Petrology, mineralogy, and chemistry of basaltic rocks at DSDP Leg 81 Holes

We detail the petrography and mineralogy of 145 basaltic rocks from the top, middle, and base of flow units identified on shipboard along with associated pyroclastic samples. Our account includes representative electron microprobe analyses of primary and secondary minerals; 28 whole-rock major-oxide analyses; 135 whole-rock analyses each for 21 trace elements; 7 whole-rock rare-earth analyses; and 77 whole-rock X-ray-diffraction analyses. These data show generally similar petrography, mineralogy, and chemistry for the basalts from all four sites; they are typically subalkaline and consanguineous with limited evolution along the tholeiite trend. Limited fractionation is indicated by immobile trace elements; some xenocrystic incorporation from more basic material also occurred. Secondary alteration products indicate early subaerial weathering followed by prolonged interaction with seawater, most likely below 150°C at Holes 552, 553A, and 554A. At Hole 555, greenschist alteration affected the deepest rocks (olivine-dolerite) penetrated, at 250-300°C.

Mg/Ca and stable oxygen measurement of the past 27 Ma of ODP Hole 120-747A

We explore the applicability of paired Mg/Ca and 18O/16O measurements on benthic foraminifera from Southern Ocean site 747 to paleoceanographic reconstructions on pre-Pleistocene timescales. We focus on the late Oligocene through Pleistocene (27-0 Ma) history of paleotemperatures and the evolution of the d18O values of seawater (d18Osw) at a temporal resolution of ~100-200 kyr. Absolute paleotemperature estimates depend on assumptions of how Mg/Ca ratios of seawater have changed over the past 27 Myr, but relative changes that occur on geologically brief timescales are robust. Results indicate that at the Oligocene to Miocene boundary (23.8 Ma), temperatures lag the increase in global ice-volume deduced from benthic foraminiferal d18O values, but the smaller-scale Miocene glaciations are accompanied by ocean cooling of -1°C. During the mid-Miocene phase of Antarctic ice sheet growth (~15-13 Ma), water temperatures cool by ~3°C. Unlike the benthic foraminiferal d18O values, which remain relatively constant thereafter, temperatures vary (by 3°C) and reach maxima at ~12 and ~8.5 Ma. The onset of significant Northern Hemisphere glaciation during the late Pliocene is synchronous with an ~4°C cooling at site 747. A comparison of our d18Osw curve to the Haq et al. (1987, doi:10.1126/science.235.4793.1156 ) sea level curve yields excellent agreement between sequence boundaries and times of increasing seawater 18O/16O ratios. At ~12-11 Ma in particular, when benthic foraminiferal d18O values do not support a further increase in ice volume, the d18Osw curve comes to a maximum that corresponds to a major mid-Miocene sea level regression. The agreement between the character of our Mg/Ca-based d18Osw curve and sequence stratigraphy demonstrates that benthic foramaniferal Mg/Ca ratios can be used to trace the d18Osw on pre-Pleistocene timescales despite a number of uncertainties related to poorly constrained temperature calibrations and paleoseawater Mg/Ca ratios. The Mg/Ca record also highlights that deep ocean temperatures can vary independently and unexpectedly from ice volume changes, which can lead to misinterpretations of the d18O record.

