Chemistry of interstitial waters of ODP Leg 112 samples

Two distinct hydrogeochemical regimes currently dominate the Peruvian continental margin. One, in shallower water (150-450 m) shelf to upper-slope regions, is characterized by interstitial waters with strong positive chloride gradients with depth. The maximum measured value of 1043 mM chloride at Site 680 at ITS corresponds to a degree of seawater evaporation of ~2 times. Major ion chemistry and strontioum isotopic composition of the interstitial waters suggest that a subsurface brine that has a marine origin and is of pre-early Miocene "age," profoundly influences the chemistry and diagenesis of this shelf environment. Site 684 at ~9°S must be closest to the source of this brine, which becomes diluted with seawater and/or interstitial water as it flows southward toward Site 686 at ~13?S (and probably beyond) at a rate of approximately 3 to 4 cm/yr, since early Miocene time. The other regime, in deep water (3000-5000 m) middle to lower-slope regions, is characterized by interstitial waters with steep negative and nonsteady-state chloride gradients with depth. The minimum measured value of 454 mM chloride, at Site 683 at ITS, corresponds to ~20% dilution of seawater chloride The most probably sources of these low-chloride fluids are gas hydrate dissociation and mineral (particularly clay) dehydration reactions. Fluid advection is consistent with (1) the extent of dilution shown in the chloride profiles, (2) the striking nonsteady-state depth profiles of chlorides at Sites 683 and 688 and of 87Sr/86Sr ratios at Site 685, and (3) the temperatures resulting from an average geothermal gradient of 50°C/km and required for clay mineral dehydration reactions. Strontium isotope data reveal two separate fluid regimes in this slope region: a more northerly one at Sites 683 and 685 that is influenced by fluids with a radiogenic continental strontium signature, and a southerly one at Sites 682 and 688 that is influenced by fluids with a nonradiogenic oceanic signatures. Stratigraphically controlled fluid migration seems to prevail in this margin. Because of its special tectonic setting, Site 679 at ITS is geochemically distinct. The interstitial waters are characterized by seawater chloride concentrations to -200 mbsf and deeper by a significantly lower chloride concentration of about two-thirds of the value in seawater, suggesting mixing with a meteoric water source. Regardless of the hydrogeochemical regime, the chemistry and isotopic compositions of the interstitial waters at all sites are markedly modified by diagenesis, particularly by calcite and dolomite crystallization.

The Antarctic ice core chronology (AICC2012)

Abstract of Bazin et al. (2013): An accurate and coherent chronological framework is essential for the interpretation of climatic and environmental records obtained from deep polar ice cores. Until now, one common ice core age scale had been developed based on an inverse dating method (Datice), combining glaciological modelling with absolute and stratigraphic markers between 4 ice cores covering the last 50 ka (thousands of years before present) (Lemieux-Dudon et al., 2010). In this paper, together with the companion paper of Veres et al. (2013), we present an extension of this work back to 800 ka for the NGRIP, TALDICE, EDML, Vostok and EDC ice cores using an improved version of the Datice tool. The AICC2012 (Antarctic Ice Core Chronology 2012) chronology includes numerous new gas and ice stratigraphic links as well as improved evaluation of background and associated variance scenarios. This paper concentrates on the long timescales between 120-800 ka. In this framework, new measurements of d18Oatm over Marine Isotope Stage (MIS) 11-12 on EDC and a complete d18Oatm record of the TALDICE ice cores permit us to derive additional orbital gas age constraints. The coherency of the different orbitally deduced ages (from d18Oatm, dO2/N2 and air content) has been verified before implementation in AICC2012. The new chronology is now independent of other archives and shows only small differences, most of the time within the original uncertainty range calculated by Datice, when compared with the previous ice core reference age scale EDC3, the Dome F chronology, or using a comparison between speleothems and methane. For instance, the largest deviation between AICC2012 and EDC3 (5.4 ka) is obtained around MIS 12. Despite significant modifications of the chronological constraints around MIS 5, now independent of speleothem records in AICC2012, the date of Termination II is very close to the EDC3 one. Abstract of Veres et al. (2013): The deep polar ice cores provide reference records commonly employed in global correlation of past climate events. However, temporal divergences reaching up to several thousand years (ka) exist between ice cores over the last climatic cycle. In this context, we are hereby introducing the Antarctic Ice Core Chronology 2012 (AICC2012), a new and coherent timescale developed for four Antarctic ice cores, namely Vostok, EPICA Dome C (EDC), EPICA Dronning Maud Land (EDML) and Talos Dome (TALDICE), alongside the Greenlandic NGRIP record. The AICC2012 timescale has been constructed using the Bayesian tool Datice (Lemieux-Dudon et al., 2010) that combines glaciological inputs and data constraints, including a wide range of relative and absolute gas and ice stratigraphic markers. We focus here on the last 120 ka, whereas the companion paper by Bazin et al. (2013) focuses on the interval 120-800 ka. Compared to previous timescales, AICC2012 presents an improved timing for the last glacial inception, respecting the glaciological constraints of all analyzed records. Moreover, with the addition of numerous new stratigraphic markers and improved calculation of the lock-in depth (LID) based on d15N data employed as the Datice background scenario, the AICC2012 presents a slightly improved timing for the bipolar sequence of events over Marine Isotope Stage 3 associated with the seesaw mechanism, with maximum differences of about 600 yr with respect to the previous Datice-derived chronology of Lemieux-Dudon et al. (2010), hereafter denoted LD2010. Our improved scenario confirms the regional differences for the millennial scale variability over the last glacial period: while the EDC isotopic record (events of triangular shape) displays peaks roughly at the same time as the NGRIP abrupt isotopic increases, the EDML isotopic record (events characterized by broader peaks or even extended periods of high isotope values) reached the isotopic maximum several centuries before. It is expected that the future contribution of both other long ice core records and other types of chronological constraints to the Datice tool will lead to further refinements in the ice core chronologies beyond the AICC2012 chronology. For the time being however, we recommend that AICC2012 be used as the preferred chronology for the Vostok, EDC, EDML and TALDICE ice core records, both over the last glacial cycle (this study), and beyond (following Bazin et al., 2013). The ages for NGRIP in AICC2012 are virtually identical to those of GICC05 for the last 60.2 ka, whereas the ages beyond are independent of those in GICC05modelext (as in the construction of AICC2012, the GICC05modelext was included only via the background scenarios and not as age markers). As such, where issues of phasing between Antarctic records included in AICC2012 and NGRIP are involved, the NGRIP ages in AICC2012 should therefore be taken to avoid introducing false offsets. However for issues involving only Greenland ice cores, there is not yet a strong basis to recommend superseding GICC05modelext as the recommended age scale for Greenland ice cores.

