(Table T1) Ice rafted debris characteristics of ODP Site 177-1092

We have carried out a multiphase analysis of samples from ODP Site 177-1092, Meteor Rise, subantarctic South Atlantic. Samples were analyzed for ice-rafted debris (IRD [see Table T1]) and stable isotopes from benthic foraminifera [see Murphy et al., 2002, doi:10.1016/S0031-0182(01)00495-3]. Both analyses were performed on the same samples. Additional work was performed to identify the paleomagnetic stratigraphy. The analyzed samples range in age from about 2.6(?) Ma to 4.6 Ma, a time span that saw considerable global warmth, but witnessed overall global refrigeration and the transition to truly bipolar glaciations. IRD arrived frequently during the Early and early Late Pliocene, but only as 'background rafting' (occasional grains per sample). The first identifiable IRD above background rafting is associated with marine isotope stage (MIS) KM4 (~3.18 Ma). Successive IRD peaks become larger, the same pattern as noted at nearby Site 114-704. A very large peak near the top of the record, approximately 2.8 Ma, is considered to represent a hiatus. Peaks below 51.3 meters composite depth (mcd) coincide with positive excursions of the oxygen isotopic record, and with negative excursions of the carbon isotopic curve, a pattern also noted at Site 114-704. However, the reasonably large IRD peak at 51 mcd (tentatively identified with MIS G11) coincides with a positive excursion on the carbon isotopic curve and negative excursion on the oxygen isotopic curve. This relationship suggests a northern hemisphere interglacial, rising sea level, destabilization of the Antarctic margin, and delivery of Antarctic icebergs to the Southern Ocean. Such a mechanism has recently been suggested by Kanfoush et al. (2000, doi:10.1126/science.288.5472.1815) for latest Pleistocene stadial/interstadial oscillations. Here we suggest that such a mechanism may have been in place on glacial/interglacial time scales as early as the Late Pliocene.

Petrological and geochemical characteristics of DSDP Hole 37-334 gabbroic cumulates (Table 1)

The gabbronoritic cumulates drilled at DSDP Site 334 (Mid-Atlantic Ridge off the FAMOUS area) are neither crystallization products of the associated basalts, nor from any MORB composition documented along ocean ridges. Their parent melts are richer in SiO2 than MORB at a given MgO content, as attested by the crystallization sequence starting with an olivine+calcic and sub-calcic pyroxene assemblages. These melts are issued from a source highly depleted in incompatible elements, likely residual peridotite left after MORB extraction. To understand the role of water in the genesis of these lithologies whose occurrence in a mid-ocean ridge setting is rather puzzling, we performed a geochemical study on clinopyroxene separates following an analytical protocol able to remove the effects of water rock interactions post-dating their crystallization. Accordingly, the measured isotopic signatures can be used to trace magma sources. We find that Site 334 clinopyroxenes depart from the global mantle correlation: normal MORB values for the 143Nd/ 144Nd ratio (0.51307-0.51315) are associated to highly radiogenic 87Sr / 86Sr (0.7034-0.7067) ratios. This indicates that the parent melts of Site 334 cumulates are issued from a MORB source but that seawater contamination occurred at some stage of their genesis. The extent of contamination, traced by the Sr isotopic signature, is variable within all cumulates but more developed for gabbronorites sensus stricto, suggesting that seawater introduction was a continuous process during all the magmatic evolution of the system, from partial melting to fractional crystallization. Simple masse balance calculations are consistent with a contaminating agent having the characters of a highly hydrated (possibly water saturated) silica-rich melt depleted in almost all incompatible major, minor and trace elements relative to MORB. Mixing in various proportions of contaminated melts similar to the parent melts of Site 334 cumulates with MORB can account for part of the variability in the Sr isotopic signature of oceanic basalts, among other to the short wavelength isotopic "noise" superimposed on regional trends. We conclude that seawater introduction into residual peridotite at shallow depth beneath mid-ocean ridges can lead mantle rocks and their melts to follow complex P-T-fH2O paths that mimic petrogenetic contexts classically attributed to subduction zone environments, like the production of boninitic-andesitic magmas.

