Total organic carbon, bitumen ratio, hopane and sterane parameters of ODP Sites 128-798 and 128-799

Notable compositional changes of organic matter are observed below the silica transition zone in thermally immature sediments. The increase of bitumen ratio, and hopane and sterane isomerization parameters indicate an acceleration of the kinetics of the chemical reactions which transform the organic matter. This phenomenon is probably due to the numerous mineral and textural changes induced by the transformation of amorphous biogenic silica into crystalline authigenic silica.

Concentrations and d13C compositions of n-alkanes, n-alcohols, n-alkanoic acids in a 34-month time series of suspended sediments from the outflow of the Congo River

The concentrations, distributions, and stable carbon isotopes (d13C) of plant waxes carried by fluvial suspended sediments contain valuable information about terrestrial ecosystem characteristics. To properly interpret past changes recorded in sedimentary archives it is crucial to understand the sources and variability of exported plant waxes in modern systems on seasonal to inter-annual timescales. To determine such variability, we present concentrations and d13C compositions of three compound classes (n-alkanes, n-alcohols, n-alkanoic acids) in a 34-month time series of suspended sediments from the outflow of the Congo River. We show that exported plant-dominated n-alkanes (C25-C35) represent a mixture of C3 and C4 end members, each with distinct molecular distributions, as evidenced by an 8.1 ± 0.7 per mil (±1Sigma standard deviation) spread in d13C values across chain-lengths, and weak correlations between individual homologue concentrations (r = 0.52-0.94). In contrast, plant-dominated n-alcohols (C26-C36) and n-alkanoic acids (C26-C36) exhibit stronger positive correlations (r = 0.70-0.99) between homologue concentrations and depleted d13C values (individual homologues average <= -31.3 per mil and -30.8 per mil, respectively), with lower d13C variability across chain-lengths (2.6 ± 0.6 per mil and 2.0 ± 1.1 per mil, respectively). All individual plant-wax lipids show little temporal d13C variability throughout the time-series (1 Sigma <= 0.9 per mil), indicating that their stable carbon isotopes are not a sensitive tracer for temporal changes in plant-wax source in the Congo basin on seasonal to inter-annual timescales. Carbon-normalized concentrations and relative abundances of n-alcohols (19-58% of total plant-wax lipids) and n-alkanoic acids (26-76%) respond rapidly to seasonal changes in runoff, indicating that they are mostly derived from a recently entrained local source. In contrast, a lack of correlation with discharge and low, stable relative abundances (5-16%) indicate that n-alkanes better represent a catchment-integrated signal with minimal response to discharge seasonality. Comparison to published data on other large watersheds indicates that this phenomenon is not limited to the Congo River, and that analysis of multiple plant-wax lipid classes and chain lengths can be used to better resolve local vs. distal ecosystem structure in river catchments.

Time series of air chemistry measurements at Georg-von-Neumayer station, Dronning Maud Land, Antarctica in the years 1982 to 1991