Impacts of passive warming chambers on soil parameters in Antarctica

Passive chambers are used to examine the impacts of summer warming in Antarctica but, so far, impacts occurring outside the growing season, or related to extreme temperatures, have not been reported, despite their potentially large biological significance. In this review, we synthesise and discuss the microclimate impacts of passive warming chambers (closed, ventilated and Open Top Chamber-OTC) commonly used in Antarctic terrestrial habitats, paying special attention to seasonal warming, during the growing season and outside, extreme temperatures and freeze-thaw events. Both temperature increases and decreases were recorded throughout the year. Closed chambers caused earlier spring soil thaw (8-28 days) while OTCs delayed soil thaw (3-13 days). Smaller closed chamber types recorded the largest temperature extremes (up to 20°C higher than ambient) and longest periods (up to 11 h) of above ambient extreme temperatures, and even OTCs had above ambient temperature extremes over up to 5 consecutive hours. The frequency of freeze-thaw events was reduced by ~25%. All chamber types experienced extreme temperature ranges that could negatively affect biological responses, while warming during winter could result in depletion of limited metabolic resources. The effects outside the growing season could be as important in driving biological responses as the mean summer warming. We make suggestions for improving season-specific warming simulations and propose that seasonal and changed temperature patterns achieved under climate manipulations should be recognised explicitly in descriptions of treatment effects.

Holocene corals from the South China Sea

The South China Sea (SCS) is well connected with the western Pacific and influenced by the East Asian monsoon. We have examined temporal variations in radiocarbon marine reservoir ages (R) and regional marine reservoir corrections (DeltaR) of the SCS during the Holocene using paired measurements of AMS 14C and TIMS 230Th on 20 pristine corals. The results show large fluctuations in both R and DeltaR values over the past 7500 years (yrs) with two distinct plateaus during 7.5-5.6 and 3.5-2.5 thousand calendar years before present (cal ka BP). The respective weighted mean DeltaR values of these plateaus are 151 ± 85 and 89 ± 59 yrs, which are significantly higher than its modern value of -23 ± 52 yrs. This suggests that using a constant modern DeltaR value to calibrate 14C dates of the SCS marine samples will introduce additional errors to the calibrated ages. Our results provide the first database for the Holocene R and DeltaR values of the SCS for improved radiocarbon calibration of marine samples. We interpret the two DeltaR plateaus as being related to two intervals with weakened El Niño - Southern Oscillation (ENSO) and intensified East Asian summer monsoon (EASM). This is because the 14C content of the SCS surface water is controlled by both the 14C concentration of the Pacific North Equatorial Current (NEC) which is in turn influenced by ENSO-induced upwelling along the Pacific equator and vertical upwelling within the SCS as a result of moisture transportation to midlatitude region to supply the EASM rainfall.

Mean chemical characteristics and volcano signatures of ice cores from Belukha, the Everest and three Svalbard sites

Ice cores from outside the Greenland and Antarctic ice sheets are difficult to date because of seasonal melting and multiple sources (terrestrial, marine, biogenic and anthropogenic) of sulfates deposited onto the ice. Here we present a method of volcanic sulfate extraction that relies on fitting sulfate profiles to other ion species measured along the cores in moving windows in log space. We verify the method with a well dated section of the Belukha ice core from central Eurasia. There are excellent matches to volcanoes in the preindustrial, and clear extraction of volcanic peaks in the post-1940 period when a simple method based on calcium as a proxy for terrestrial sulfate fails due to anthropogenic sulfate deposition. We then attempt to use the same statistical scheme to locate volcanic sulfate horizons within three ice cores from Svalbard and a core from Mount Everest. Volcanic sulfate is <5% of the sulfate budget in every core, and differences in eruption signals extracted reflect the large differences in environment between western, northern and central regions of Svalbard. The Lomonosovfonna and Vestfonna cores span about the last 1000 years, with good extraction of volcanic signals, while Holtedahlfonna which extends to about AD1700 appears to lack a clear record. The Mount Everest core allows clean volcanic signal extraction and the core extends back to about AD700, slightly older than a previous flow model has suggested. The method may thus be used to extract historical volcanic records from a more diverse geographical range than hitherto.