H, O, Sr, and Nd isotope ratios and water, Rb, Sr, Sm, and Nd content of ODP Hole 116-717C and 116-718C samples (Table 2)

Mineralogical and H, O, Sr, and Nd isotope compositions have been analyzed on a set of representative samples from the 17-m.y. section in ODP Leg 116 Holes 717C and 718C. Based on the mineralogical composition of the fraction <2 µm together with the lithogenic-biogenic composition of the fraction >63 µm, the whole section can be subdivided into three major periods of sedimentation. Between 17.1 and 6 m.y., and between 0.8 m.y. to present, the sediments are characterized by sandy and silty turbiditic inputs with a high proportion of minerals derived from a gneissic source without alteration. In the fraction <2 µm, illite and chlorite are dominant over smectite and kaolinite. The granulometric fraction >63 µm contains quartz, muscovite, biotite, chlorite, and feldspars. The 6-to 0.8-m.y. period is represented by an alternation of sandy/silty horizons, muds, and calcareous muds rich in smectite, and kaolinite (50% to 85% of the fraction <2 µm) and bioclastic material. The presence of smectite and kaolinite, as well as the 18O/16O and the 87Sr/86Sr ratios of the fraction <2 µm, imply an evolution in a soil environment and exchanges with meteoric ground water. The ranges of isotopic compositions are limited throughout the section: d18O quartz = 11.7 to 13.3 per mil, 87Sr/86Sr = 0.733 to 0.760 and epsilon-Nd (0) = -17.4 to -13.8. These values are within those of the High Himalaya Crystalline series, and they are considered to reflect this source region. The data imply that, since 17 Ma, this formation has supplied the major part of the eroded material.

Physical and chemical analysis of firn cores from Ronne Ice Shelf, Antarctica

This data on the distribution of the accumulation rate and 18O content of near-surface layers in the eastern part of the Ronne Ice Shelf, Antarctica, were derived from an analysis of 16 firn cores. The firn cores were drilled along the traverse route of the Filchner-V-Campaign in 1995. The traverse followed an ice flowline of the Foundation Ice Stream and reached the margin of the inland ice, an area which has not yet been investigated. On the ice shelf the accumulation rates decrease with distance from the coast. Ascending to the inland ice the accumulation rates again reach almost coastal values. This regional distribution is in agreement with the temperature gradient along the traverse. The 18O content of the near-surface layers is closely related to the 10 m firn temperature. They strongly decrease from the grounding line towards the inland ice. At the southernmost site at 1100 m a.s.l., the mean d18O value of the firn decreases to -40?. Ice with that isotopic signature was found in cores from the central part of the Ronne Ice Shelf just above the marine ice layer, indicating that it originates from this area. All ice deposited as snow further south was melted beneath the ice shelf after passing the grounding-line area. The time series of accumulation rate and 18O content reveal no climatic trend during the last 30-50 years.

