Results from ikaite investigations in the Kara Sea

The authigenic carbonate mineral ikaite is specific of low-temperature high latitude environments. The depletion of ikaite carbon in 13C isotopes in most cases implies a causal relation of ikaite generation with methane geochemistry. In this paper we present new data on ikaite minerals in Holocene sediments sampled along the Yenisei channel at the southern (74°N) and northern (77°N) ends. Stable carbon isotopes of the ikaite crystals were studied in conjunction with the hydrochemistry and isotope geochemistry of the sediments. Pore water and natural gas samples were separated from sediments to describe the methane carbon isotope distribution pattern throughout two sedimentary sequences embedding the ikaite crystals of different isotope composition (-24 per mil and -42 per mil). The biogenic nature of the methane is indicated by 51 C values being as low as -104.4 per mil. In the case of the moderately depleted sample (-24 per mil) from the southern location the small-scale ikaite formation fits best into the concept of a 'closed» sediment system, with a limited diagenetic carbon dioxide source being present. In the second case, formation of highly abundant and isotopically depleted ikaite crystals (-42 per mil) were caused by upwards flux of biogenic methane from below. Contribution of two main carbon sources to the ikaite crystals was estimated by using a isotope-mass balance equation. Organic-derived CO2 constitutes the principal source in both samples, amounting to 50 % of the total carbon of the strongly depleted ikaite crystals (-42 per mil) sampled at the northern end and 83 % for the moderately (-24 per mil) depleted crystals from the southern end. Methane-derived CO2 comes to 42 % for the isotopically light ikaite crystals and to 9% for the isotopically heavy crystals. The importance of sediment lithology and diffusive transport for ikaite formation is emphazied.

Sulphur isotope analyses in the southern ocean and the central Dronning Maud Land, East Antarctica

Sulphur isotope analyses are an important tool for the study of the natural sulphur cycle. On the northern hemisphere such studies of the atmospheric part of the cycle are practically impossible due to the high emission rate of anthropogenic sulphur. Merely in remote areas of the world such as the Antarctic 34S analyses can be used to identify the various sulphur sources (sea spray, biogenic und volcanic sources). We report here results of 34S measurements on sulphates from recent atmospheric precipitations (snow), lake waters, and salt efflorescences sampled in the Schirmacher Oasis and the Gruber Mountains, central Dronning Maud Land, East Antarctica. By plotting the delta 34S of precipitation versus % sea-spray sulphate the isotopic composition of the excess sulphate (which is probably of marine-biogenic origin) is extrapolated to be +4 per mil. Lake water sulphate and atmospheric precipitations have a comparable sulphur isotope composition (about +5 per mil). The analyzed secondary sulphates from the salt efflorescences, mainly gypsum and a few water-soluble sulphatcs (hexahydrite, epsomite, burkeite. and pickeringite), vary in their isotopic composition between about -12 and +8 per mil. This wide scatter is probably due to chemical weathering of primary sulphides having different delta 34S values in the substratum.

Lithology, stage, organic carbon, d13C, hydrocarbons and fatty acids at DSDP Hole 93-603B

Organic-matter-rich Upper Cretaceous claystones from DSDP Hole 603B, lower continental rise, had organic carbon values ranging from 1.7 to 13.7%, C/N ratios from 32 to 72, and d13C values from -23.5 to -27.1 per mil. Lipid class maxima for the unbound alkanes (C29 and C31), unbound fatty acids (C28 and C30), and bound fatty acids (C24, C26 , and C28) and the strong odd-carbon and even-carbon preferences, respectively, suggested that the organic matter in these sediments was partially the result of input from continental plant waxes. Transport of the organic-matter-rich sediments to the deep sea from the near-shore environment probably resulted from turbiditic flow under oxygen-stressed conditions.

Geochemistry of Atlantis Massif serpentinites

The Lost City hydrothermal system at the southern Atlantis Massif (Mid-Atlantic Ridge, 30°N) provides a natural laboratory for studying serpentinization processes, the temporal evolution of ultramafic-hosted hydrothermal systems, and alteration conditions during formation and emplacement of an oceanic core complex. Here we present B, O, and Sr isotope data to investigate fluid/rock interaction and mass transfer during detachment faulting and exhumation of lithospheric sequences within the Atlantis Massif. Our data indicate that extensive serpentinization was a seawater-dominated process that occurred predominately at temperatures of 150-250 °C and at high integrated W/R ratios that led to a marked boron enrichment (34-91 ppm). Boron removal from seawater during serpentinization is positively correlated with changes in d11B (11-16 per mil) but shows no correlation with O-isotope composition. Modeling indicates that B concentrations and isotope values of the serpentinites are controlled by transient temperature-pH conditions. In contrast to prior studies, we conclude that low-temperature marine weathering processes are insignificant for boron geochemistry of the Atlantis Massif serpentinites. Talc- and amphibole-rich fault rocks formed within a zone of detachment faulting at temperatures of approximately 270-350 °C and at low W/R ratios. Talc formation in ultramafic domains in the massif was subsequent to an early stage of serpentinization and was controlled by the access of Si-rich fluids derived through seawater-gabbro interactions. Replacement of serpentine by talc resulted in boron loss and significant lowering of d11B values (9-10 per mil), which we model as the product of progressive extraction of boron. Our study provides new constraints on the boron geochemical cycle at oceanic spreading ridges and suggests that serpentinization associated with ultramafic-hosted hydrothermal systems may have important implications for the behavior of boron in subduction zone settings.