Petrology and geochemistry of early cretaceous bimodal continental flood volcanism of the NW Etendeka, Namibia. Part 2: Characteristics and petrogenesis of the high-Ti latite and high-Ti and low-Ti voluminous quartz latite eruptives

As a result of their relative concentration towards the respective Atlantic margins, the silicic eruptives of the Parana (Brazil)-Etendeka large igneous province are disproportionately abundant in the Etendeka of Namibia. The NW Etendeka silicic units, dated at similar to132 Ma, occupy the upper stratigraphic levels of the volcanic sequences, restricted to the coastal zone, and comprise three latites and five quartz latites (QL). The large-volume Fria QL is the only low-Ti type. Its trace element and isotopic signatures indicate massive crustal input. The remaining NW Etendeka silicic units are enigmatic high-Ti types, geochemically different from low-Ti types. They exhibit chemical affinities with the temporally overlapping Khumib high-Ti basalt (see Ewart et al. Part 1) and high crystallization temperatures (greater than or equal to980 to 1120degreesC) inferred from augite and pigeonite phenocrysts, both consistent with their evolution from a mafic source. Geochemically, the high-Ti units define three groups, thought genetically related. We test whether these represent independent liquid lines of descent from a common high-Ti mafic parent. Although the recognition of latites reduces the apparent silica gap, difficulty is encountered in fractional crystallization models by the large volumes of two QL units. Numerical modelling does, however, support large-scale open-system fractional crystallization, assimilation of silicic to basaltic materials, and magma mixing, but cannot entirely exclude partial melting processes within the temporally active extensional environment. The fractional crystallization and mixing signatures add to the complexity of these enigmatic and controversial silicic magmas. The existence, however, of temporally and spatially overlapping high-Ti basalts is, in our view, not coincidental and the high-Ti character of the silicic magmas ultimately reflects a mantle signature.

Relationship between bicarbonate retention and bone characteristics in broiler chickens

Determination of the bicarbonate retention factor (BRF) is an important step during development of the indicator amino acid oxidation technique for use in a new model. A series of 4-h oxidation experiments were performed to determine the BRF of broilers aged 7, 14, 21, 28, 35, and 42 d using 4 birds per age group. A priming dose of 1.2 mu Ci of (NaHCO3)-C-14, followed by eight half-hourly doses of 1 mu Ci of (NaHCO3)-C-14 were given orally to each of 4 birds per age. The percentage of 14 C dose expired by the bird at a steady state was measured. These birds, as well as 12 additional birds matched for age and BW, were killed, and femur bone mineral density was measured by quantitative computed tomography to determine the relationship between bone development and bicarbonate retention at each age. There was a correlation (r = 0.50; P < 0.05) between total cross-sectional femur bone mineral density and bicarbonate retention at each age. A prediction equation (Y = 6.95 x 10(-2) X - 3.51 x 10(5)X(2) + 27.58; P < 0.0001, R-2 = 0.79) where Y = bicarbonate retention and X = BW was generated to predict Y as a function of X. Bicarbonate retention values peaked at 28 d, during the stage of the most rapid bone deposition and the highest growth rate. A constant BRF was found from 1,900 to 2,700 g of BW of 35.15 +/- 1.095% (mean SEM). This retention factor will allow the accurate correction of oxidation of C-14-labeled substrates in broilers of different ages and BW in future indicator amino acid oxidation studies.