Site characteristics and ice speed at four sites on Kangiata Nunata Sermia glacier, southwest Greenland

We present subdaily ice flow measurements at four GPS sites between 36 and 72 km from the margin of a marine-terminating Greenland outlet glacier spanning the 2009 melt season. Our data show that >35 km from the margin, seasonal and shorter-time scale ice flow variations are controlled by surface melt-induced changes in subglacial hydrology. Following the onset of melting at each site, ice motion increased above background for up to 2 months with resultant up-glacier migration of both the onset and peak of acceleration. Later in our survey, ice flow at all sites decreased to below background. Multiple 1 to 15 day speedups increased ice motion by up to 40% above background. These events were typically accompanied by uplift and coincided with enhanced surface melt or lake drainage. Our results indicate that the subglacial drainage system evolved through the season with efficient drainage extending to at least 48 km inland during the melt season. While we can explain our observations with reference to evolution of the glacier drainage system, the net effect of the summer speed variations on annual motion is small (~1%). This, in part, is because the speedups are compensated for by slowdowns beneath background associated with the establishment of an efficient subglacial drainage system. In addition, the speedups are less pronounced in comparison to land-terminating systems. Our results reveal similarities between the inland ice flow response of Greenland marine- and land-terminating outlet glaciers.

Shear experiments from IODP Expedition 322 and 333 samples

The mechanical behavior of the plate boundary fault zone is of paramount importance in subduction zones, because it controls megathrust earthquake nucleation and propagation as well as the structural style of the forearc. In the Nankai area along the NanTroSEIZE (Kumano) drilling transect offshore SW Japan, a heterogeneous sedimentary sequence overlying the oceanic crust enters the subduction zone. In order to predict how variations in lithology, and thus mechanical properties, affect the formation and evolution of the plate boundary fault, we conducted laboratory tests measuring the shear strengths of sediments approaching the trench covering each major lithological sedimentary unit. We observe that shear strength increases nonlinearly with depth, such that the (apparent) coefficient of friction decreases. In combination with a critical taper analysis, the results imply that the plate boundary position is located on the main frontal thrust. Further landward, the plate boundary is expected to step down into progressively lower stratigraphic units, assisted by moderately elevated pore pressures. As seismogenic depths are approached, the décollement may further step down to lower volcaniclastic or pelagic strata but this requires specific overpressure conditions. High-taper angle and elevated strengths in the toe region may be local features restricted to the Kumano transect.

Establishment, expansion and regeneration of aspen (Populus tremula) in the Torneträsk area, subarctic Sweden

In subarctic Sweden, recent decadal colonization and expansion of aspen (Populus tremula L.) were recorded. Over the past 100 years, aspen became c. 16 times more abundant, mainly as a result of increased sexual regeneration. Moreover, aspen now reach tree-size (>2 m) at the alpine treeline, an ecotone that has been dominated by mountain birch (Betula pubescens ssp. czerepanovii) for at least the past 4000 years. We found that sexual regeneration in aspen probably occurred seven times or more within the last century. Whereas sexual regeneration occurred during moist years following a year with an exceptionally high June-July temperature, asexual regeneration was favored by warm and dry summers. Disturbance to the birch forest by cyclic moth population outbreaks was critical in aspen establishment in the subalpine area. At the treeline, aspen colonization was less determined by these moth outbreaks, and was mainly restricted by summer temperature. If summer warming persists, aspen spread may continue in subarctic Sweden, particularly at the treeline. However, changing disturbance regimes, future herbivore population dynamics and the responses of aspen's competitors birch and pine to a changing climate may result in different outcomes.

P-wave velocities and applied bed thickness and velocity changes for synthetic seismograms, ODP Leg 188 and Leg 119 sites

Synthetic seismograms provide a crucial link between lithologic variations within a drill hole and reflectors on seismic profiles crossing the site. In essence, they provide a ground-truth for the interpretation of seismic data. Using a combination of core and logging data, we created synthetic seismograms for Ocean Drilling Program Sites 1165 and 1166, drilled during Leg 188, and Site 742, drilled during Leg 119, all in Prydz Bay, Antarctica. Results from Site 1165 suggest that coring penetrated a target reflector initially thought to represent the onset of drift sedimentation, but the lithologic change across the boundary does not show a change from predrift to drift sediments. The origin of a shallow reflector packet in the seismic line across Site 1166 and a line connecting Sites 1166 and 742 was resolved into its constituent sources, as this reflector occurs in a region of large-scale, narrowly spaced impedance changes. Furthermore, Site 1166 was situated in a fluvio-deltaic system with widely variable geology, and bed thickness changes were estimated between the site and both seismic lines.