Age determination and geochemical composition of sediment core DA04-31P

There is limited knowledge pertaining to the history of the Greenland Ice Sheet (GIS) during the last glacial-interglacial transition as it retreated from the continental margins to an inland position. Here we use multiproxy data, including ice-rafted debris (IRD); planktonic isotopes; alkenone temperatures; and tephra geochemistry from the northern Labrador Sea, off southwest Greenland, to investigate the deglacial response of the GIS and evaluate its implications for the North Atlantic deglacial development. The results imply that the southern GIS retreated in three successive stages: (1) early deglaciation of the East Greenland margins, by tephra-rich IRD that embrace Heinrich Event 1; (2) progressive retreat during Allerød culminating in major meltwater releases (d18O depletion of 1.2 per mil) at the Allerød-Younger Dryas transition (12.8-13.0 kyr B.P.); and (3) a final stage of glacial recession during the early Holocene (~9-11 kyr B.P.). Rather than indicating local temperatures of ambient surface water, the alkenones likely were transported to the core site by the Irminger Current. We attribute the timing of GIS retreat to the incursion of warm intermediate waters along the base of grounded glaciers and below floating ice shelves on the continental margin. The results lend support to the view that GIS meltwater presented a forcing factor for the Younger Dryas cooling.

Sulfur isotopic variations in nodular and disseminated pyrite at DSDP Hole 93-603B

Analyses of modern marine sediments have suggested that availability and type of organic matter, sedimentation rate, and openness of the sulfate system influence the degree of isotopic fractionation between seawater sulfate and sedimentary iron sulfides. Isotopic studies of ancient sulfides should, therefore, provide insights into conditions of deposition and early diagenesis. Analysis of d34S of disseminated pyrite from Cretaceous sediments of Hole 603B yielded fractionations relative to coeval seawater sulfate ranging from 40 to 55 per mil, which are within the range for modern oxic marine sediments reported by others. Sulfur/carbon ratios are similar to those found from modern marine sediments and suggest that disseminated pyrite formation was dependent upon available organic carbon. These results imply that depositional and early diagenetic conditions during the Cretaceous in Hole 603B were similar to those occurring in initially oxic marine environments today. Macroscopic (nodular) pyrite from Hole 603B is isotopically variable (d34S values = - 48 to + 33 per mil), but generally more positive than disseminated pyrite. The isotopic evidence suggests that macroscopic pyrite formed during late stages of sulfate reduction in a system closed with respect to sulfate. However, detailed analyses of large pyrite nodules did not yield a consistent pattern of isotopic variation from center to rim.

Oxygen isotopes and hydrocarbon composition of gas hydrate and hydrate water from ODP Leg 165 sites

Ocean Drilling Program (ODP) Leg 164 recovered a number of large solid gas hydrate from Sites 994, 996, and 997 on the Blake Ridge. Sites 994 and 997 samples, either nodular or thick massive pieces, were subjected to laboratory analysis and measurements to determine the structure, molecular and isotopic composition, thermal conductivity, and equilibrium dissociation conditions. X-ray computed tomography (CT) imagery, X-ray diffraction, nuclear magnetic resonance (NMR), and Raman spectroscopy have revealed that the gas hydrates recovered from the Blake Ridge are nearly 100% methane gas hydrate of Structure I, cubic with a lattice constant of a = 11.95 ± 0.05 angström, and a molar ratio of water to gas (hydration number) of 6.2. The d18O of water is 2.67 per mil to 3.51 per mil SMOW, which is 3.5-4.0 heavier than the ambient interstitial waters. The d13C and dD of methane are -66 per mil to -70 per mil and -201 per mil to -206 per mil, respectively, suggesting that the methane was generated through bacterial CO2 reduction. Thermal conductivity values of the Blake Ridge hydrates range from 0.3 to 0.5 W/(m K). Equilibrium dissociation experiments indicate that the three-phase equilibrium for the specimen is 3.27 MPa at 274.7 K. This is almost identical to that of synthetic pure methane hydrate in freshwater.