Some like it wet - biological characteristics underpinning tolerance of extreme water stress events in Antarctic bryophytes

Antarctic bryophyte communities presently tolerate physiological extremes in water availability, surviving both desiccation and submergence events. We investigated the relative ability of three Antarctic moss species to tolerate physiological extremes in water availability and identified physiological, morphological, and biochemical characteristics that assist species performance under such conditions. Tolerance of desiccation and submergence was investigated using chlorophyll fluorescence during a series of field- and laboratory-based water stress events. Turf water retention and degree of natural habitat submergence were determined from gametophyte shoot size and density, and delta C-13 signatures, respectively. Finally, compounds likely to assist membrane structure and function during desiccation events (fatty acids and soluble carbohydrates) were determined. The results of this study show significant differences in the performance of the three study species under contrasting water stress events. The results indicate that the three study species occupy distinctly different ecological niches with respect to water relations, and provide a physiological explanation for present species distributions. The poor tolerance of submergence seen in Ceratodon purpureus helps explain its restriction to drier sites and conversely, the low tolerance of desiccation and high tolerance of submergence displayed by the endemic Grimmia antarctici is consistent with its restriction to wet habitats. Finally the flexible response observed for Bryum pseudotriquetrum is consistent with its co-occurrence with the other two species across the bryophyte habitat spectrum. The likely effects of future climate change induced shifts in water availability are discussed with respect to future community dynamics.

Interspecific variation in the elemental and stable isotope content of seagrasses in South Florida

The elemental (C, N, and P) and isotope (δ13C, δ15N) content of leaves of the seagrasses Thalassia testudinum, Halodule wrightii, and Syringodium filiforme were measured across a 10 000 km2 survey of the seagrass communities of South Florida, USA, in 1999 and 2000. Trends at local and broad spatial scales were compared to examine interspecific variation in the seagrass characteristics often used as ecological indicators. The elemental and stable isotope contents of all species were variable and demonstrated marked interspecific variation. At broad spatial scales, mean N:P ratios were lowest for T. testudinum (36.5 ± 1.1) and S. filiforme (38.9 ± 1.3), and highest for H. wrightii (44.1 ± 1.8). Stable carbon isotope ratios (δ13C) were highest for S. filiforme (–6.2 ± 0.2‰), intermediate for T. testudinum (–8.6 ± 0.2‰), and lowest for H. wrightii (–10.6 ± 0.3‰). Stable nitrogen isotopes (δ15N) were heaviest for T. testudinum (2.0 ± 0.1‰), and lightest for H. wrightii (1.0 ± 0.3‰) and S. filiforme (1.6 ± 0.2‰). Site depth was negatively correlated to δ13C for all species, while δ15N was positively correlated to depth for H. wrightii and S. filiforme. Similar trends were observed in local comparisons, suggesting that taxon-specific physiological/ecological properties strongly control interspecific variation in elemental and stable isotope content. Temporal trends in δ13C were measured, and revealed that interspecific variation was displayed throughout the year. This work documents interspecific variation in the nutrient dynamics of 3 common seagrasses in South Florida, indicating that interpretation of elemental and stable isotope values needs to be species specific.

Weathering characteristics and lithology of samples from the Rauer Group, Antarctica, obtained in February/March 2007, and conducted with field support of POLARSTERN cruise ANT-XXIII/9

The presence of glacial sediments across the Rauer Group indicates that the East Antarctic ice sheet formerly covered the entire archipelago and has since retreated at least 15 km from its maximum extent. The degree of weathering of these glacial sediments suggests that ice retreat from this maximum position occurred sometime during the latter half of the last glacial cycle. Following this phase of retreat, the ice sheet margin has not expanded more than ~1 km seaward of its present position. This pattern of ice sheet change matches that recorded in Vestfold Hills, providing further evidence that the diminutive Marine Isotope Stage 2 ice sheet advance in the nearby Larsemann Hills may have been influenced by local factors rather than a regional ice-sheet response to climate and sea-level change.

