Geochemical analysis of sediments from three coring sites in the Mediterranean

In a gravity core from the eastern Mediterranean Sea, a chemically and mineralogically distinct, 5.5-cm-thick layer is present above sapropel S-1 and overlain by hemipelagic marls. Calcite is completely absent in this exotic layer, dolomite is present only in small amounts, and the Cr concentrations are significantly enhanced. The layer was deposited primarily under reducing conditions, but the distributions of redox-sensitive elements show that a large part of the exotic layer is now oxidised by a downward-progressing oxidation front. Sediments from within the nearby anoxic, hypersaline Urania Basin are similar to those from the exotic layer, in particular in S-, C-, and O-isotope distributions of pyrite and dolomite, as well as increased Cr concentrations. Mud expulsion due to expansion of gas-rich mud is proposed to explain the presence of the exotic layer outside the Urania Basin. The deposition of an anoxic layer above S-1 shielded the sapropel from oxidation which resulted in the rare occurrence of a complete preservation of S-1 and provides the first minimum age for the start of anoxic mud accumulation in the Urania Basin.

Pore water (SO4, CH4, alkalinity, HS-, Ca, Sr, Mg, Ba) and solid phase (Ca, Sr, Mg, Ba) data measured in pockmark sediments of the Northern Congo Fan

This study focuses on the vertical distribution of authigenic carbonates (aragonite and high Mg-calcite) in the form of finely disseminated precipitates as well as massive carbonate concretions present in and above gas hydrate bearing sediments of the Northern Congo Fan. Analyses of Ca, Mg, Sr and Ba in pore water, bulk sediments and authigenic carbonates were carried out on gravity cores taken from three pockmark structures (Hydrate Hole, Black Hole and Worm Hole). In addition, a background core was retrieved from an area not influenced by fluid seepage. Pore water Sr/Ca and Mg/Ca ratios are used to reveal the current depths of carbonate formation as well as the mineralogy of the authigenic precipitates. The Sr/Ca and Mg/Ca ratios of bulk sediments and massive carbonate concretions were applied to infer the presence and depth distribution of authigenic aragonite and high Mg-calcite, based on the approach presented by Bayon et al. [Bayon et al. (2007). Sr/Ca and Mg/Ca ratios in Niger Delta sediments: Implications for authigenic carbonate genesis in cold seep environments. Marine Geology 241(1-4), 93-109, doi:10.1016/j.margeo.2007.03.007]. We show that the approach developed by Bayon et al. (2007) for sediments of cold seeps of the Niger Delta is also suitable to identify the mineralogy of authigenic carbonates in pockmark sediments of the Congo Deep-Sea Fan. We expand this approach by combining interstitial with solid phase Sr/Ca and Mg/Ca ratios, which demonstrate that high Mg-calcite is the predominant authigenic carbonate that currently forms at the sulfate/methane reaction zone (SMRZ). This is the first study which investigates both solid phase and pore water signatures typical for either aragonite or high Mg-calcite precipitation for the same sediment cores and thus is able to identify active and fossil carbonate precipitation events. At all investigated pockmark sites fossil horizons of the SMRZ were deduced from high Mg-calcite located above and below the current depths of the SMRZ. Additionally, aragonite enrichments typical for high seepage rates were detected close to the sediment surface at these sites. However, active precipitation of aragonite as indicated by pore water characteristics only occurs at the Black Hole site. Dissolved and solid phase Ba concentrations were used to estimate the time the SMRZ was fixed at the current depths of the diagenetic barite fronts. The combined pore water and solid phase elemental ratios (Mg/Ca, Sr/Ca) and Ba concentrations allow the reconstruction of past changes in methane seepage at the investigated pockmark sites. At the Hydrate Hole and Worm Hole sites the time of high methane seepage was estimated to have ceased at least 600 yr BP. In contrast, a more recent change from a high flux to a more dormant stage must have occurred at the Black Hole site as evidenced by active aragonite precipitation at the sediment surface and a lack of diagenetic Ba enrichments.

