Percentages of sand-sized material and biogenic components in sediment core GIK12392-1

The paleo-oceanography of the southeastern North Atlantic Ocean during the last 150,000 yr has been studied using biogenous and terrigenous components of hemipelagic sediments sampled close to the northwest African continental margin. Variations of oxygen isotope ratios in shells of benthic calcareous foraminifers in two cores allow the assignment of absolute ages to these cores (in the best case at 1000 yr increments). The uncorrected bulk sedimentation rates of the longest core range from 3.4 to 7.6 cm/ 1000 yr during Interglacial conditions, and from 6.5 to 9.9 cm/1000 yr during Glacial conditions; all other cores have given results of the same order of magnitude, but with generally increasing values towards the continental edge. The distribution of sediment components allow us to make inferences about paleo-oceanographic changes in this region. Frequencies of biogenic components from benthic organisms, oxygen isotope ratios measured in benthic calcareous foraminiferal shells, the total carbonate contents of the sediment and distributions of biogenic components from planktonic organisms often fluctuate in concert. However, all fluctuations which can be attributed to changes of the bottom water masses (North Atlantic Deep Water) seem to precede by several thousand years those which can be linked to changes of the surface water mass distributions or to changes of the climate over the neighboring land masses. Late Quaternary planktonic foraminiferal assemblages in the cores from the northwest African continental margin can be defined satisfactorily in the way that distributions of assemblages found in sediment surface samples from the northeast Atlantic Ocean have been explained. The distributions of assemblages in the northwest African cores can also be used to estimate past sea surface temperatures and salinities. The downcore record of these estimates reveals two warm periods during the last 150,000 yr, the lower one corresponding to the oxygen isotope stage 5 e (equivalent to the Eemian proper in Europe), the upper one to the younger half of the Holocene. Winter surface water temperatures during oxygen isotope stages 6, 4, 3, and 2 are remarkably constant in most cores, while summer sea surface temperatures during stage 3 reach values comparable to those of the warm periods during the Late Holocene and Eemian. Estimated winter sea surface temperatures range from > 16 °C to < 11°C, the summer sea surface temperatures from > 22 °C to < 15 °C during the last 150,000 yr. Estimates of the winter sea surface salinities fluctuate between 36.6? and 35.5?, the higher values being restricted to the warm periods since the penultimate Glacial. Estimates for sea surface temperatures and salinities for two cores from the center of today's coastal upwelling region show less pronounced fluctuations than the record of the open ocean cores in the case of the station 12379 off Cape Barbas, more pronounced in the case of station 12328 off Cape Blanc. Seasonal differences between winter and summer sea surface temperatures derived from the estimated temperatures are today more pronounced in the boundary region of the ocean to the continent than further away from the continent. The differences are generally higher during warm climatic periods of the last 150,000 yr than during cooler ones. The abundance of terrigenous grains in the coarse fractions generally decreases with increasing distance from the continental edge, and also from south to north. The dominant portion of the terrigenous detritus is carried out into the ocean during the relatively cool climatic periods (stage 6, 4, later part of stage 3, stage 2 and oldest part of stage 1). The enhanced precision of dating combined with the stratigraphic resolution of these high deposition rate cores make it clear that the peaks of the terrigenous input off this part of the northwest African continental margin occur simultaneously with times of rapid sea level fluctuations resulting from large volume changes of the large Glacial ice sheets.

Mineral provinces and material provenance of the surficial sediments near the Zhongsha Islands in the South China Sea

Characteristics and distribution patterns of elastic minerals (0.063 similar to 0.125 mm) in bottom sediments represent a significant indicator for the identification of the origin of sediment. One hundred and fourteen surface sediment samples, which were collected from the area near the Zhongsha Islands in the South China Sea, were analysed to identify the mineral suites and their distributions in the study area. The area can be divided into three mineral provinces: ( I) a province of biogenic minerals, which mainly originate from the Zhongsha Atoll; ( H) a province of volcanogenic minerals, which are mainly derived from local basaltic seamounts and small-scale volcanoes that are probably erupting, with some influences from the island-are volcanic region around the South China Sea; and (II) a mixed mineral province whose material source includes biogenic minerals, volcanogenic minerals and terrigenous minerals; the last province can be subdivided into a mixed mineral sub-province of the northeastern part of the study area, in which terrigenous minerals are mainly derived from China's Mainland and do not exceed 17 degrees N, and a mixed mineral sub-province of the southeastern part of the study area, in which terrigenous minerals are derived from Kalimantan and Indochina Peninsula and might be further transported into the deep sea basin through submarine canyons.