Magnesium isotope ratios of pore-fluids and dolomites

Magnesium concentrations in deep-sea sediment pore-fluids typically decrease down core due to net precipitation of dolomite or clay minerals in the sediments or underlying crust. To better characterize and differentiate these processes, we have measured magnesium isotopes in pore-fluids and sediment samples from Ocean Drilling Program sites (1082, 1086, 1012, 984, 1219, and 925) that span a range of oceanographic settings. At all sites, magnesium concentrations decrease with depth. At sites where diagenetic reactions are dominated by the respiration of organic carbon, pore-fluid d26Mg values increase with depth by as much as 2 per mil. Because carbonates preferentially incorporate 24Mg (low d26Mg), the increase in pore-fluid d26Mg values at these sites is consistent with the removal of magnesium in Mg-carbonate (dolomite). In contrast, at sites where the respiration of organic carbon is not important and/or weatherable minerals are abundant, pore-fluid d26Mg values decrease with depth by up to 2 per mil. The decline in pore-fluid d26Mg at these sites is consistent with a magnesium sink that is isotopically enriched relative to the pore-fluid. The identity of this enriched magnesium sink is likely clay minerals. Using a simple 1D diffusion-advection-reaction model of pore-fluid magnesium, we estimate rates of net magnesium uptake/removal and associated net magnesium isotope fractionation factors for sources and sinks at all sites. Independent estimates of magnesium isotope fractionation during dolomite precipitation from measured d26Mg values of dolomite samples from sites 1082 and 1012 are very similar to modeled net fractionation factors at these sites, suggesting that local exchange of magnesium between sediment and pore-fluid at these sites can be neglected. Our results indicate that the magnesium incorporated in dolomite is 2.0-2.7 per mil depleted in d26Mg relative to the precipitating fluid. Assuming local exchange of magnesium is minor at the rest of the studied sites, our results suggest that magnesium incorporated into clay minerals is enriched in d26Mg by 0 per mil to +1.25 per mil relative to the precipitating fluid. This work demonstrates the utility of magnesium isotopes as a tracer for magnesium sources/sinks in low-temperature aqueous systems.

Oxygen isotopic composition of interstitial waters from ODP Leg 207 sites

We determined oxygen isotopic compositions of interstitial water (IW) recovered during Ocean Drilling Program Leg 207. Five sites were cored (3200- to 1900-m water depth) on Demerara Rise off Suriname, South America, recovering a Cenomanian-Paleogene sedimentary sequence consisting of black shales and chalks. A total of 115 IW oxygen isotopic analyses are presented.

Sulphate concentrations and sulphur isotopic composition in pore fluids from ODP Leg 168 sites

A numerical model of sulfate reduction and isotopic fractionation has been applied to pore fluid SO4**2- and d34S data from four sites drilled during Ocean Drilling Program (ODP) Leg 168 in the Cascadia Basin at 48°N, where basement temperatures reach up to 62°C. There is a source of sulfate both at the top and the bottom of the sediment column due to the presence of basement fluid flow, which promotes bacterial sulfate reduction below the sulfate minimum zone at elevated temperatures. Pore fluid d34S data show the highest values (135 per mil) yet found in the marine environment. The bacterial sulfur isotopic fractionation factor, a, is severely underestimated if the pore fluids of anoxic marine sediments are assumed to be closed systems and Rayleigh fractionation plots yield erroneous values for a by as much as 15 per mil in diffusive and advective pore fluid regimes. Model results are consistent with a = 1.077+/-0.007 with no temperature effect over the range 1.8 to 62°C and no effect of sulfate reduction rate over the range 2 to 10 pmol/ccm/day. The reason for this large isotopic fractionation is unknown, but one difference with previous studies is the very low sulfate reduction rates recorded, about two orders of magnitude lower than literature values that are in the range of µmol/ccm/day to tens of nmol/ccm/day. In general, the greatest 34S depletions are associated with the lowest sulfate reduction rates and vice versa, and it is possible that such extreme fractionation is a characteristic of open systems with low sulfate reduction rates.