Geochemistry and radiogenic isotope ratios of the volcanic sequences from Izu-Bonin Arc, Japan

New radiogenic isotope and trace element data are presented for the volcanic sequences along 600 km of the active Izu-Bonin arc, the Oligocene Izu arc, and their associated rift basins. As with many intra-oceanic island arcs, the Pliocene-Recent Izu-Bonin frontal-arc lavas are highly depleted in Zr, Nb and the rare-earth elements relative to typical mid-ocean ridge basalt (MORB), indicating that the mantle wedge source has undergone a previous episode of melting. Ratios between these elements (such as Nb/Zr and La/Sm), as well as 143Nd/144Nd, do not vary significantly along the length of the frontal-arc. These parameters suggest that each of the arc volcanoes is derived from similar melt fractions of the mantle wedge. However, Ba/Zr, Ba/Rb and 87Sr/86Sr increase along the frontal-arc to the north. This leads us to propose that a variable enrichment in Ba and radiogenic Sr is superimposed on the mantle wedge. Sr-Nd and Pb-Nd isotope variation indicate that both Sr and Pb become more radiogenic after fluid addition. However, Pb isotope ratios do not correlate with increases in Pb concentration or ratios such as Ba/Zr and Nb/Pb. In other words, the Pb isotopic composition of the arc lavas appears to be independent of the amount of Pb introduced by subduction fluids into the mantle source. This buffering of Pb isotopes along the frontal-arc means that the isotopic composition of the lavas is indistinguishable from that of the fluid. Isotopic mixing models presented for the arc are only illustrative of the many plausible combinations of components and quantities. Despite this, we are able to determine that the mantle wedge has isotopic characteristics similar to Indian Ocean MORB, and that the subduction-fluid solute is primarily derived from subducted oceanic basalt with a <2% contribution from subducted sediment. Lavas in the Oligocene Izu arc and fore-arc basin were derived from a mantle wedge of similar composition to the active arc. Despite levels of Pb enrichment comparable to those of the modern arc, the Pb isotopes of the Oligocene volcanics indicate a lower sediment input into the melting region.

Geomicrobiology, bulk sediment characteristics and pore water chemistry of sediment cores from Laguna Potrok Aike, southern Patagonia

Authigenic minerals can form in the water column and sediments of lakes, either abiotically or mediated by biological activity. Such minerals have been used as paleosalinity and paleoproductivity indicators and reflect trophic state and early diagenetic conditions. They are also considered potential indicators of past and perhaps ongoing microbial activity within sediments. Authigenic concretions, including vivianite, were described in late glacial sediments of Laguna Potrok Aike, a maar lake in southernmost Argentina. Occurrence of iron phosphate implies specific phosphorus sorption behavior and a reducing environment, with methane present. Because organic matter content in these sediments was generally low during glacial times, there must have been alternative sources of phosphorus and biogenic methane. Identifying these sources can help define past trophic state of the lake and diagenetic processes in the sediments. We used scanning electron microscopy, phosphorus speciation in bulk sediment, pore water analyses, in situ ATP measurements, microbial cell counts, and measurements of methane content and its carbon isotope composition (d13C CH4) to identify components of and processes in the sediment. The multiple approaches indicated that volcanic materials in the catchment are important suppliers of iron, sulfur and phosphorus. These elements influence primary productivity and play a role in microbial metabolism during early diagenesis. Authigenic processes led to the formation of pyrite framboids and revealed sulfate reduction. Anaerobic oxidation of methane and shifts in pore water ion concentration indicated microbial influence with depth. This study documents the presence of active microbes within the sediments and their relationship to changing environmental conditions. It also illustrates the substantial role played by microbes in the formation of Laguna Potrok Aike concretions. Thus, authigenic minerals can be used as biosignatures in these late Pleistocene maar sediments.