U-series ages from calcitic cold-water corals from the Amundsen Sea

Radiocarbon and uranium-thorium dating results are presented from a genus of calcitic Antarctic cold-water octocorals (family Coralliidae), which were collected from the Marie Byrd Seamounts in the Amundsen Sea (Pacific sector of the Southern Ocean) and which to date have not been investigated geochemically. The geochronological results are set in context with solution and laser ablation-based element/Ca ratios (Li, B, Mg, Mn, Sr, Ba, U, Th). Octocoral radiocarbon ages on living corals are in excellent agreement with modern ambient deep-water D14C, while multiple samples of individual fossil coral specimens yielded reproducible radiocarbon ages. Provided that local radiocarbon reservoir ages can be derived for a given time, fossil Amundsen Sea octocorals should be reliably dateable by means of radiocarbon. In contrast to the encouraging radiocarbon findings, the uranium-series data are more difficult to interpret. The uranium concentration of these calcitic octocorals is an order of magnitude lower than in the aragonitic hexacorals that are conventionally used for geochronological investigations. While modern and Late Holocene octocorals yield initial d234U in good agreement with modern seawater, our results reveal preferential inward diffusion of dissolved alpha-recoiled 234U and its impact on fossil coral d234U. Besides alpha-recoil related 234U diffusion, high-resolution sampling of two fossil octocorals further demonstrates that diagenetic uranium mobility has offset apparent coral U-series ages. Combined with the preferential alpha-recoil 234U diffusion, this process has prevented fossil octocorals from preserving a closed system U-series calendar age for longer than a few thousand years. Moreover, several corals investigated contain significant initial thorium, which cannot be adequately corrected for because of an apparently variable initial 232Th/230Th. Our results demonstrate that calcitic cold-water corals are unsuitable for reliable U-series dating. Mg/Ca ratios within single octocoral specimens are internally strikingly homogeneous, and appear promising in terms of their response to ambient temperature. Magnesium/lithium ratios are significantly higher than usually observed in other deep marine calcifiers and for many of our studied corals are remarkably close to seawater compositions. Although this family of octocorals is unsuitable for glacial deep-water D14C reconstructions, our findings highlight some important differences between hexacoral (aragonitic) and octocoral (calcitic) biomineralisation. Calcitic octocorals could still be useful for trace element and some isotopic studies, such as reconstruction of ambient deep water neodymium isotope composition or pH, via boron isotopic measurements.

Nd isotope composition of fossil fish teeth of ODP Hole 119-738B

We report an optimized method for extracting neodymium (Nd) from fossil fish teeth with a single-stage column (125 µl stem volume; LN Resin, Eichrom Industries, Darien Illinois) for isotopic analysis by multi-collector inductively coupled mass spectrometry (MC-ICMPS). Three reference materials (basalt: BCR-2, BHVO-2; phosphate: fossil bone composite) and splits of fossil fish teeth samples previously processed with existing two-stage column methods were processed using the single-stage column method. 143Nd/144Nd values of reference materials agree within error with published values, and the values for fish teeth correspond with sample splits processed with two-stage columns. Precision to ± ~0.23 epsilon-Nd was achieved for 30 ng Nd samples of reference materials, and Nd isotope measurements of fossil fish tooth sample replicates as small as 7 ng Nd were reproducible within long term instrumental uncertainty. We demonstrate the utility of the new method with the first high resolution Nd isotope record spanning the ~40.0 Ma middle Eocene Climatic Optimum, which shows an excursion of 0.65 epsilon-Nd during the peak warming at the study site (Ocean Drilling Program Leg 119, Site 738; 30 kyr sample spacing from 40.3 to 39.6 Ma). LN Resin is already used in standard methods for separating Nd, and Nd isotopes are routinely measured by MC-ICPMS with high efficiency inlet systems. Our innovation is a single, small volume LN Resin column for Nd separation. The streamlined approach results in a 10X increase in sample throughput.