Rainforest Aerosols as Biogenic Nuclei of Clouds and Precipitation in the Amazon

The Amazon is one of the few continental regions where atmospheric aerosol particles and their effects on climate are not dominated by anthropogenic sources. During the wet season, the ambient conditions approach those of the pristine pre-industrial era. We show that the fine submicrometer particles accounting for most cloud condensation nuclei are predominantly composed of secondary organic material formed by oxidation of gaseous biogenic precursors. Supermicrometer particles, which are relevant as ice nuclei, consist mostly of primary biological material directly released from rainforest biota. The Amazon Basin appears to be a biogeochemical reactor, in which the biosphere and atmospheric photochemistry produce nuclei for clouds and precipitation sustaining the hydrological cycle. The prevailing regime of aerosol-cloud interactions in this natural environment is distinctly different from polluted regions.

Stereochemical transfer to atmospheric aerosol particles accompanying the oxidation of biogenic volatile organic compounds

Asymmetric emission profiles of the stereoisomers of plant-derived volatile organic compounds vary with season, geography, plant type, and stress factors. After oxidation of these compounds in the atmosphere, the low-vapor pressure products ultimately contribute strongly to the particle-phase material of the atmosphere. In order to explore the possibility of stereochemical transfer to atmospheric aerosol particles during the oxidation of biogenic volatile organic compounds, second-order coherent vibrational spectra were recorded of the particle-phase organic material produced by the oxidation of different stereoisomeric mixes of alpha-pinene. The spectra show that the stereochemical configurations are not scrambled but instead are transferred from the gas-phase molecular precursors to the particle-phase molecules. The spectra also show that oligomers formed in the particle phase have a handed superstructure that depends strongly and nonlinearly on the initial stereochemical composition of the precursors. Because the stereochemical mix of the precursors for a material can influence the physical and chemical properties of that material, our findings suggest that chirality is also important for such properties of plant-derived aerosol particles. Citation: Ebben, C. J., S. R. Zorn, S.-B. Lee, P. Artaxo, S. T. Martin, and F. M. Geiger (2011), Stereochemical transfer to atmospheric aerosol particles accompanying the oxidation of biogenic volatile organic compounds, Geophys. Res. Lett., 38, L16807, doi: 10.1029/2011GL048599.

Mass spectral characterization of submicron biogenic organic particles in the Amazon Basin

Submicron atmospheric particles in the Amazon Basin were characterized by a high-resolution aerosol mass spectrometer during the wet season of 2008. Patterns in the mass spectra closely resembled those of secondary-organic-aerosol (SOA) particles formed in environmental chambers from biogenic precursor gases. In contrast, mass spectral indicators of primary biological aerosol particles (PBAPs) were insignificant, suggesting that PBAPs contributed negligibly to the submicron fraction of particles during the period of study. For 40% of the measurement periods, the mass spectra indicate that in-Basin biogenic SOA production was the dominant source of the submicron mass fraction, contrasted to other periods (30%) during which out-of-Basin organic-carbon sources were significant on top of the baseline in-Basin processes. The in-Basin periods had an average organic-particle loading of 0.6 mu g m(-3) and an average elemental oxygen-to-carbon (O:C) ratio of 0.42, compared to 0.9 mu g m(-3) and 0.49, respectively, during periods of out-of-Basin influence. On the basis of the data, we conclude that most of the organic material composing submicron particles over the Basin derived from biogenic SOA production, a finding that is consistent with microscopy observations made in a concurrent study. This source was augmented during some periods by aged organic material delivered by long-range transport. Citation: Chen, Q., et al. (2009), Mass spectral characterization of submicron biogenic organic particles in the Amazon Basin, Geophys. Res. Lett., 36, L20806, doi: 10.1029/2009GL039880.