Boron concentrations and isotope ratios of authigenic carbonates from the Oregon margin

Boron contents and boron, carbon and oxygen stable isotopes were determined for authigenic carbonates recovered from Ocean Drilling Program Leg 146, Oregon margin. Carbonate precipitates are the most widespread authigenic phase in the shallow accretionary wedge and carry chemical information about long-term variations in pore fluid origin and flow paths in the Cascadia subduction zone. Drilling the first ridge (toe area including the frontal thrust) and the second ridge (or Hydrate Ridge) of the prism demonstrated different fluid regimes, with higher B contents in the authigenic precipitates at the toe. The delta11B of 18 authigenic precipitates analysed ranges from 13.9 per mil to as high as 39.8 per mil, extending the upper range of previously reported carbonate delta11B values considerably. When related to the delta11B ratio of their parent solutions, these data are characteristic of fluid-related processes in accretionary prisms. Together with delta13C and delta18O, delta11B ratios of the carbonate concretions, nodules and crusts allow one to distinguish between precipitation influenced by (i) seawater, (ii) fluid reservoirs at different depth levels within the accretionary prism and (iii) cage water from dissociated gas hydrates, the latter possibly indicating a fluctuation of the bottom simulating reflector during most recent Earth's history. From this first systematic boron study on authigenic precipitates from an accretionary prism it is suggested that B contents of such carbonate crusts and concretions exceed those reported for other marine carbonates. Given the abundance of such precipitates at convergent margins, they represent a significant B sink in geochemical cycling. Isotopic compositions of the parent fluids to the carbonates mirror B chemistry of modern pore waters from convergent margins. The precipitates carry information of different subduction-related fluid processes over a certain period of time, and hence are a crucial tracer in the investigation of palaeo-fluid flow.

(Table 1) Tie points between IODP Site 306-U1314 benthic d18O and the global benthic d18O stack LR04

Stable carbon and oxygen isotopes from benthic and planktic foraminifers, planktic foraminifer assemblages and ice rafted debris from the North Atlantic Site U1314 (Integrated Ocean Drilling Program Expedition 306) were examined to investigate orbital and millennial-scale climate variability in the North Atlantic and its impact on global circulation focusing on the development of glacial periods during the mid-Pleistocene (ca 800-400 ka). Glacial initiations were characterized by a rapid cooling (6-10 °C in less than 7 kyr) in the mean annual sea surface temperature (SST), increasing benthic d18O values and high benthic d13C values. The continuous increase in benthic d18O suggests a continuous ice sheet growth whereas the positive benthic d13C values indicate that the flow of the Iceland Scotland Overflow water (ISOW) was vigorous. Strong deep water formation in the Norwegian Greenland Sea promoted a high transfer of freshwater from the ocean to the continents. However, low SSTs at Site U1314 suggest a subpolar gyre cooling and freshening that may have reduced deep water formation in the Labrador Sea during glacial initiations. Once the 3.5 per mil threshold in the benthic d18O record was exceeded, ice rafting started and ice sheet growth was punctuated by millennial-scale waning events which returned to the ocean part of the freshwater accumulated on the continents. Ice-rafting events were associated with a rapid reduction in the ISOW (benthic d13C values dropped 0.5-1?) and followed by millennial-scale warmings. The first two millennial-scale warm intervals of each glacial period reached interglacial temperatures and were particularly abrupt (6-10 °C in ~3 kyr). Subsequent millennial-scale warm events were cooler probably because the AMOC was rather reduced as suggested by the low benthic d13C values. These two abrupt warming events that occurred at early glacial periods were also observed in the Antarctic temperature and CO2 records, suggesting a close correlation between both Hemispheres. The comparison of the sea surface proxies with the benthic d18O record (as the Southern sign) indicates the presence of a millennial-scale seesaw pattern similar to that seen during the Last Glacial period.

(Table 2) d13C from the Lusklint section

The carbon isotope composition (d13C) of bulk organic matter and two palynomorph groups (scolecodonts and chitinozoans) from the Llandovery-Wenlock strata of Gotland (E Sweden) are compared to gain knowledge about carbon cycling in the Silurian (sub)tropical shelf environment. The d13C values of the palynomorphs are mostly lower than the d13C values of the bulk organic matter, and the d13C values of the benthic scolecodonts are lower than those of the planktonic chitinozoans. While the difference between bulk and palynomorph d13C may be in part a function of trophic state, the lower values of the scolecodonts relative to those of chitinozoans, which are assumed to live in the well-mixed water column, might imply an infaunal mode of life for the polychaetes that carried the scolecodonts. Lower d13C for the scolecodonts in the middle of the section may represent variations in primary marine productivity (supported by acritarch abundance data), oxidation of organic matter in the bottom waters, or genera effects. In general, however, trends between the three data sets are parallel, indicating similarities in the low frequency, environmentally forced controls. The d13C data show a decreasing trend from the base of the section, up to a horizon well below the base of the Upper Visby Formation. At this level, and therefore probably several 10 kyr before the d13C increase in the carbonates, the d13C organic values increase by ~1 per mil. This perhaps is an expression of a changed composition of the bulk organic matter associated with the extinction events prior to the Llandovery-Wenlock boundary.