Chlorine concentrations and stable isotope ratios in Izu Bonin tephra

d37Cl values were determined for Izu Bonin arc magmas erupted 0-44 Ma in order to better understand the time-dependent processing of volatiles in subduction zones. Pristine ash-sized particles (glass, pumice, scoria, and rock fragments) were handpicked from tephra drilled at ODP Site 782. d37Cl values for these particles span a large range from -2.1 to +1.7 per mil (error = ± 0.3 per mil) vs. SMOC (Standard Mean Ocean Chloride, defined as 0 per mil). The temporal data extend the previously reported range of d37Cl values of -2.6 to 0.4 per mil (bulk ash) and -5.4 to -0.1 per mil (volcanic gases) from the Quaternary Izu Bonin-Mariana volcanic front to more positive values. Overall, the temporal data indicate a time-progressive evolution, from isotopically negative Eocene and Oligocene magmas (-0.7 ± 1.1 per mil, n = 10) to Neogene magmas that have higher ?37Cl values on average (+0.3 ± 1.1 per mil; n = 13). The increase is due to the emergence of positive d37Cl values in the Neogene, while minimum d37Cl values are similar through time. The range in d37Cl values cannot be attributed to fractionation during melt formation and differentiation, and must reflect the diversity of Cl present in the arc magma sources. Cl clearly derives from the slab (> 96% Cl in arc magmas), but d37Cl values do not correlate with isotope tracers (e.g. 207Pb/204Pb and 87Sr/86Sr) that are indicative of the flux from subducting sedimentary and igneous crust. Given the steady, high Cl flux since at least 42 Ma, the temporal variability of d37Cl values is best explained by a flux from subducting isotopically positive and negative serpentinite formed in the ocean basins that mingles with and possibly overprints the isotopically negative flux from sediment and igneous crust at arc front depths. The change in the d37Cl values before and after backarc spreading may reflect either a tectonically induced change in the mechanism of serpentinite formation on the oceanic plate, or possibly the integration of isotopically positive wedge serpentinite as arc fluid source during the Neogene. Our study suggests that serpentinites are important fluid sources at arc front depth, and implies the return of isotopically positive and negative Cl from the Earth surface to the mantle.

(Table DR1) Argon isotope data and dating for individual >63 µm amphibole grains from Labrador Sea sediments, ODP Hole 105-647A

Variations of global and regional silicate weathering rates and paleo-ocean circulation patterns are estimated by using radiogenic isotope records, but the effects of changes in provenance are generally ignored. Here sediment provenance has been constrained through the use of Ar-Ar ages for individual detrital minerals from the Labrador Sea, which can be compared directly to the radiogenic isotope compositions from the same core material. Dramatic changes in the radiogenic isotope composition of North Atlantic Deep Water through the Quaternary Period are shown to reflect discrete changes in both sources and weathering processes accompanying Northern Hemisphere glaciation. Changes in the different radiogenic isotope systems reflect the influence of source, physical weathering, and chemical weathering, and not simply changes in the underlying weathering rate or ocean circulation patterns that are typically inferred.

(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.

(Table 1) Stable isotope records of clathrite and water

Aragonitic clathrites are methane-derived precipitates that are found at sites of massive near-seafloor gas hydrate (clathrate) accumulations at the summit of southern Hydrate Ridge, Cascadia margin. These platy carbonate precipitates form inside or in proximity to gas hydrate, which in our study site currently coexists with a fluid that is highly enriched in dissolved ions as salts are excluded during gas hydrate formation. The clathrites record the preferential incorporation of 18O into the hydrate structure and hence the enrichment of 16O in the surrounding brine. We measured d18O values as high as 2.27 per mil relative to Peedee belemnite that correspond to a fluid composition of -1.18 per mil relative to standard mean ocean water. The same trend can be observed in Ca isotopes. Ongoing clathrite precipitation causes enrichment of the 44Ca in the fluid and hence in the carbonates. Carbon isotopes confirm a methane source for the carbonates. Our triple stable isotope approach that uses the three main components of carbonates (Ca, C, O) provides insight into multiple parameters influencing the isotopic composition of the pore water and hence the isotopic composition of the clathrites. This approach provides a tool to monitor the geochemical processes during clathrate and clathrite formation, thus recording the evolution of the geochemical environment of gas hydrate systems.