Relative roles of biogenic emissions and Saharan dust as ice nuclei in the Amazon basin

Some aerosol particles, known as ice nuclei, can initiate ice formation in clouds, thereby influencing precipitation, cloud dynamics and the amount of incoming and outgoing solar radiation. In the absence of biomass burning, aerosol mass concentrations in the Amazon basin are low(1). Tropical forests emit primary biological particles directly into the atmosphere; secondary organic aerosols form from the emission and oxidation of biogenic gases(2). In addition, particles derived from biomass burning in central Africa, marine aerosols, and windblown dust from North Africa(3-5) often reach the central part of the Amazon basin during the wet season. The contribution of these aerosol sources to ice nucleation in the region is uncertain. Here we present observations of the concentration and elemental composition of ice nuclei in the Amazon basin during the wet season. Using transmission electron microscopy combined with energy-dispersive X-ray spectroscopy, we show that ice nuclei are primarily composed of carbonaceous material and dust. We show that biological particles dominate the carbonaceous fraction, whereas import of Saharan dust explains the intermittent appearance of dust-containing nuclei. We conclude that ice-nucleus concentration and abundance can be explained almost entirely by local emissions of biological particles supplemented by import of Saharan dust. Using a simple model, we tentatively suggest that the contribution of local biological particles to ice nucleation is increased at higher atmospheric temperatures, whereas the contribution of dust particles is increased at lower temperatures.

Biogenic emission of halocarbons

Within this doctoral thesis, biogenic emissions of several globally relevant halocarbons (methyl chloride, methyl bromide, methyl iodide, dibromomethane, chloroform and bromoform) have been investigated in different environments. An airborne study was focused on the tropical rainforest ecosystem, while shipborne measurements investigated naturally occurring oceanic plankton blooms. Laboratory experiments using dried plant material were made to elucidate abiotic production mechanisms occurring in organic matter. Airborne measurements over the tropical rainforest of Suriname and French Guyana (3 - 6 °N, 51 - 59 °W) revealed net fluxes of 9.5 (± 3.8 2σ) µg m-2 h-1 methyl chloride and 0.35 (± 0.15 2σ) µg m-2 h-1 chloroform emitted in the long dry season (October) 2005. An extrapolation of these numbers to all tropical forests helped to narrow down the range of the recently discovered and poorly quantified methyl chloride source from tropical ecosystems. The value for methyl chloride obtained (1.5 (± 0.6 2σ) Tg yr-1) affirms that the contribution of the tropical forest ecosystem is the major source in the global budget of methyl chloride. The extrapolated global net chloroform flux from tropical forests (56 (± 23 2σ) Gg yr-1) is of minor importance (5 - 10 %) compared to the global sources. A source of methyl bromide from this region could not be verified. The abiotic formation of methyl chloride and methyl bromide from dead plant material was tested in a laboratory study. The release from plant tissue representative of grassland, deciduous forest, agricultural areas and coastal salt marshes (hay, ash, tomato and saltwort) has been monitored. Incubations at different temperatures (25 - 50 °C) revealed significant emissions even at ambient temperature, and that the emissions increased exponentially with temperature. The strength of the emission was found to be additionally dependent on the availability of halide and the methoxyl group within the plant tissue. However, high water content in the plant material was found to inhibit methyl halide emissions. The abiotic nature of the reaction yielding methyl halides was confirmed by its high activation energy calculated via Arrhenius plots. Shipborne measurements of the atmospheric mixing ratios of methyl chloride, methyl bromide, methyl iodide, dibromomethane and bromoform have been conducted along a South Atlantic transect from the 27.01. - 05.02.2007 to characterize halocarbon emissions from a large-scale natural algae bloom encountered off the coast of Argentina. Mixing ratios of methyl chloride and methyl bromide were not significantly affected by the occurrence of the phytoplankton bloom. Emissions of methyl iodide, dibromomethane and bromoform showed pronounced mixing ratio variations, triggered by phytoplankton abundance. Methyl iodide was strongly correlated with dimethyl sulfide throughout the sampled region. A new technique combining satellite derived biomass marker (chlorophyll a) data with back trajectory analysis was successfully used to attribute variations in mixing ratios to air masses, which recently passed over areas of enhanced biological production.