Arctic aboveground tundra biomass dynamics between 1982 and 2010

Numerous studies have evaluated the dynamics of Arctic tundra vegetation throughout the past few decades, using remotely sensed proxies of vegetation, such as the normalized difference vegetation index (NDVI). While extremely useful, these coarse-scale satellite-derived measurements give us minimal information with regard to how these changes are being expressed on the ground, in terms of tundra structure and function. In this analysis, we used a strong regression model between NDVI and aboveground tundra phytomass, developed from extensive field-harvested measurements of vegetation biomass, to estimate the biomass dynamics of the circumpolar Arctic tundra over the period of continuous satellite records (1982-2010). We found that the southernmost tundra subzones (C-E) dominate the increases in biomass, ranging from 20 to 26%, although there was a high degree of heterogeneity across regions, floristic provinces, and vegetation types. The estimated increase in carbon of the aboveground live vegetation of 0.40 Pg C over the past three decades is substantial, although quite small relative to anthropogenic C emissions. However, a 19.8% average increase in aboveground biomass has major implications for nearly all aspects of tundra ecosystems including hydrology, active layer depths, permafrost regimes, wildlife and human use of Arctic landscapes. While spatially extensive on-the-ground measurements of tundra biomass were conducted in the development of this analysis, validation is still impossible without more repeated, long-term monitoring of Arctic tundra biomass in the field.

ERA-CLIM Historical Upper-Air Data 1900-1972

Historical, i.e. pre-1957, upper-air data are a valuable source of information on the state of the atmosphere, in some parts of the World back to the early 20th century. However, to date reanalyses have only partially made use of these data, and only of observations made after 1948. Even for the period between 1948 (the starting year of the NCEP/NCAR reanalysis) and the International Geophysical Year in 1957 (the starting year of the ERA-40 reanalysis), when the global upper-air coverage reached more or less its current status, many observations have not been digitised until now. The Comprehensive Historical Upper-Air Network (CHUAN) already compiled a large collection of pre-1957 upper-air data. In the framework of the European project ERA-CLIM, significant amounts of additional upper-air data have been catalogued (> 1.3 mio station days), imaged (> 200,000 images) and digitised (> 700,000 station days) in order to prepare a new input dataset for upcoming reanalyses. The records cover large parts of the globe, focussing on so far less well covered regions such as the Tropics, the polar regions and the Oceans, and on very early upper-air data from Europe and the US. The total number of digitised/inventoried records is 61/101 for moving upper-air data, i.e. data from ships etc., and 735/1,783 for fixed upper-air stations. Here, we give a detailed description of the resulting dataset including the metadata and the quality checking procedures applied. The data will be included in the next version of CHUAN.

Geochemistry of tetrapyrrole, tetraterpenoid, and perylene pigments in sediments from the Gulf of California

