Characterization of insoluble organic matter in sediments at DSDP Site 87-582

Lipids, humic acids, and kerogens were isolated from Site 582 sediment cores. The amount of each organic fraction in the samples taken from 5.6 to 694 m sub-bottom is almost unrelated to depth of the sample. A study of the oxidation of organic matter by the alkaline KMnO4 method reveals that distribution of polymethylene chain lengths of the kerogens and humic acids in the marine sediments differ from those in lacustrine sediments. The order of abundance of these chains in the sediments is: kerogens, 52-66% of total methylene chains; humic acids, 25-33%; and lipids, 8-16%. The results suggest that polyunsaturated fatty acids (>=4 double bonds) may be important in the formation of polymethylene chains of kerogens and humic acids in marine sediments.

Miocene through Pleistocene dinoflagellates from ODP Site 170-1039

Palynological data from offshore Costa Rica, allow us to investigate the relationship between dinoflagellate cyst assemblages and changes in regional oceanic primary productivity. From Miocene to Pleistocene, productivity at ODP Site 1039 was influenced by tectonic drift, as Site 1039 approached the continent, from the Equator to its current position at ~10°N. In addition, dinoflagellate abundance is modulated by regional productivity events, which modified primary productivity, as also indicated by available data on calcareous nannofossils, diatoms, TOC, and CaCO3 content. Five palynomorph intervals are defined. The early-late Miocene one, dominated by Batiacasphaera, represents relatively stable, productive oceanic conditions before the closure of the Indonesian and Panama Seaways. The late Miocene decrease in palynomorph recovery is related to the Carbonate Crash Event. The high abundance and diversity of the assemblages at the end of the late Miocene to early Pliocene indicate increased productivity related to the Global Biogenic Bloom, and a change in dominance from Batiacasphaera to Impagidinium to Nematosphaeropsis. The low abundance of the late Pliocene interval is related to El Niño-like conditions, and there is another change related to the disappearance of Batiacasphaera and dominance of Impagidinium, Nematosphaeropsis, and Operculodinium. The abundant Pleistocene assemblages represent increased marine productivity, and a high influx of continental palynomorphs and bissacate pollen, associated with the proximity of the Costa Rica Dome. Pleistocene dinoflagellates are characterized by Spiniferites and Selenopemphix, together with rare Impagidinium and Nematosphaeropsis.

Lignin and chemical elements in the surface layer of bottom sediments from the Kandalaksha Bay of the White Sea

Chemical composition of the upper layer of sediments (0-1 cm) in the Kolvits and Knazhaya inlets, and also in the deep-water part of the Kandalaksha Bay is considered. It is shown that silts are richer in Fe, TOC, and heavy metals, than sands. The highest concentration of these elements is found in sediments under mixing zones of riverine and sea waters. Correlations of P, Zn, Cd, and Cu with iron are high, and correlations of Pb and Cu with organic carbon are also high. Very high concentration of Pb in the Kandalaksha Bay indicate technogenic pollution of sediments. Lignin makes significant contribution to formation of organic matter in the sediments. Composition of lignin in bottom sediments of the Kandalaksha Bay is defined by composition of lignin in soils and aerosols. Vanillin and syringyl structures prevail in molecular composition of lignin in bottom sediments. Their sources are coniferous vegetations, soils, and mosses. Ratios of certain types of phenol compounds indicate pollution of the upper layer of sediments by technogenic lignin. Lead and copper correlate well with this technogenic lignin.