Bulk sediment and diatom silica carbon isotope composition from Antarctic coastal marine sediments

Organic carbon occluded in diatom silica is assumed to be protected from degradation in the sediment. d13C from diatom carbon (d13C(diatom)) therefore potentially provides a signal of conditions during diatom growth. However, there have been few studies based on d13C(diatom). Numerous variables can influence d13C of organic matter in the marine environment (e.g., salinity, light, nutrient and CO2 availability). Here we compare d13C(diatom) and d13C(TOC) from three sediment records from individual marine inlets (Rauer Group, East Antarctica) to (i) investigate deviations between d13C(diatom) and d13C(TOC), to (ii) identify biological and environmental controls on d13C(diatom) and d13C(TOC), and to (iii) discuss d13C(diatom) as a proxy for environmental and climate reconstructions. The records show individual d13C(diatom) and d13C(TOC) characteristics, which indicates that d13C is not primarily controlled by regional climate or atmospheric CO2 concentration. Since the inlets vary in water depths offsets in d13C are probably related to differences in water column stratification and mixing, which influences redistribution of nutrients and carbon within each inlet. In our dataset changes in d13C(diatom) and d13C(TOC) could not unequivocally be ascribed to changes in diatom species composition, either because the variation in d13C(diatom) between the observed species is too small or because other environmental controls are more dominant. Records from the Southern Ocean show depleted d13C(diatom) values (1-4 per mil) during glacial times compared to the Holocene. Although climate variability throughout the Holocene is low compared to glacial/interglacial variability, we find variability in d13C(diatom), which is in the same order of magnitude. d13C of organic matter produced in the costal marine environment seems to be much more sensitive to environmental changes than open ocean sites and d13C is of strongly local nature.

Sediment and ice characteristics at a buried ice-wedge system at Barrow

Barrow, the northernmost point in Alaska, is one of the most intensively studied areas in the Arctic. However, paleoenvironmental evidence is limited for northern Alaska for the Lateglacial-Holocene transition. For a regional paleoenvironmental reconstruction, we investigated a permafrost ice-wedge tunnel near Barrow, Alaska. The studied site was first excavated in the early 1960s and intercepts a buried ice-wedge system at 3-6 m depth below the surface. A multi-methodological approach was applied to this buried ice-wedge system and the enclosing sediments, which in their combination, give new insight into the Late Quaternary environmental and climate history. Results of geochronological, sedimentological, cryolithological, paleoecological, isotope geochemical and microbiological studies reflect different stages of mid to late Wisconsin (MW to LW), Allerod (AD), Younger Dryas (YD), Preboreal (PB), and Late Holocene paleoenvironmental evolution. The LW age of the site is indicated by AMS dates in the surrounding sediments of 21.7 kyr BP at the lateral contact of the ice-wedge system as well as 39.5 kyr BP below the ice-wedge system. It is only recently that in this region, stable isotope techniques have been employed, i.e. to characterize different types of ground ice. The stable isotope record (oxygen: d18O; hydrogen: dD) of two intersecting ice wedges suggests different phases of the northern Alaskan climate history from AD to PB, with radiocarbon dates from 12.4 to 9.9 kyr BP (ranging from 14.8 to 10.6 kyr cal BP). Stable isotope geochemistry of ice wedges reveals winter temperature variations of the Lateglacial-Holocene transition including a prominent YD cold period, clearly separated from the warmer AD and PB phases. YD is only weakly developed in summer temperature indicators (such as pollen) for the northern Alaska area, and by consequence, the YD cold stadial was here especially related to the winter season. This highlights that the combination of winter and summer indicators comprehensively describes the seasonality of climate-relevant processes in discrete time intervals. The stable isotope record for the Barrow buried ice-wedge system documents for the first time winter climate change at the Lateglacial-Holocene transition continuously and at relatively high (likely centennial) resolution.

Pb and Ba concentrations and Pb isotope ratios in EPICA Dome C ice 2-217 ky BP

A record of Pb isotopic compositions and Pb and Ba concentrations are presented for the EPICA Dome C ice core covering the past 220 ky, indicating the characteristics of dust and volcanic Pb deposition in central East Antarctica. Lead isotopic compositions are also reported in a suite of soil and loess samples from the Southern Hemisphere (Australia, Southern Africa, Southern South America, New Zealand, Antarctica) in order to evaluate the provenance of dust present in Antarctic ice. Lead isotopic compositions in Dome C ice support the contention that Southern South America was an important source of dust in Antarctica during the last two glacial maxima, and furthermore suggest occasional dust contributions from local Antarctic sources. The isotopic signature of Pb in Antarctic ice is altered by the presence of volcanic Pb, inhibiting the evaluation of glacial-interglacial changes in dust sources and the evaluation of Australia as a source of dust to Antarctica. Consequently, an accurate evaluation of the predominant source(s) of Antarctic dust can only be obtained from glacial maxima, when dust-Pb concentrations were greatest. These data confirm that volcanic Pb is present throughout Antarctica and is emitted in a physical phase that is free from Ba, while dust Pb is transported within a matrix containing Ba and other crustal elements.