Development and application of an analytical method for the determination of total atmospheric biogenic non-methane organic carbon

Ein wesentlicher Anteil an organischem Kohlenstoff, der in der Atmosphäre vorhanden ist, wird als leichtflüchtige organische Verbindungen gefunden. Diese werden überwiegend durch die Biosphäre freigesetzt. Solche biogenen Emissionen haben einen großen Einfluss auf die chemischen und physikalischen Eigenschaften der Atmosphäre, indem sie zur Bildung von bodennahem Ozon und sekundären organischen Aerosolen beitragen. Um die Bildung von bodennahem Ozon und von sekundären organischen Aerosolen besser zu verstehen, ist die technische Fähigkeit zur genauen Messung der Summe dieser flüchtigen organischen Substanzen notwendig. Häufig verwendete Methoden sind nur auf den Nachweis von spezifischen Nicht-Methan-Kohlenwasserstoffverbindungen fokussiert. Die Summe dieser Einzelverbindungen könnte gegebenenfalls aber nur eine Untergrenze an atmosphärischen organischen Kohlenstoffkonzentrationen darstellen, da die verfügbaren Methoden nicht in der Lage sind, alle organischen Verbindungen in der Atmosphäre zu analysieren. Einige Studien sind bekannt, die sich mit der Gesamtkohlenstoffbestimmung von Nicht-Methan-Kohlenwasserstoffverbindung in Luft beschäftigt haben, aber Messungen des gesamten organischen Nicht-Methan-Verbindungsaustauschs zwischen Vegetation und Atmosphäre fehlen. Daher untersuchten wir die Gesamtkohlenstoffbestimmung organische Nicht-Methan-Verbindungen aus biogenen Quellen. Die Bestimmung des organischen Gesamtkohlenstoffs wurde durch Sammeln und Anreichern dieser Verbindungen auf einem festen Adsorptionsmaterial realisiert. Dieser erste Schritt war notwendig, um die stabilen Gase CO, CO2 und CH4 von der organischen Kohlenstofffraktion zu trennen. Die organischen Verbindungen wurden thermisch desorbiert und zu CO2 oxidiert. Das aus der Oxidation entstandene CO2 wurde auf einer weiteren Anreicherungseinheit gesammelt und durch thermische Desorption und anschließende Detektion mit einem Infrarot-Gasanalysator analysiert. Als große Schwierigkeiten identifizierten wir (i) die Abtrennung von CO2 aus der Umgebungsluft von der organischen Kohlenstoffverbindungsfaktion während der Anreicherung sowie (ii) die Widerfindungsraten der verschiedenen Nicht-Methan-Kohlenwasserstoff-verbindungen vom Adsorptionsmaterial, (iii) die Wahl des Katalysators sowie (iiii) auftretende Interferenzen am Detektor des Gesamtkohlenstoffanalysators. Die Wahl eines Pt-Rd Drahts als Katalysator führte zu einem bedeutenden Fortschritt in Bezug auf die korrekte Ermittlung des CO2-Hintergrund-Signals. Dies war notwendig, da CO2 auch in geringen Mengen auf der Adsorptionseinheit während der Anreicherung der leichtflüchtigen organischen Substanzen gesammelt wurde. Katalytische Materialien mit hohen Oberflächen stellten sich als unbrauchbar für diese Anwendung heraus, weil trotz hoher Temperaturen eine CO2-Aufnahme und eine spätere Abgabe durch das Katalysatormaterial beobachtet werden konnte. Die Methode wurde mit verschiedenen leichtflüchtigen organischen Einzelsubstanzen sowie in zwei Pflanzenkammer-Experimenten mit einer Auswahl an VOC-Spezies getestet, die von unterschiedlichen Pflanzen emittiert wurden. Die Pflanzenkammer-messungen wurden durch GC-MS und PTR-MS Messungen begleitet. Außerdem wurden Kalibrationstests mit verschiedenen Einzelsubstanzen aus Permeations-/Diffusionsquellen durchgeführt. Der Gesamtkohlenstoffanalysator konnte den tageszeitlichen Verlauf der Pflanzenemissionen bestätigen. Allerdings konnten Abweichungen für die Mischungsverhältnisse des organischen Gesamtkohlenstoffs von bis zu 50% im Vergleich zu den begleitenden Standardmethoden beobachtet werden.