Petrology and isotope characteristics of basalts from ODP Hole 111-504B

Petrography and isotope geochemical characteristics of H, O, S, Sr, and Nd have been described for basalts recovered from Hole 504B during Leg 111 of the Ocean Drilling Program. The petrographic and chemical features of the recovered basalts are similar to those obtained previously (DSDP Legs 69, 70, and 83); they can be divided into phyric (plagioclase-rich) and aphyric (Plagioclase- and clinopyroxene-rich) basalts and show low abundances of TiO2, Na2O, K2O, and Sr. This indicates that the basalts belong to Group D, comprising the majority of the upper section of the Hole 504B. The diopside-rich nature of the clinopyroxene phenocrysts and Ca-rich nature of the Plagioclase phenocrysts are also consistent with the preceding statement. The Sr and Nd isotope systematics (average 87Sr/86Sr = 0.70267 ± 0.00007 and average 143Nd/144Nd = 0.513157 ± 0.000041) indicate that the magma sources are isotopically heterogeneous, although the analyzed samples represent only the lowermost 200-m section of Hole 504B. The rocks were subjected to moderate hydrothermal alteration throughout the section recovered during Leg 111. Alteration is limited to interstices, microfractures, and grain boundaries of the primary minerals, forming chlorite, actinolite, talc, smectite, quartz, sphene, and pyrite. In harmony with the moderate alteration, the following alteration-sensitive parameters show rather limited ranges of variation: H2O = 1.1 ±0.2 wt%, dD = - 38 per mil ± 4 per mil, d180 = 5.4 per mil ± 0.3 per mil, total S = 562 ± 181 ppm, and d34S = 0.8 per mil ± 0.3 per mil. Based on these data, it was estimated that the hydrothermal fluids had dD and d180 values only slightly higher than those of seawater, the water/rock ratios were as low as 0.02-0.2, and the temperature of alteration was 300°-400°C. Sulfur exists predominantly as pyrite and in minor quantities as chalcopyrite. No primary monosulfide was detected. This and the d34S values of pyrite (d34S = 0.8 per mil) suggest that primary pyrrhotite was almost completely oxidized to pyrite by reaction with hydrothermal fluids containing very little sulfate.

Mineralogy and geochemistry of Mg-phyllosilicates from Middle Valley, northern Juan de Fuca Ridge

We present results of a detailed mineralogical and geochemical study of the progressive hydrothermal alteration of clastic sediments recovered at ODP Site 858 in an area of active hydrothermal venting at the sedimented, axial rift valley of Middle Valley (northern Juan de Fuca Ridge). These results allow a characterization of newly formed phyllosilicates and provide constraints on the mechanisms of clay formation and controls of mineral reactions on the chemical and isotopic composition of hydrothermal fluids. Hydrothermal alteration at Site 858 is characterized by a progressive change in phyllosilicate assemblages with depth. In the immediate vent area, at Hole 858B, detrital layers are intercalated with pure hydrothermal precipitates at the top of the section, with a predominance of hydrothermal phases at depth. Sequentially downhole in Hole 858B, the clay fraction of the pure hydrothermal layers changes from smectite to corrensite to swelling chlorite and finally to chlorite. In three pure hydrothermal layers in the deepest part of Hole 858B, the clay minerals coexist with neoformed quartz. Neoformed and detrital components are clearly distinguished on the basis of morphology, as seen by SEM and TEM, and by their chemical and stable isotope compositions. Corrensite is characterized by a 24 Å stacking sequence and high Si- and Mg-contents, with Fe/(Fe+Mg) ratio of = 0.08. We propose that corrensite is a unique, possibly metastable, mineralogical phase and was precipitated directly from seawater-dominated hydrothermal fluids. Hydrothermal chlorite in Hole 858B has a stacking sequence of 14 Å with Fe/(Fe+Mg) ratios of ? 0.35. The chemistry and structure of swelling chlorite suggest that it is a corrensiteychlorite mixed-layer phase. The mineralogical zonation in Hole 858B is accompanied by a systematic decrease in d18O, reflecting both the high thermal gradients that prevail at Site 858 and extensive sediment-fluid interaction. Precipitation of the Mg-phyllosilicates in the vent region directly controls the chemical and isotopic compositions of the pore fluids. This is particularly evident by decreases in Mg and enrichments in deuterium and salinity in the pore fluids at depths at which corrensite and chlorite are formed. Structural formulae calculated from TEM-EDX analyses were used to construct clay-H2O oxygen isotope fractionation curves based on oxygen bond models. Our results suggest isotopic disequilibrium conditions for corrensite-quartz and swelling chlorite-quartz precipitation, but yield an equilibrium temperature of 300° C ± 30° for chlorite-quartz at 32 m below the surface. This estimate is consistent with independent estimates and indicates steep thermal gradients of 10-11°/m in the vent region.