New dimeric supramolecular structure of mixed (phthalocyaninato)(porphyrinato)-europium(III) sandwiches : preparation and spectroscopic characteristics

The mixed double-decker Eu\[Pc(15C5)4](TPP) (1) was obtained by base-catalysed tetramerisation of 4,5-dicyanobenzo-15-crown-5 using the half-sandwich complex Eu(TPP)(acac) (acac = acetylacetonate), generated in situ, as the template. For comparative studies, the mixed triple-decker complexes Eu2\[Pc(15C5)4](TPP)2 (2) and Eu2\[Pc(15C5)4]2(TPP) (3) were also synthesised by the raise-by-one-story method. These mixed ring sandwich complexes were characterised by various spectroscopic methods. Up to four one-electron oxidations and two one-electron reductions were revealed by cyclic voltammetry (CV) and differential pulse voltammetry (DPV). As shown by electronic absorption and infrared spectroscopy, supramolecular dimers (SM1 and SM3) were formed from the corresponding double-decker 1 and triple-decker 3 in the presence of potassium ions in MeOH/CHCl3.

Vibrational spectroscopy of phthalocyanine and naphthalocyanine in sandwich-type (na)phthalocyaninato and porphyrinato rare earth complexes : (Part 10) The infrared and Raman characteristics of phthalocyanine in heteroleptic bis(phthalocyaninato) rare earth complexes with decreased molecular symmetry

The infrared (IR) spectroscopic data for a series of eleven heteroleptic bis(phthalocyaninato) rare earth complexes MIII(Pc)[Pc(α-OC5H11)4] (M = Sm–Lu, Y) [H2Pc = unsubstituted phthalocyanine, H2Pc(α-OC5H11)4 = 1,8,15,22-tetrakis(3-pentyloxy)phthalocyanine] have been collected with 2 cm−1 resolution. Raman spectroscopic properties in the range of 500–1800 cm−1 for these double-decker molecules have also been comparatively studied using laser excitation sources emitting at 632.8 and 785 nm. Both the IR and Raman spectra for M(Pc)[Pc(α-OC5H11)4] are more complicated than those of homoleptic bis(phthalocyaninato) rare earth analogues due to the decreased molecular symmetry of these double-decker compounds, namely C4. For this series, the IR Pc√− marker band appears as an intense absorption at 1309–1317 cm−1, attributed to the pyrrole stretching. With laser excitation at 632.8 nm, Raman vibrations derived from isoindole ring and aza stretchings in the range of 1300–1600 cm−1 are selectively intensified. In contrast, when excited with laser radiation of 785 nm, the ring radial vibrations of isoindole moieties and dihedral plane deformations between 500 and 1000 cm−1 for M(Pc)[Pc(α-OC5H11)4] intensify to become the strongest scatterings. Both techniques reveal that the frequencies of pyrrole stretching, isoindole breathing, isoindole stretchings, aza stretchings and coupling of pyrrole and aza stretchings depend on the rare earth ionic size, shifting to higher energy along with the lanthanide contraction due to the increased ring-ring interaction across the series. The assignments of the vibrational bands for these compounds have been made and discussed in relation to other unsubstituted and substituted bis(phthalocyaninato) rare earth analogues, such as M(Pc)2 and M(OOPc)2 [H2OOPc = 2,3,9,10,16,17,23,24-octakis(octyloxy)phthalocyanine].