Dioxin-like and non-dioxin like contaminants in the herring Clupea harengus in the Norwegian and North Sea

The Norwegian spring spawning (NSS) herring is an ecologically important fish stock in the Norwegian Sea, and with a catch volume exceeding one million tons a year it is also economically important and a valuable food source. In order to provide a baseline of the levels of contaminants in this fish stock, the levels of organohalogen compounds were determined in 800 individual herring sampled at 29 positions in the Norwegian Sea and off the coast of Norway. Due to seasonal migration, the herring were sampled where they were located during the different seasons. Concentrations of dioxins and dioxin-like PCBs, non-dioxin-like PCBs (PCB7) and PBDEs were determined in fillet samples of individual herring, and found to be relatively low, with means (min-max) of 0.77 (0.24-3.5) ngTEQ/kg wet weight (ww), 5.0 (1.4-24) µg/kg ww and 0.47 (0.091-3.1) µg/kg ww, respectively. The concentrations varied throughout the year due to the feeding- and spawning cycle: Starved, pre-spawning herring caught off the Norwegian coast in January-February had the highest levels and those caught in the Norwegian Sea in April-June, after further starvation and spawning, had the lowest levels. These results show that the concentrations of organohalogen compounds in NSS herring are relatively low and closely tied to their physiological condition, and that in the future regular monitoring of NSS herring should be made in the spawning areas off the Norwegian coast in late winter.

Dinoflagellate cysts and pollen distribution of marine surface sediments off West Africa

An organic-walled dinoflagellate cyst analysis was carried out on 53 surface sediment samples from West Africa (17-6°N) to obtain insight in the relationship between their spatial distribution and hydrological conditions in the upper water column as well as marine productivity in the study area. Multivariate analysis of the dinoflagellate cyst relative abundances and environmental parameters of the water column shows that sea-surface temperature, salinity, marine productivity and bottom water oxygen are the factors that relate significantly to the distribution patterns of individual species in the region. The composition of cyst assemblages and dinoflagellate cyst concentrations allows the identification of four hydrographic regimes; 1) the northern regime between 17 and 14°N characterized by high productivity associated with seasonal coastal upwelling, 2) the southern regime between 12 and 6°N associated with high-nutrient waters influenced by river discharge 3) the intermediate regime between 14 and 12°N influenced mainly by seasonal coastal upwelling additionally associated with fluvial input of terrestrial nutrients and 4) the offshore regime characterized by low chlorophyll-a concentrations in upper waters and high bottom water oxygen concentrations. Our data show that cysts of Polykrikos kofoidii, Selenopemphix quanta, Dubridinium spp., Echinidinium species, cysts of Protoperidinium monospinum and Spiniferites pachydermus are the best proxies to reconstruct the boundary between the NE trade winds and the monsoon winds in the subtropical eastern Atlantic Ocean. The association of Bitectatodinium spongium, Lejeunecysta oliva, Quinquecuspis concreta, Selenopemphix nephroides, Trinovantedinium applanatum can be used to reconstruct past river outflow variations within this region.

