm, Ti, Y, and middle-heavy REE, (2) light REE-enrichment, (3) low contents of Nb and Ta relative to Th, Rb, or La, (4) high contents of Na and Al, and (5) Pb isotopes on the Northern Hemisphere Reference Line. This component is unlike any subduction component from active arc volcanoes in the Izu-Mariana region or elsewhere. Modeling suggests that these characteristics fit a trondhjemitic melt from slab fusion in amphibolite facies. The resulting metasomatized mantle may have contained about 0.15 wt% water. The overall melting regime is constrained by experimental data to shallow depths and high temperatures (1250? C and 1.5 kb for an average boninite) of boninite segregation. We thus envisage that boninites were generated by decompression melting of a diapir of metasomatized residual MORB mantle leaving the harzburgites as the uppermost, most depleted residue from this second stage of melting. Thermal constraints require that both subducted lithosphere and overlying oceanic lithosphere of the mantle wedge be very young at the time of boninite genesis. This conclusion is consistent with models in which an active transform fault offsetting two ridge axes is placed under compression or transpression following the Eocene plate reorganization in the Pacific. Comparison between Leg 125 boninites and boninites and related rocks elsewhere in the Western Pacific highlights large regional differences in petrogenesis in terms of mantle mineralogy, degree of partial melting, composition of subduction components, and the nature of pre-subduction lithosphere. It is likely that, on a regional scale, the initiation of subduction involved subducted crust and lithospheric mantle wedge of a range of ages and compositions, as might be expected in this type of tectonic setting.

Fractional abundance and indices for brGDGTs and crenarchaeol in dust samples, surface water samples and surface sediment samples

Branched glycerol dialkyl glycerol tetraethers (brGDGTs) are membrane lipids produced by soil bacteria and occur in near coastal marine sediments as a result of soil organic matter input. Their abundance relative to marine-derived crenarchaeol, quantified in the BIT index, generally decreases offshore. However, in distal marine sediments, low relative amounts of brGDGTs can often still be observed. Sedimentary in situ production as well as dust input have been suggested as potential, though as yet not well constrained, sources. In this study brGDGT distributions in dust were examined and compared with those in distal marine sediments. Dust was sampled along the equatorial West African coast and brGDGTs were detected in most of the samples, albeit in low abundance. Their degree of methylation and cyclisation, expressed in the MBT' (methylation index of branched tetraethers) and DC (degree of cyclisation) indices, respectively, were comparable with those for African soils, their presumed source. Comparison of DC index values for brGDGTS in global soils, Congo deep-sea river fan sediments and dust with those of distal marine sediments clearly showed, however, that distal marine sediments had significantly higher values. This distinctive distribution is suggestive of sedimentary in situ production as a source of brGDGTs in marine sediments, rather than dust input. The presence of in situ produced brGDGTs in marine sediments means that caution should be exercised when applying the MBT'-CBT palaeothermometer to sediments with low BIT index values, i.e. < 0.1, based on our dataset.

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) Estimated e-Nd(0) input calculated using the relative fraction of ODP Hole 105-647A amphibole grains originated from different provinces of the North America

Many marine radiogenic isotope records show both spatial and temporal variations, reflecting both the degree of mixing of distinct sources in the oceans and changes in the distribution of chemical weathering on the continents. However, changes in weathering and transport processes may themselves affect the composition of radiogenic isotopes released into seawater. The provenance of physically weathered material in the Labrador Sea, constrained through the use of Ar-Ar ages of individual detrital minerals, has been used to estimate the relative contributions of chemically weathered terranes releasing radiogenic isotopes into the Labrador Sea. A simple box-model approach for balancing observed Nd-isotope variations has been used to constrain the relative importance of localised input in the Labrador Sea, and the subsequent mixing of Labrador Sea Water into North Atlantic Deep-Water. The long-term pattern of erosion and deep-water formation around the North Atlantic seems to have been a relatively stable feature since 1.5 Ma, although there has been a dramatic shift in the nature of physical and chemical weathering affecting the release of Hf and Pb isotopes. The modelled Nd isotopes imply a relative decrease in water mass advection into the Labrador Sea between 2.4 and 1.5 Ma, accompanied by a decrease in the rate of overturning, possibly caused by an increased freshwater input into the Labrador Sea.

(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.

(Table 1) B content, d11B, d18O, degree of alteration, and lithology of basalts from ODP Hole 504B

Boron contents and boron isotopic compositions were determined for the uppermost 1.3 km section of typical 6.2 Ma oceanic crust from DSDP/ODP Hole 504B, Costa Rica Rift, Galapagos Spreading Center. Both the boron content and the d11B value in the oceanic crust are controlled by two types of alteration: 1. (1) low-temperature alteration (0 to 60°C; Zones I and II) and 2. (2) high-temperature hydrothermal alteration (200 to 400°C; Zones III and IV). Basalts subjected to the low-temperature alteration are characterized by their relatively high boron contents (0.69 to 19.3 ppm) and high d11B values (+2.2 to +10.6?), indicating uptake of boron into secondary phases in equilibrium with seawater or evolved seawater. Hydrothermally altered basalts contain less abundant boron (0.17 to 0.52 ppm) and relatively constant d11B values (?0.1 to +1.0?). Although basalts from the upper part of these hydrothermal zones (<1300 mbsf) show equilibrated boron content and d11B value with aqueous fluid, effective leaching of boron from basalt is predominant in the lower part (>1300 mbsf). Original boron content and d11B value of the Hole 504B MORB were 0.35 ppm and +0.2?, respectively. The present data provide fundamental information in understanding of the distribution of boron and boron isotopes in the oceanic crust.