Alkenones and coccolithophorids in late Quaternary sediments from the Walvis Ridge

Sea surface temperatures (SSTs) derived from the alkenone UK'37) record of Quaternary sediments may be subject to bias if algae with different temperature sensitivities have contributed to the sedimentary alkenone record. The alkenone-derived SST records are usually based on a UK'37-temperature relationship which was measured in culture experiments using the coccolithophorid Emiliania huxleyi (F.G. Prahl, L.A. Muehlhausen and D.L. Zahnle, 1988. Further evaluation of long-chain alkenones as indicators of paleoceanographic conditions. Geochim. Cosmochim. Acta 52, 2303-2310). To assess possible effects of past species changes on the UK'37-temperature signal, we have analyzed long-chain alkenones and coccolithophorids in a late Quaternary sediment core from the Walvis Ridge and compared the results to SST estimates extracted from the d18O record of the planktonic foraminifer Globigerinoides ruber. Alkenones and isotopes were determined over the entire 400-kyr core record while the coccolithophorid study was confined to the last 200 kyr when the most pronounced changes in alkenone content occurred. Throughout oxygen-isotope stages 6 and 5, species of the genus Gephyrocapsa were the predominating coccolithophorids. E. huxleyi began to increase systematically in relative abundance since the stage 5/4 transition, became dominant over Gephyrocapsa spp. during stage 3 and reached the highest abundances in the Holocene. Carbon-normalized alkenone concentrations are inversely related to the relative abundances of E. huxleyi, and directly related to that of Gephyrocapsa spp., suggesting that species of this genus were the principal alkenone contributors to the sediments. Nevertheless, SST values obtained from the UK'37-temperature relationship for E. huxleyi compare favourably to the isotope-derived temperatures. The recently reported UK'37-temperature relationship for a single strain of Gephyrocapsa oceanica (J.K. Volkman. S.M. Barrett, S.I. Blackburn and E.L. Sikes, 1995. Alkenones in Gephyrocapsa oceanica: Implications for studies of paleoclimate. Geochim. Cosmochim. Acta 59, 513-520) produces unrealistically high SST values indicating that the temperature response of the examined strain is not typical for the genus Gephyrocapsa. This is supported by the C37:C38, alkenone ratios of the sediments which are comparable to average ratios reported for E. huxleyi, but significantly higher than for the G. oceanica strain. Most notably, the general accordance of the alkenone characteristics between sediments and E. huxleyi persists through stages 8 to 5 and even in times that predate the first appearance of this species (268 ka; H.R. Thierstein, K.R. Geitzenauer and B. Molfino, 1977. Global synchroneity of late Quaternary coccolith datum levels: Validation by oxygen isotopes. Geology 5, 400-404). Our results suggest that UK'37-temperature relationships based on E. huxleyi produce reasonable paleo-SST estimates even for late Quaternary periods when this species was scarce or absent because other alkenone-synthesizing algae, e.g. of the genus Gephyrocapsa.

Stable isotopic and carbonate cyclicity in deep sea sediments from different DSDP Holes

Oxygen and carbon isotopic variability of the dominant (<38 µm) carbonate fraction within bedded, organic-carbon rich Lower Cretaceous sediment intervals from various DSDP sites are closely correlated with preservational changes in the carbonates. Isotopic fluctuations are absent where carbonate contents vary little and where the carbonate fraction is dominated by biogenic phytoplankton remains. Within each of the studied intervals oxygen and carbon isotopic ratios become increasingly more negative in samples with carbonate contents higher than about 60% in which the proportion of diagenetic microcarbonate increases rapidly. Carbon isotopic ratios show a trend towards positive values in samples with carbonate contents of less than 40% and strong signs of dissolution. The taxonomic composition of nannofossil assemblages varies little within single intervals, despite significant differential diagenesis among individual beds; this points towards ecological stability of oceanic surface waters during the deposition of alternating beds. Bedding is, however, closely related to changing bioturbation intensity, indicating repeated fluctuations of the deep-water renewal rates and oxygen supply. Various microbial decomposition processes of organic matter leading to bed-specific differential carbonate diagenesis resulted in an amplification of primary bedding features and are considered responsible for most of the observed fluctuations in the stable isotopic ratios and carbonate contents.

Carbon and carbonate concentrations of recent and Pleistocene sediments of the Norwegian-Greenland Sea

Surface sediment samples from the Norwegian-Greenland Sea were investigated to reconstruct the spatial distribution of recent carbonate dissolution on the seafloor. Additionally, carbonate dissolution records of Ocean Drilling Program sites 985 and 987 are presented to outline the development of Pleistocene carbonate preservation. Today, well-preserved carbonate tests can be observed along the inflow of warm Atlantic surface water, extending as far as into the northernmost Norwegian-Greenland Sea. Increased dissolution is indicated along the continental margins and in the deepest parts of the Greenland Basin. Factors favoring carbonate preservation were found to be supersaturation of the water column with respect to calcium carbonate, high carbonate rain and probably excess alkalinity of bottom waters supplied by the arctic river discharge. Supralysoklinal dissolution is most important for recent carbonate dissolution in the Norwegian-Greenland Sea, whereas the deepest parts of the Greenland Basin reaches the calcite saturation horizon. Pleistocene dissolution records show some prominent peaks of extreme carbonate dissolution. During the Brunhes chron, carbonate dissolution maxima can be related to meltwater pulses, which probably inhibited deep-water formation in the Norwegian-Greenland Sea during deglaciation events. Long-term severe carbonate dissolution is evident during the late Matuyama chron. This can be probably related to low carbonate rain, due to a more eastwards located East Greenland Current and the nearly absence of the not yet polar adapted Neogloboquadrina pachyderma sin. during that period. Extreme dissolution events during the late Matuyama indicate strongly reduced deep-water formation.