The first Air Chemistry Observatory at the German Antarctic station Georg von Neumayer (GvN) was operated for 10 years from 1982 to 1991. The focus of the established observational programme was on characterizing the physical properties and chemical composition of the aerosol, as well as on monitoring the changing trace gas composition of the background atmosphere, especially concerning greenhouse gases. The observatory was designed by the Institut für Umweltphysik, University of Heidelberg (UHEIIUP). The experiments were installed inside the bivouac lodge, mounted on a sledge and put upon a snow hill to prevent snow accumulation during blizzards. All experiments were under daily control and daily performance protocols were documented. A ventilated stainless steel inlet stack (total height about 3-4 m above the snow surface) with a 50% aerodynamic cut-off diameter around 7-10 µm at wind velocities between 4-10 m/s supplied all experiments with ambient air. Contamination free sampling was realized by several means: (i) The Air Chemistry Observatory was situated in a clean air area about 1500 m south of GvN. Due to the fact that northern wind directions are very rare, contamination from the base can be excluded for most of the time. (ii) The power supply (20 kW) is provided by a cable from the main station, thus no fuel-driven generator is operated in the very vicinity. (iii) Contamination-free sampling is controlled by the permanently recorded wind velocity, wind direction and by condensation particle concentration. Contamination was indicated if one of the following criteria were given: Wind direction within a 330°-30° sector, wind velocity <2.2 m/s or >17.5 m/s, or condensation particle concentrations >2500/cm**3 during summer, >800/cm**3 during spring/autumn and >400/cm**3 during winter. If one or a definable combination of these criteria were given, high volume aerosol sampling and part of the trace gas sampling were interrupted. Starting at 1982 through 1991-01-14 surface ozone was measured with an electrochemical concentration cell (ECC). Surface ozone mixing ratio are given in ppbv = parts per 10**9 by volume. The averaging time corresponds to the given time intervals in the data sheet. The accuracy of the values are better than ±1 ppbv and the detection limit is around 1.0 ppbv. Aerosols were sampled on two Whatman 541 cellulose filters in series and analyzed by ion chromatography at the UHEI-IUP. Generally, the sampling period was seven days but could be up to two weeks on occasion. The air flow was around 100 m**3/h and typically 10000-20000 m**3 of ambient air was forced through the filters for one sample. Concentration values are given in nanogram (ng) per 1 m**3 air at standard pressure and temperature (1013 mbar, 273.16 K). Uncertainties of the values were approximately ±10% to ±15% for the main components MSA, chloride, nitrate, sulfate and sodium, and between ±20% and ±30% for the minor species bromide, ammonium, potassium, magnesium and calcium.

(Table 2) Stable carbon and nitrogen isotope ratios and molar C/N ratio for euchaetid and aetideid copepods during POLARSTERN cruise ANT-XXIII/5

Stable isotope (SI) ratios of carbon (d13C) and nitrogen (d15N) were measured in omnivorous and carnivorous deep-sea copepods of the families Euchaetidae and Aetideidae across the Atlantic sector of the Southern Ocean to establish their trophic positions. Due to high and variable C/N ratios related to differences in lipid content, d13C was corrected using a lipid-normalisation model. d15N signals ranged from 3.0-6.9 per mil in mesopelagic species to 7.0-9.5 per mil in bathypelagic congeners. Among the carnivorous Paraeuchaeta species, the epi- to mesopelagic species Paraeuchaeta antarctica had lower d15N values than the mesopelagic P. rasa and bathypelagic P. barbata. The same trend was observed among omnivorous Aetideidae, but was not significant. In the most abundant species P. antarctica, individuals from the western Atlantic had higher d13C and d15N values than specimens at the eastern stations. These longitudinal changes in d13C and d15N values were attributed to regional differences in hydrography and sea surface temperature (SST), in particular related to a northward extension of the Antarctic Polar Front (APF) at the easternmost stations. The results indicate that even in a mesopelagic carnivorous species, the changes in surface stable isotope signatures are pronounced.

(Table 1) Ratio of hydroxy-GDGT vs. the total core GDGT was calculated based on the detection of hydroxy-GDGT

Hydroxylated glycerol dialkyl glycerol tetraethers (hydroxy-GDGTs) were detected in marine sediments of diverse depositional regimes and ages. Mass spectrometric evidence, complemented by information gleaned from two-dimensional (2D) 1H-13C nuclear magnetic resonance (NMR) spectroscopy on minute quantities of target analyte isolated from marine sediment, allowed us to identify one major compound as a monohydroxy-GDGT with acyclic biphytanyl moieties (OH-GDGT-0). NMR spectroscopic and mass spectrometric data indicate the presence of a tertiary hydroxyl group suggesting the compounds are the tetraether analogues of the widespread hydroxylated archaeol derivatives that have received great attention in geochemical studies of the last two decades. Three other related compounds were assigned as acyclic dihydroxy-GDGT (2OH-GDGT-0) and monohydroxy-GDGT with one (OH-GDGT-1) and two cyclopentane rings (OH-GDGT-2). Based on the identification of hydroxy-GDGT core lipids, a group of previously reported unknown intact polar lipids (IPLs), including the ubiquitously distributed H341-GDGT (Lipp J. S. and Hinrichs K. -U. (2009) Structural diversity and fate of intact polar lipids in marine sediments. Geochim. Cosmochim. Acta 73, 6816-6833), and its analogues were tentatively identified as glycosidic hydroxy-GDGTs. In addition to marine sediments, we also detected hydroxy-GDGTs in a culture of Methanothermococcus thermolithotrophicus. Given the previous finding of the putative polar precursor H341-GDGT in the planktonic marine crenarchaeon Nitrosopumilus maritimus, these compounds are synthesized by representatives of both cren- and euryarchaeota. The ubiquitous distribution and apparent substantial abundance of hydroxy-GDGT core lipids in marine sediments (up to 8% of total isoprenoid core GDGTs) point to their potential as proxies.