Results and discussion cover pigment analyses of 36 sediment samples recovered by Deep Sea Drilling Project Leg 64, and six samples from the Leg 64 site-survey cruise in the Guaymas Basin (Scripps Institution of Oceanography, Leg 3). Pigments investigated were tetrapyrroles, tetraterpenoids, and the PAH compound perylene. Traces of mixed nickel and copper ETIO-porphyrins were ubiquitous in all sediment samples, except for the very surface (i.e., <2 m sub-bottom), and their presence is taken as an indication of minor influxes of previously oxidized allochthonous (terrestrial) organic matter. Phorbides and chlorins isolated from Site 479 sediment samples (i.e., the oxygen-minimum locale, northeast of the Guaymas Basin) well represent the reductive diagenesis ("Treibs Scheme"; see Baker and Palmer, 1978; Treibs, 1936) of chlorophyll derivatives. Three forms of pheophytin-a, plus a variety of phorbides, were found to give rise to freebase porphyrins, nickel phylloerythrin, and nickel porphyrins, with increasing depth of burial (increasing temperature). Sediments from Sites 481, 10G, and 18G yielded chlorophyll derivatives characteristic of early oxidative alterations. Included among these pigments are allomerized pheophytin-a, purpurin-18, and chlorin-p6. The high thermal gradient imposed upon the late Quaternary sediments of Site 477 greatly accelerated chlorophyll diagenesis in the adjacent overlying sediments, that is, the production of large quantities of free-base desoxophylloerythroetioporphyrin (DPEP) occurred in a section (477-7-5) presently only 49.8 meters sub-bottom. Present depth and age of these sediments are such that only chlorins and phorbides would be expected. Carotenoid (i.e., tetraterpenoids) concentrations were found to decrease rapidly with increasing sub-bottom depth. Less deeply buried sediments (e.g., 0-30 m) yielded mixtures of carotenes and oxygen-substituted carotenoids. Oxygencontaining (oxy-, oxo-, epoxy-) carotenoids were found to be lost preferentially with increased depth of burial. Early carotenoid diagenesis is suggested as involving interacting reductions and dehydrations whereby dehydro-, didehydro-, and retro-carotenes are generated. Destruction of carotenoids as pigments may involve oxidative cleavage of the isoprenoid chain through epoxy intermediates, akin to changes in the senescent cells of plants. Perylene was found to be a common component of the extractable organic matter from all sediments investigated. The generation of alkyl perylenes was found to parallel increases in the existing thermal regime at all sites. Igneous sills and sill complexes within the sediment profile of Site 481 altered (i.e., scrambled) the otherwise straightforward thermally induced alkylation of perylene. The degree of perylene alkylation is proposed as an indicator of geothermal stress for non-contemporaneous marine sediments.

Molecular composition in surface and subsurface sediments of the Helgoland mud area, North Sea

The role of microorganisms in the cycling of sedimentary organic carbon is a crucial one. To better understand relationships between molecular composition of a potentially bioavailable fraction of organic matter and microbial populations, bacterial and archaeal communities were characterized using pyrosequencing-based 16S rRNA gene analysis in surface (top 30 cm) and subsurface/deeper sediments (30-530 cm) of the Helgoland mud area, North Sea. Fourier Transform Ion Cyclotron Resonance Mass Spectrometry (FT-ICR MS) was used to characterize a potentially bioavailable organic matter fraction (hot-water extractable organic matter, WE-OM). Algal polymer-associated microbial populations such as members of the Gammaproteobacteria, Bacteroidetes, and Verrucomicrobia were dominant in surface sediments while members of the Chloroflexi (Dehalococcoidales and candidate order GIF9) and Miscellaneous Crenarchaeota Groups (MCG), both of which are linked to degradation of more recalcitrant, aromatic compounds and detrital proteins, were dominant in subsurface sediments. Microbial populations dominant in subsurface sediments (Chloroflexi, members of MCG, and Thermoplasmata) showed strong correlations to total organic carbon (TOC) content. Changes of WE-OM with sediment depth reveal molecular transformations from oxygen-rich [high oxygen to carbon (O/C), low hydrogen to carbon (H/C) ratios] aromatic compounds and highly unsaturated compounds toward compounds with lower O/C and higher H/C ratios. The observed molecular changes were most pronounced in organic compounds containing only CHO atoms. Our data thus, highlights classes of sedimentary organic compounds that may serve as microbial energy sources in methanic marine subsurface environments.