Microscopic and spectroscopic analysis of biogenic aerosols

Aerosol particles are important actors in the Earth’s atmosphere and climate system. They scatter and absorb sunlight, serve as nuclei for water droplets and ice crystals in clouds and precipitation, and are a subject of concern for public health. Atmospheric aerosols originate from both natural and anthropogenic sources, and emissions resulting from human activities have the potential to influence the hydrological cycle and climate. An assessment of the extent and impacts of this human force requires a sound understanding of the natural aerosol background. This dissertation addresses the composition, properties, and atmospheric cycling of biogenic aerosol particles, which represent a major fraction of the natural aerosol burden. The main focal points are: (i) Studies of the autofluo-rescence of primary biological aerosol particles (PBAP) and its application in ambient measure-ments, and (ii) X-ray microscopic and spectroscopic investigations of biogenic secondary organic aerosols (SOA) from the Amazonian rainforest.rnAutofluorescence of biological material has received increasing attention in atmospheric science because it allows real-time monitoring of PBAP in ambient air, however it is associated with high uncertainty. This work aims at reducing the uncertainty through a comprehensive characterization of the autofluorescence properties of relevant biological materials. Fluorescence spectroscopy and microscopy were applied to analyze the fluorescence signatures of pure biological fluorophores, potential non-biological interferences, and various types of reference PBAP. Characteristic features and fingerprint patterns were found and provide support for the operation, interpretation, and further development of PBAP autofluorescence measurements. Online fluorescence detection and offline fluorescence microscopy were jointly applied in a comprehensive bioaerosol field measurement campaign that provided unprecedented insights into PBAP-linked biosphere-atmosphere interactions in a North-American semi-arid forest environment. Rain showers were found to trigger massive bursts of PBAP, including high concentrations of biological ice nucleators that may promote further precipitation and can be regarded as part of a bioprecipitation feedback cycle in the climate system. rnIn the pristine tropical rainforest air of the Amazon, most cloud and fog droplets form on bio-genic SOA particles, but the composition, morphology, mixing state and origin of these particles is hardly known. X-ray microscopy and spectroscopy (STXM-NEXAFS) revealed distinctly different types of secondary organic matter (carboxyl- vs. hydroxy-rich) with internal structures that indicate a strong influence of phase segregation, cloud and fog processing on SOA formation, and aging. In addition, nanometer-sized potassium-rich particles emitted by microorganisms and vegetation were found to act as seeds for the condensation of SOA. Thus, the influence of forest biota on the atmospheric abundance of cloud condensation nuclei appears to be more direct than previously assumed. Overall, the results of this dissertation suggest that biogenic aerosols, clouds and precipitation are indeed tightly coupled through a bioprecipitation cycle, and that advanced microscopic and spectroscopic techniques can provide detailed insights into these mechanisms.rn

Radiocarbon, isotope, biogenic, and 230Th measurements for sediment core RC10-196

The subarctic North Pacific Ocean holds a large CO2 reservoir that is currently isolated from the atmosphere by a low-salinity layer. It has recently been hypothesized that the reorganization of these high-CO2 waters may have played a crucial role in the degassing of carbon dioxide to the atmosphere during the last deglaciation. This reorganization would leave some imprint on paleo-productivity records. Here we present 230Th-normalized biogenic fluxes from an intermediate depth sediment core in the Northwest Pacific (RC10-196, 54.7°N, 177.1°E, 1007 m) and place them within the context of a synthesis of previously-published biogenic flux data from 49 deep-sea cores north of 20°N, ranging from 420 to 3968 m water depth. The 230Th-normalized opal, carbonate, and organic carbon fluxes from RC10-196 peak approximately 13,000 calendar years BP during the Bølling/Allerød (B/A) period. Our data synthesis suggests that biogenic fluxes were in general lowest during the last glacial period, increased somewhat in the Northwest Pacific during Heinrich Event 1, and reached a maximum across the entire North Pacific during the B/A period. We evaluate several mechanisms as possible drivers of deglacial change in biogenic fluxes in the North Pacific, including changes in preservation, sediment focusing, sea ice extent, iron inputs, stratification, and circulation shifts initiated in the North Atlantic and North Pacific. Our analysis suggests that while micronutrient sources likely contributed to some of the observed changes, the heterogeneity in timing of glaciogenic retreat and sea level make these mechanisms unlikely causes of region-wide contemporaneous peaks in export production. We argue that paleo-observations are most consistent with ventilation increases in both the North Pacific (during H1) and North Atlantic (during B/A) being the primary drivers of increases in biogenic flux during the deglaciation, as respectively they were likely to bring nutrients to the surface via increased vertical mixing and shoaling of the global thermocline.

