Biogenic and mineral composition and foraminiferal stratigraphy of sediment cores obtained in northern Germany

The Ratekau boring ended in clays of the so-called Asterigerina-Zone; these clays have shallow-water features in the uppermost samples. The clays are overlain by deep-water clays with pteropods; this formation is split into two parts by a shallow-water deposit. The fossiliferous series ends upward in sandy deposits with shallow-water fossils. The question is raised whether the two deep-water deposits might correspond to the Lower Doberg Beds (Eochattian) and the Upper Doberg Beds (Neochattian) at the Doberg hill, closer to the rim of the basin. All fossiliferous samples from this boring are thought to be of Late Oligocene age; the boundary towards the Middle Oligocene, however, could not be ascertained. The Vaale boring ended in rather typical Septaria clay of the Middle Oligocene. This clay is capped by some metres of unfossiliferous glauconite clays, which in turn are overlain by silts and silty clays with planktonic fossils identical to those found at Dingden locality. These deposits are tentatively dated as Early Miocene. The next higher series of samples consists of sands and clays deposited in shallower waters. They contain a rich fauna of benthic molluscs, which, according to the current notion in stratigraphy, would have a Reinbek Age. In addition, they contain a set of planktonic fossils which differs from the 'Lower Miocene' assemblages. These sands and clays are overlain by a thick series of marine sands very poor in fossils. Finally, four metres of clay with foraminifera, having Younger Miocene affinities, form the top of the fossiliferous sequence. The borings at Wulksfelde and Langenhorn were not far apart and their sediments are easily correlated. Both wells start below in continental 'Lignite Sands' and contain overlying shallow water sands and clays. These yielded Hemmoor benthic mollusca, supposed to indicate Lower Miocene in the relevant literature; however, we encountered their planktonic foraminifera in the uppermost Miocene as well. The same planktonic species were found in all samples of both borings. These deposits under discussion furthermore contain a particular pteropod species. They are overlain by a thick series of gypsiferous clays, with scarce fossils. The uppermost fossiliferous clays (probably Langenfelde Age) contain another pteropod species, not met with in other samples. The discrepancies between the plankton zonation and the traditional subdivision according to benthic molluscs in the borings of Vaale, Wulksfelde and Langenhorn (and in samples from Twistringen, Dingden and Antwerp localities as well) renders the time-stratigraphic value of the denominations Reinbek and Hemmoor rather doubtful. The samples of the Westerland boring can be placed in the Gram and Sylt stages of local chronostratigraphy on the strength of the Astarte series established by HINSCH. The Gram samples contain a typical pteropod species; both groups of samples contain the same planktonic foraminifera as the borings Wulksfelde and Langenhorn. Our material did not bring the problem of the Miocene-Pliocene boundary in this region any closer to a solution. In conclusion, it can be claimed that this investigation provides strong arguments that the usual recognition of Hemmoor and Reinbek does not correspond to well-defined chronostratigraphical units. A better chronostratigraphic subdivision has to be based on the examination of many more samples, and on a better understanding of the paleoecology of the fossils involved.

Chemical composition and solubility of ocean phosphatized rocks in seawater

In order to elucidate possibility of limestone phosphatization during contact with seawater two sets of experiments were carried out: that of solubility of natural phosphates in seawater and that of deposition of phosphorus onto calcareous phase. Concentration of phosphorus in seawater used for solubility experiments varied from 39 to 338 µ/l, temperature was 5.5-17.5°C and pH 7.8-7.9. The lowest solubility was characteristic of ancient crystallized samples. The deposition experiments showed that in case when concentration of dissolved phosphate in seawater reaches 3 mg/l it might be sorbed on solid CaCO3 phase without forming its own mineral. The latter is able to form rapidly but only if magnesium is not present in solution. In magnesium-free water calcium phosphates precipitate when concentration of dissolved phosphorus is higher than 0.9-1.2 mg/l. These results show that phosphatization of limestones in marine environment takes place during their contact with pore water but not with marine bottom water.

Ba/Ca ratios in benthic foraminifera from recent core tops

The carbon isotope ratio (delta13C) and cadmium content (Cd/Ca) of benthic foraminifera shells have been used to reconstruct deep-water circulation patterns of the glacial oceans. These tracers co-vary with phosphorus in the modern ocean because they are nearly quantitatively regenerated from sinking biological debris in the upper water column. Hence they can be used to reconstruct the distribution of labile nutrients in glacial water masses. Independent constraints on glacial deep-ocean circulation patterns could be provided by a tracer of the distribution of silica and alkalinity, the deeply regenerated constituents of planktonic hard parts. Barium shares key aspects of its behaviour with these refractory nutrients because it is removed from solution in surface waters and incorporated into sinking particles which slowly dissolve deep in the water column and in the sediments. The fractionation of Ba between deep-water masses of the major ocean basins is largely controlled by thermohaline circulation patterns, so Ba conforms to different boundary conditions from Cd and 13C. As Ba substitutes into trigonal carbonates, it is a potential palaeoceano-graphic tracer if the Ba content of foraminifera shells reflects ambient dissolved Ba concentrations. Here we present data from Recent core-top benthic foraminifera which indicate that the Ba content of some recent calcitic benthic foraminifera does co-vary with bottom-water Ba.

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.

In situ d18O and Mg/Ca analyses of ODP Site 143-865 samples

We report d18O and minor element (Mg/Ca, Sr/Ca) data acquired by high-resolution, in situ secondary ion mass spectrometry (SIMS) from planktic foraminiferal shells and 100-500 µm sized diagenetic crystallites recovered from a deep-sea record (ODP Site 865) of the Paleocene-Eocene thermal maximum (PETM). The d18O of crystallites (~1.2 per mil Pee Dee Belemnite (PDB)) is ~4.8 per mil higher than that of planktic foraminiferal calcite (-3.6 per mil PDB), while crystallite Mg/Ca and Sr/Ca ratios are slightly higher and substantially lower than in planktic foraminiferal calcite, respectively. The focused stratigraphic distribution of the crystallites signals an association with PETM conditions; hence, we attribute their formation to early diagenesis initially sourced by seafloor dissolution (burndown) ensued by reprecipitation at higher carbonate saturation. The Mg/Ca ratios of the crystallites are an order of magnitude lower than those predicted by inorganic precipitation experiments, which may reflect a degree of inheritance from "donor" phases of biogenic calcite that underwent solution in the sediment column. In addition, SIMS d18O and electron microprobe Mg/Ca analyses that were taken within a planktic foraminiferal shell yield parallel increases along traverses that coincide with muricae blades on the chamber wall. The parallel d18O and Mg/Ca increases indicate a diagenetic origin for the blades, but their d18O value (-0.5 per mil PDB) is lower than that of crystallites suggesting that these two phases of diagenetic carbonate formed at different times. Finally, we posit that elevated levels of early diagenesis acted in concert with sediment mixing and carbonate dissolution to attenuate the d18O decrease signaling PETM warming in "whole-shell" records published for Site 865.

Table 2. Performance summary of K-based sorbents capturing CO2

This article reviews the progress made in CO2 capture, storage, and utilization in Chinese Academy of Sciences (CAS). New concepts such as adsorption using dry regenerable solid sorbents as well as functional ionic liquids (ILs) for CO2 capture are thoroughly discussed. Carbon sequestration, such as geological sequestration, mineral carbonation and ocean storage are also covered. The utilization of CO2 as a raw material in the synthesis of chemicals and liquid energy carriers which offers a way to mitigate the increasing CO2 buildup is introduced.