Mg/Ca ratio, Sr/Ca ratio and stable isotopes of the foraminifera Oridorsalis umbonatus in surface sediment samples

We investigate the influence of carbonate system parameters (carbonate ion concentration, [CO3**2-]; carbonate ion saturation, Delta [CO3**2-]) on the trace element and stable isotope ratios in the endobenthic foraminifera Oridorsalis umbonatus. Data from modern core top samples from the Namibian continental slope suggest that the shell composition of this species is influenced by the chemistry of the pore-water. For these organic-rich sediments, the impact of ocean bottom water properties on both pore-water and shell chemistry is surprisingly small. Sr/Ca correlates positively with [CO3**2-] and to a lesser extent with Delta [CO3**2-], which is opposed to previous results. A [CO3**2-] decrease of 10 µmol/kg leads to an increase of 0.05 mmol/mol in Sr/Ca. We observe a correlation between shell d18O (corrected for temperature and d18O seawater) and [CO3**2-], however, the variability of the corrected d18O is close to the analytical limit. No clear dependences were observed for d13C and Mg/Ca.

Lead/Calcium profiles in the common time window 1770-2010 of the three Arctica islandica shells

In the study, we establish centennial records of anthropogenic lead pollution at different locations in the North Atlantic (Iceland, USA, and Europe) by means of lead deposited in shells of the long-lived bivalve Arctica islandica. Due to local oceanographic and geological conditions we conclude that the lead concentrations in the Icelandic shell reflect natural influxes of lead into Icelandic waters. In comparison, the lead profile of the US shell is clearly driven by anthropogenic lead emissions transported from the continent to the ocean by westerly surface winds. Lead concentrations in the European North Sea shell, in contrast, are dominantly driven by local lead sources resulting in a much less conspicuous 1970s gasoline lead peak. In conclusion, the lead profiles of the three shells are driven by different influxes of lead, and yet, all support the applicability of Pb/Ca analyses of A. islandica shells to reconstruct location specific anthropogenic lead pollution.

Ratio of Diene/Triene of sediment core MD03-2601

Micropaleontological and biomarker data from two high-accumulation marine sites from the Coastal and Continental Shelf Zone (CCSZ) off East Antarctica (Adélie Land at w140°E and eastern Prydz Bay at w77°E) are used to reconstruct Holocene changes in sea ice and wind stress at the basin-wide scale. These data demonstrate congruent increase in sea-ice concentration/persistence and wind stress-related sea-surface turbulence in the two regions since 7 cal ka BP, with a particularly strong signal since 4.5 - 3.5 cal ka BP. Comparison of these high latitude records with sea ice and turbulence records from the southern mid-latitudes highlights distinctive climatic evolutions according to the different latitudinal bands. Sea-ice persistence and turbulence increase in East Antarctica CCSZ are opposite to sea-surface warming and sea-ice retreat recorded after 4.5 - 3.5 cal ka BP in the East Atlantic and Indian sector between 55 and 45°S. At the same period, paleodata suggest SST cooling in all major coastal upwelling systems of the southern hemisphere, caused by the northward transport of subpolar surface waters as a response to southern Westerlies reinforcement. We therefore propose, as suggested for the northern hemisphere, that Holocene changes in the latitudinal insolation gradient, primarily forced by obliquity and precession and amplified by sea-ice and glacial-ice expansions in the Antarctic realm, are responsible for the observed contrasted latitudinal patterns of southern latitudes.