Sediments in arctic sea ice - entrainment, characterization and quantification

Sediments in Arctic sea ice are important for erosion and redistribution and consequently a factor for the sediment budget of the Arctic Ocean. The processes leading to the incorporation of sediments into the ice are not understood in detail yet. In the present study, experiments on the incorporation of sediments were therefore conducted in ice tanks of The Hamburg Ship Model Basin (HSVA) in winter 1996/1997, These experiments showed that on average 75 % of the artificial sea-ice sediments were located in the brine-channel system. The sediments were scavenged from the water column by frazil ice. Sediments functioning as a nucleus for the formation of frazil ice were less important for the incorporation. Filtration in grease ice during relatively calm hydrodynamic conditions was probably an effective process to enrich sediments in the ice. Wave fields did not play an important role for the incorporation of sediments into the artificial sea ice. During the expedition TRANSDRIFT III (TDIII, October 1995), different types of natural, newly-formed sea ice (grease ice, nilas and young ice) were sampled in the inner Laptev Sea at the time of freeze-up. The incorporation of sediments took place during calm meteorological conditions then. The characteristics of the clay mineral assemblages of these sedirnents served as references for sea-ice sediments which were sampled from first-year drift ice in the outer Laptev Sea and the adjacent Arctic Ocean during the POLARSTERN expedition ARK-XI/1 (July-September 1995). Based on the clay mineral assemblages, probable incorporation areas for the sedirnents in first-year drift ice could be statistically reconstructed in the inner Laptev Sea (eastern, central, and Western Laptev Sea) as well as in adjacent regions. Comparing the amounts of particulate organic carbon (POC) in sea-ice sediments and in surface sediments from the shelves of potential incorporation areas often reveals higher values in sea-ice sediments (TDIII: 3.6 %DM; ARK-XI/1: 2.3 %DM). This enrichment of POC is probably due to the incorporation process into the sea ice, as could be deducted from maceral analysis and Rock-Eval pyrolysis. Both methods were applied in the present study to particulate organic material (POM) from sea-ice sediments for the first time. It was shown that the POM of the sea-ice sediments from the Laptev Sea and the adjacent Arctic Ocean was dominated by reworked, strongly fragmented, allochthonous (terrigenous) material. This terrigenous component accounted for more than 75 % of all counted macerals. The autochthonous (marine) component was also strongly fragmented, and higher in the sediments from newly-formed sea ice (24 % of all counted macerals) as compared to first-year drift ice (17 % of all counted macerals). Average hydroge indices confirmed this pattern and were in the transition zone between kerogen types II and III (TDIII: 275 mg KW/g POC; ARK-XI/1: 200 mg KW/g POC). The sediment loads quantified in natural sea ice (TDIII: 33.6 mg/l, ARK-XI/1: 49.0 mg/l) indicated that sea-ice sediments are an important factor for the sediment budget in the Laptev Sea. In particular during the incorporation phase in autumn and early winter, about 12 % of the sediment load imported annually by rivers into the Laptev Sea can be incorporated into sea ice and redistributed during calm meteorological conditions. Single entrainment events can incorporate about 35 % of the river input into the sea ice (ca. 9 x 10**6 t) and export it via the Transpolar Drift from the Eurasian shelf to the Fram Strait.

Distribution of organic-walled dinoflagellate cysts in surface sediments of the Benguela upwelling system

To obtain insight in the relationship between the spatial distribution of organic-walled dinoflagellate cysts (dinocysts) and local environmental conditions, fifty-eight surface sediment samples from the coastal shelf off SW Africa were investigated on their dinocyst content with special focus on the two main river systems and the active upwelling that characterise this region. To avoid possible overprint by species-selective preservation, samples have been selected mainly from shelf sites where high sedimentation rates and/or low bottom water oxygen concentrations prevail. Multivariate ordination analyses have been carried out to investigate the relationship between the distribution patterns of individual species to environmental parameters of the upper water column and sediment transport processes. The main oceanographical variables at the surface (temperature, salinity, nutrients chlorophyll-a) in the region show onshore-offshore gradients. This pattern is reflected in the dinocyst associations with high relative abundances of heterotrophic dinocyst species in neritic regions characterised by high chlorophyll-aand low salinity conditions in surface waters. Phototrophic dinocyst species, notably Operculodinium centrocarpum, dominate in the more oceanic area. Differences in the distribution of phototrophic dinocyst species can be related to sea surface salinity and sea surface temperature gradients and to a lesser extent to chlorophyll-a concentrations. Apart from longitudinal gradients the dinocyst distribution clearly reflects regional environmental features. Six groups of species can be distinguished, characteristic for (1) coastal regions (cysts of Polykrikos kofoidii and Selenopemphix quanta), (2) the vicinity of active upwelling (Brigantedinium spp., Echinidinium aculeatum, Echinidinium spp. and Echinidinium transparantum), (3) river mouths (Lejeunecysta oliva, cysts of Protoperidinium americanum, Selenopemphix nephroides and Votadinium calvum), (4) slope and open ocean sediments (Dalella chathamense, Impagidinium patulum and Operculodinium centrocarpum, (5) the southern Benguela region (south of 24°S) (Spiniferites ramosus) and (6) the northern Benguela region (north of 24°S) (Nematosphaeropsis labyrinthus and Pyxidinopsis reticulata). No indication of overprint of the palaeo-ecological signal by lateral transport of allochthonous species could be observed.