Molybdenum and sulphur isotope ratios of early Pleistocene sapropels of ODP Hole 160-969D

Organic-rich sediments (sapropels) deposited in the Mediterranean are presumed to have formed during periods of increased productivity, and/or deep water oxygen depletion, possibly including the development of sulfidic conditions (euxinia). Geochemical redox proxies (Re, Mo, Mo isotopes, V, Fe/Al, and multiple S isotopes) in 8 sapropels from the Pleistocene confirm water column euxinic conditions of varying intensity during sapropel deposition. These same proxies indicate an oxic origin for hemipelagic sediments deposited between sapropel-forming episodes. In one intensively sampled sapropel, deposited between 1.450 and 1.458 Ma, changing concentrations of organic carbon, Ba, Re, Mo, V, and Fe/Al track one another closely, reflecting coupling between water column euxinia and biological productivity. Multiple S isotope data from this sapropel suggest that the redox interface where oxidative sulfur cycling occurred was present in the sediments during hemipelagic sedimentation, but moved into the water column during sapropel deposition. Molybdenum isotopes of these 8 sapropels encompass a range of values (d98Mo = +0.2 to +1.7), but are all 98Mo-depleted relative to seawater (d98Mo = +2.3 per mil), suggesting that quantitative removal of Mo did not occur. This finding contrasts with modern Black Sea sediments. In general, Re/Mo ratios in sapropels are greater than in modern seawater, implying that the water column was not sufficiently sulfidic during sapropel-forming episodes to induce complete removal of both these elements. Surprisingly, the heaviest d98Mo values are found within hemipelagic sediments. Very few of the hemipelagic samples preserve the negative d98Mo values commonly associated with modern oxic marine sediments. Many of the hemipelagic samples also contained higher concentrations of Re and Mo than are common in oxic sediments. These features may be attributable to diffusion from the sapropels of a 98Mo-enriched component into the hemipelagic sediments.

Diatom isotope data (d18Odiatom and d30Sidiatom) from IODP Site 303-U1304 (North Atlantic)

The Last Interglacial (LIG), corresponding to Marine Isotope Stage (MIS) 5e, provides a reference of interglacial climate variability in the absence of anthropogenic forcing. Using an expanded section of the LIG gained at Integrated Ocean Drilling Program Site U1304 in the Subarctic Atlantic, we demonstrate that the early MIS 5e was marked by oceanographic conditions conducive for high diatom production and accumulation. The appearance of diatom-dominated laminated oozes ~3 k.y. after the beginning of MIS 5e at ca. 125 ka coincides with a shift to higher d30Sidiat values together with the dominance of Thalassiothrix longissima, indicative of increased nutrient availability and silicic acid utilization in surface waters. Though the Subarctic Front provided the physical conditions for high diatom production and deposition, these processes alone are insufficient to explain the high rates of siliceous productivity and the formation of diatomaceous sediments. Instead, the additional presence of an increased nutrient pool provided by Subantarctic Mode Water played the decisive role in initiating and sustaining diatom production. The high diatom productivity and the occurrence of diatomaceous sediments in the late Quaternary challenge the current hypothesis of a silica-depleted North Atlantic during the LIG.

(Table 1) Results of pore water analyses, including boron content and boron isotope ratios

Drilling a transect of holes across the Costa Rica forearc during ODP Leg 170 demonstrated the margin wedge to be of continental, non accretionary origin, which is intersected by permeable thrust faults. Pore waters from four drillholes, two of which penetrated the décollement zone and reached the underthrust lower plate sedimentary sequence of the Cocos Plate, were examined for boron contents and boron isotopic signatures. The combined results show dilution of the uppermost sedimentary cover of the forearc, with boron contents lower than half of the present-day seawater values. Pore fluid "refreshening" suggests that gas hydrate water has been mixed with the sediment interstitial water, without profoundly affecting the d11B values. Fault-related flux of a deeply generated fluid is inferred from high B concentration in the interval beneath the décollement, being released from the underthrust sequence with incipient burial. First-order fluid budget calculations over a cross-section across the Costa Rica forearc indicate that no significant fluid transfer from the lower to the upper plate is inferred from boron fluid profiles, at least within the frontal 40 km studied. Expulsed lower plate pore water, which is estimated to be 0.26-0.44 km3 per km trench, is conducted efficiently along and just beneath the décollement zone, indicating effective shear-enhanced compaction. In the upper plate forearc wedge, dewatering occurs as diffuse transport as well as channelled flow. A volume of approximately 2 km3 per km trench is expulsed due to compaction and, to a lesser extent, lateral shortening. Pore water chemistry is influenced by gas hydrate instability, so that it remains unknown whether deep processes like mineral dehydration or hydrocarbon formation may play a considerable role towards the hinterland.