Composition and fluxes of sinking particulate material and bottom sediments in the northeast Black Sea in 1998-1999

For the first time deep-sea mooring stations with sediment traps were deployed in the northeast Black Sea. One sediment trap for long-term studies was located at Station 1 (44°15'N, 37°43'E, deployment depth 1800 m, depth 1900 m). The trap collected sinking sedimentary material from January to May 1998. Material collectors were changed every 15 days. Other stations with sediment traps for short-term studies (September-October 1999) were located on the shelf: Station 2 (44°16'N, 38°37'E, deployment depth 45 m, depth 50 m) and on the bottom of the canyon: Station 3 (44°16'N, 38°22'E, deployment depth 1145 m, depth 1150 m), Station 4 (44°11'N, 38°21'E, deployment depths 200, 1550, 1650 m, depth 1670 m). Collected material indicates that vertical particle fluxes are controlled by seasonal changes of in situ production and by dynamics of terrigenous matter input. Higher vertical particle flux of carbonate and biogenic silica was in spring due to bloom of plankton organisms. Maximum of coccolith bloom is in April-May. Bloom of diatoms begins in March. In winter and autumn lithogenic material dominates in total flux. Its amount strongly depends on storms and river run-off. Suspended particle material differs from surface shelf sediments by finer particles (mainly clay fraction) and high content of clay minerals and biogenic silica. This material may form lateral fluxes with higher concentration of particles transported along the bottom of deep-sea canyons from the shelf to the deep basin within the nepheloid layer. In winter such transportation of sedimentary material is more intensive due to active vertical circulation of water masses.

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.

Phosphorus components, CaCO3 and biogenic opal in sediments from ODP Leg 167 sites

The ocean history of reactive phosphorus (P) (i.e., dissolved P available to fuel oceanic primary productivity) is of interest because of the role of P as a biolimiting nutrient, and knowledge of P burial in marine sediments is key to testing hypotheses about temporal changes in P input or output fluxes. Our understanding of the history of the P cycle over the Cenozoic has increased substantially with temporal records of reactive P mass accumulation rates from open-ocean Pacific and Atlantic equatorial sites. However, questions about the relative importance of nutrient burial in ocean-margin sediments relative to burial in open-ocean sediments and about the extent of P remobilization in organic-rich, reducing environments characteristic of margin sediments remain unresolved. Nutrient burial in oceanic boundary current systems has been suggested to have a controlling role in oceanic nutrient budgets in certain time intervals (Vincent and Berger, 1985, doi:10.1029/GM032p0455), with higher sediment accumulation rates balancing the limited spatial extent of these sediments. Some investigators suggest that remobilization of P from reducing sediments in margin settings is a significant positive feedback to primary productivity (e.g., Van Cappellan and Ingall, 1994, doi:10.1029/94PA01455), whereas other results indicate that both P uptake and P release may occur in these settings depending on the balance of organic carbon and iron supply to the sediments and on the oxygenation of bottom waters (McManus et al., 1997, doi:10.1016/S0016-7037(97)00138-5). It is important to quantitatively understand the geochemistry of reactive P in margin sediments, where productivity and delivery of organic-rich material to the sediments in relatively shallow-water settings is often sufficient to promote anoxia in interstitial waters. To address these questions, we determined the P concentrations and geochemistry in sediment samples from eight sites drilled during Ocean Drilling Program (ODP) Leg 167, California margin (Sites 1010-1012, 1014, 1016-1017, and 1021-1022). These results are the first records of reactive P concentrations on long time scales-required for the calculation of P accumulation rates-for sediments from a highly productive eastern boundary current setting. In addition, we determined calcium carbonate contents and biogenic silica concentrations to define the environments of sedimentary production, burial, and diagenesis.

Composition of dissolved, particulate and sinking material in hydrothermal plumes above the TAG and Broken Spur hydrothermal fields

The paper reports data on distribution of dissolved (Mn, Zn, Cu, Pb, and Cd) and particulate (Fe, Mn, Zn, Cu, Pb, Ni, and Co) species of metals in hydrothermal plumes above the active TAG and Broken Spur hydrothermal fields (26° N and 29° N in the MAR rift valley, respectively). Sediment trap data on fluxes of hydrothermal sedimentary material in the areas indicate that (i) the predominant Zn source for metalliferous sediments at the TAG field is material precipitating from the neutrally buoyant plume, and (ii) the predominant source of Fe and Co is re-deposited ore material coming from the area of extensive settling of sulfides.