Low-temperature experiments of sediment core GeoB6229-6 at the South American continental margin off the Rio de la Plata estuary

With various low-temperature experiments performed on magnetic mineral extracts of marine sedimentary deposits from the Argentine continental slope near the Rio de la Plata estuary, a so far unreported style of partial magnetic self-reversal has been detected. In these sediments the sulphate-methane transition (SMT) zone is situated at depths between 4 and 8 m, where reductive diagenesis severely alters the magnetic mineral assemblage. Throughout the sediment column magnetite and ilmenite are present together with titanomagnetite and titanohematite of varying compositions. In the SMT zone (titano-)magnetite only occurs as inclusions in a siliceous matrix and as intergrowths with lamellar ilmenite and titanium-rich titanohematite, originating from high temperature deuteric oxidation within the volcanic host rocks. These abundant structures were visualized by scanning electron microscopy and analysed by energy dispersive spectroscopy. Warming of field-cooled and zero-field-cooled low-temperature saturation remanence displays magnetic phase transitions of titanium-rich titanohematite below 50 K and the Verwey transition of magnetite. A prominent irreversible decline characterizes zero-field cooling of room temperature saturation remanence. It typically sets out at ~210 K and is most clearly developed in the lower part of the SMT zone, where low-temperature hysteresis measurements identified ~210 K as the blocking temperature range of a titanohematite phase with a Curie temperature of around 240 K. The mechanism responsible for the marked loss of remanence is, therefore, sought in partial magnetic self-reversal by magnetostatic interaction of (titano-)magnetite and titanohematite. When titanohematite becomes ferrimagnetic upon cooling, its spontaneous magnetic moments order antiparallel to the (titano-)magnetite remanence causing an drastic initial decrease of global magnetization. The loss of remanence during subsequent further cooling appears to result from two combined effects (1) magnetic interaction between the two phases by which the (titano-)magnetite domain structure is substantially modified and (2) low-temperature demagnetization of (titano-)magnetite due to decreasing magnetocrystalline anisotropy. The depletion of titanomagnetite and superior preservation of titanohematite is characteristic for strongly reducing sedimentary environments. Typical residuals of magnetic mineral assemblages derived from basaltic volcanics will be intergrowths of titanohematite lamellae with titanomagnetite relics. Low-temperature remanence cycling is, therefore, proposed as a diagnostic method to magnetically characterize such alteration (palaeo-)environments.

Geochemistry and kinetic models od Cretaceous samples

The source rock potential of Cretaceous organic rich whole rock samples from deep sea drilling project (DSDP) wells offshore southwestern Africa was investigated using bulk and quantitative pyrolysis techniques. The sample material was taken from organic rich intervals of Aptian, Albian and Turonian aged core samples from DSDP site 364 offshore Angola, DSDP well 530A north of the Walvis Ridge offshore Namibia, and DSDP well 361 offshore South Africa. The analytical program included TOC, Rock-Eval, pyrolysis GC, bulk kinetics and micro-scale sealed vessel pyrolysis (MSSV) experiments. The results were used to determine differences in the source rock petroleum type organofacies, petroleum composition, gas/oil ratio (GOR) and pressure-volume-temperature (PVT) behavior of hydrocarbons generated from these black shales for petroleum system modeling purposes. The investigated Aptian and Albian organic rich shales proved to contain excellent quality marine kerogens. The highest source rock potential was identified in sapropelic shales in DSDP well 364, containing very homogeneous Type II and organic sulfur rich Type IIS kerogen. They generate P-N-A low wax oils and low GOR sulfur rich oils, whereas Type III kerogen rich silty sandstones of DSDP well 361 show a potential for gas/condensate generation. Bulk kinetic experiments on these samples indicate that the organic sulfur contents influence kerogen transformation rates, Type IIS kerogen being the least stable. South of the Walvis Ridge, the Turonian contains predominantly a Type III kerogen. North of the Walvis Ridge, the Turonian black shales contain Type II kerogen and have the potential to generate P-N-A low and high wax oils, the latter with a high GOR at high maturity. Our results provide the first compositional kinetic description of Cretaceous organic rich black shales, and demonstrate the excellent source rock potential, especially of the Aptian-aged source rock, that has been recognized in a number of the South Atlantic offshore basins.