(Table 1) Stable isotope record of Middle Cretaceous benthic foraminifera

Preservation of planktic foraminiferal calcite has received widespread attention in recent years, but the taphonomy of benthic foraminiferal calcite and its influence on the deep-sea palaeotemperature record have gone comparatively unreported. Numerical modeling indicates that the carbonate recrystallization histories of deep-sea sections are dominated by events in their early burial history, meaning that the degree of exchange between sediments and pore fluids during the early postburial phase holds the key to determining the palaeotemperature significance of diagenetic alteration of benthic foraminifera. Postburial sedimentation rate and lithology are likely to be important determinants of the paleoceanographic significance of this sediment-pore fluid interaction. Here we report an investigation of the impact of extreme change in sedimentation rate (a prolonged and widespread Upper Cretaceous hiatus in the North Atlantic Ocean) on the preservation and d18O of benthic foraminifera of Middle Cretaceous age (nannofossil zone NC10, uppermost Albian/lowermost Cenomanian, ~99 Ma ago) from multiple drill sites. At sites where this hiatus immediately overlies NC10, benthic foraminifera appear to display at least moderate preservation of the whole test. However, on closer inspection, these tests are shown to be extremely poorly preserved internally and yield d18O values substantially higher than those from contemporaneous better preserved benthic foraminifera at sites without an immediately overlying hiatus. These high d18O values are interpreted to indicate alteration close to the seafloor in cooler waters during the Late Cretaceous hiatus. Intersite differences in lithology modulate the diagenetic impact of this extreme change in sedimentation rate. Our results highlight the importance of thorough examination of benthic foraminiferal wall structures and lend support to the view that sedimentation rate and lithology are key factors controlling the paleoceanographic significance of diagenetic alteration of biogenic carbonates.

(Appendix A) Oxygen and carbon isotope results of detrital carbonate grains of Heinrich layers from HU90-013-028 and IODP Sites 303-U1302/U1303/U1308 in the North Atlantic Ocean

We report oxygen and carbon isotope results of detrital carbonate grains from Heinrich layers at three sites in the North Atlantic located along a transect from the Labrador Sea to the eastern North Atlantic. Oxygen isotopic values of individual detrital carbonate grains from six Heinrich layers at all sites average - 5.6 ppm ± 1.5 ppm (1sigma; n = 166), reflecting values of dolomitic limestone derived from source areas in northeastern Canada. The d18O of bulk carbonate at Integrated Ocean Drilling Program (IODP) Site U1308 (re-occupation of Deep Sea Drilling Project (DSDP) Site 609) in the eastern North Atlantic records the proportion of detrital to biogenic carbonate and d18O decreases to - 5 ppm during Heinrich (H) events 1, 2, 4 and 5 relative to a background value of ~ 1 to 2 ppm for biogenic carbonate. Bulk d18O also decreases during H3 and H6 but only attains values of - 1ppm, indicating either a greater proportion of biogenic-to-detrital carbonate or a different source. Because the d18O of detrital carbonate is ~ 9 ppm lower than foraminifer carbonate, any fine-grained detrital carbonate not removed from the inner test chambers will lower foraminifer d18O. We conclude bulk carbonate d18O is a sensitive proxy for detrital carbonate and may be useful for identifying Heinrich layers in cores within and near the margins of the North Atlantic ice-rafted detritus (IRD) belt.

U, FE, AND LI ISOTOPE RATIOS IN THE MINERALIZED AND BARREN AREAS OF THE KOMBOLGIE BASIN

The Paleo- to Meso-Proterozoic Jabiluka unconformity related uranium mine is located within the Alligator River Uranium Field, found in the Northern Territories, Australia. The uranium ore is hosted in the late middle Paleoproterozoic Cahill Formation, which is unconformably overlain by a group of unmetamorphosed conglomerates known as the Kombolgie subgroup. The Kombolgie subgroup provided the source for oxidized basinal brines, carrying U as the mobile form U(VI), which interacted with reducing lithologies in the Cahill formation, thus reducing U(VI) to the solid U(IV), and leading to the precipitation of uraninite (UO2). In order to characterize fluid interaction with the ore body and compare that to areas without mineralization, several isotopic tracers were studied on a series of clay samples from drill core at Jabiluka as well as in barren areas throughout the ARUF. Among the potential tracers, three were selected: U (redox sensitive and recent fluid mobilization), Fe (redox sensitive), and Li (fractionated by hydrothermal fluids and adsorption reactions). δ238U values were found to be closely linked to the mineralogy, with samples with higher K/Al ratios (indicating high illite and low chlorite concentrations) having higher δ238U values. This demonstrates that 235U preferentially absorbs onto the surface of chlorite during hydrothermal circulation. In addition, δ234U values lie far from secular equilibrium (δ234U of 30‰), indicating there was addition or removal of 234U from the surface of the samples from recent (<2.5Ma) interactions of mobile fluids. δ57Fe values were found to be related to lithology and spatially to known uranium deposits. Decreasing δ57Fe values were found with increasing depth to the unconformity in a drill hole directly above the ore zone, but not in drill holes in the barren area. Similarly to δ238U, δ7Li is found to correlate with mineralogy, with higher δ7Li values associated with samples with more chlorite. In addition, higher δ7Li values are found at greater depth throughout the basin, indicating that the direction of the mineralizing fluid circulation was upwards from the Cahill formation to the Kombolgie subgroup.