Environmental characteristics and gas composition of Lost Hammer, Canadian Arctic

We report the first microbiological characterization of a terrestrial methane seep in a cryo-environment in the form of an Arctic hypersaline (~24% salinity), subzero (-5 C), perennial spring, arising through thick permafrost in an area with an average annual air temperature of -15 C. Bacterial and archaeal 16S rRNA gene clone libraries indicated a relatively low diversity of phylotypes within the spring sediment (Shannon index values of 1.65 and 1.39, respectively). Bacterial phylotypes were related to microorganisms such as Loktanella, Gillisia, Halomonas and Marinobacter spp. previously recovered from cold, saline habitats. A proportion of the bacterial phylotypes were cultured, including Marinobacter and Halomonas, with all isolates capable of growth at the in situ temperature (-5 C). Archaeal phylotypes were related to signatures from hypersaline deep-sea methane-seep sediments and were dominated by the anaerobic methane group 1a (ANME-1a) clade of anaerobic methane oxidizing archaea. CARD-FISH analyses indicated that cells within the spring sediment consisted of ~84.0% bacterial and 3.8% archaeal cells with ANME-1 cells accounting for most of the archaeal cells. The major gas discharging from the spring was methane (~50%) with the low CH4/C2 + ratio and hydrogen and carbon isotope signatures consistent with a thermogenic origin of the methane. Overall, this hypersaline, subzero environment supports a viable microbial community capable of activity at in situ temperature and where methane may behave as an energy and carbon source for sustaining anaerobic oxidation of methane-based microbial metabolism. This site also provides a model of how a methane seep can form in a cryo-environment as well as a mechanism for the hypothesized Martian methane plumes.

1000 year ice-core records from Berkner Island, Antarctica

Two medium-depth ice cores were retrieved from Berkner Island by a joint project between the Alfred-Wegener-Institut and the British Antarctic Survey in the 1994/95 field season. A 151m deep core from the northern dome (Reinwarthhöhe) of Berkner Island spans 700 years, while a 181m deep core from the southern dome (Thyssenhöhe) spans approximately 1200 years. Both cores display clear seasonal cycles in electrical conductivity measurements, allowing dating by annual-layer counting and the calculation of accumulation profiles. Stable-isotope measurements (both d18O and dD), together with the accumulation data, allow us to estimate changes in climate for most of the past millennium: the data show multi-decadal variability around a generally stable long-term mean. In addition, a full suite of major chemistry measurements is available to define the history of aerosol deposition at these sites: again, there is little evidence that the chemistry of the sites has changed over the past six centuries. Finally, we suggest that the southern dome, with an ice thickness of 950 m, is an ideal site from which to gain a climate history of the late stages of the last glacial and the deglaciation for comparison with the records from the deep Antarctic ice cores, and with other intermediate-depth cores such asTaylor Dome and Siple Dome.

Light hydrocarbons in sediments of ODP Site 124-768

Geochemical investigations on gases and interstitial waters from ODP Site 768 (Sulu Trench/Philippines) demonstrate the application of molecular gas composition in combination with stable isotope analyses to the genetic classification of light hydrocarbons. 13C/12C and D/H ratios of methane from gas pockets in cores and gases desorbed from frozen sediments by a vacuum/acid treatment suggest a microbial generation of methane by a CO2 reducing process in sediments with low sulfate concentrations. Isotope data and molecular composition of sediment gases liberated by the vacuum/acid treatment seem to be affected by a secondary desorption process during sampling. A comparison between the D/H ratios of methane from gas pockets and interstitial H2O points to an in-situ generation of methane down to a sub-bottom depth of approx. 720 m. Below this depth hydrogen isotope data indicate a migration of light hydrocarbons into pyroclastic sediments at this site. The occurrence of higher hydrocarbons (propane to pentane) in gases from gas pockets coincides with the vertical distribution of mature organic matter. Gases within the zone of mature organic matter are gases of a mixed microbial and thermal origin.