Calcium carbonate contents and carbon and oxygen isotope compositions of bulk carbonate, ODP Leg 165 sediments

Two recently drilled Caribbean sites contain expanded sedimentary records of the late Paleocene thermal maximum, a dramatic global warming event that occurred at ca. 55 Ma. The records document significant environmental changes, including deep-water oxygen deficiency and a mass extinction of deep-sea fauna, intertwined with evidence for a major episode of explosive volcanism. We postulate that this volcanism initiated a reordering of ocean circulation that resulted in rapid global warming and dramatic changes in the Earth's environment.

Palynofacies investigation of Callovian sediments of DSDP Hole 79-534A

During the extension of Deep Sea Drilling Project (DSDP) Leg 76 a new and previously unpenetrated lithological unit composed mainly of claystones was cored above basalt basement at Site 534 in the Blake-Bahama Basin. The Callovian part of the new unit contains interbedded 'black shales' which were hitherto unexpected in this part of the section. This Paper presents a brief palynological examination of lithofacies-kerogen relationships in these sediments and shows that their organic content is almost entirely a function of the re-deposition of terrestial and marine organic matter versus the ambient redox conditions of the depositional environment. Allochthonous organic matter inputs are highest in the interbedded turbidites and decline progressively toward the pelagic black shales in which marine organic matter is comparatively well preserved. The significance of various kerogen and palynomorph indices are discussed. The study emphasizes the absolute necessity for sedimentologically-aware sampling in all palynological and geochemical work on lithologically heterogeneous sequences.

Composition of bottom sediments, rocks, and ores from the Tropical Atlantic

Geological features of some areas of the Tropical Atlantic (stratigraphy, tectonic structure, lithology, distribution of ore components in bottom sediments, petrography of bedrocks, etc.) are under consideration in the book. Regularities of concentration of trace elements in iron-manganese nodules, features of these nodules in bottom sediments, distribution of phosphorite nodules and other phosphorites have been studied. Much attention is paid to rocks of the ocean crust. A wide range of mineralization represented by magnetite, chromite, chalcopyrite, pyrite, pentlandite, and other minerals has been found.

Chemical and isotopic compositions of authigenic carbonates from bottom sediments of Northwest Pacific marginal seas

The paper presents data on authigenic carbonate distribution in Holocene - Upper Pleistocene deposits of the Okhotsk, Japan, East China, Philippine and South China Seas. Description of carbonate samples, their chemical and isotope compositions are given. Chemical analysis of the samples indicates that almost all authigenic carbonates are composed of calcite or magnesian calcite; and only in one case, of siderite. Oxygen isotopic composition (d18O) ranges from +37.7 to +26.1 per mil (SMOW); it is, probably, connected with different temperatures of carbonate formation. A distinct geographic regularity is traced. Decrease in d18O values is observed from the cold Okhotsk Sea to the warm South China Sea. A very wide range of carbon isotopic composition (d13C from -42 to +3.8 per mil) indicates different sources of carbonic acid required for formation of these carbonates. As a basis for carbon isotopic composition we can distinguish three sources of carbonic acid in the studied sediments: microbiological methane oxidation, organic matter destruction during sediment diagenesis, and dissolved organogenic limestone. Thus, formation of authigenic carbonates in sediments from the marginal seas of the Northwest Pacific results from: 1) sediment diagenesis, 2) methane oxidation in zones of gas anomalies, 3) their precipitation from the supersaturated by carbonates sea shoal waters of tropical sea lagoons.

Benthic foraminifera in Northwest Indian Ocean surface sediments

The relationship between the distribution of benthic foraminifera and sediment type and depositional environment in the Arabian Sea is discussed. The benthic foraminiferal fauna were sampled in nineteen Recent surface sediment samples, and geochemical variables of the sediment of the same samples were measured. The water depths for the box core samples varies from 440 to 4040 m. A total of 103 species and six species-complexes were identified. The geochemical properties were found to correspond well to the sediment type and depositional environment and six different sediment/depositional environment types could be distinguished. Analysis of the benthic foraminiferal fauna reveals specific faunal assemblages that are closely related to these sediment/depositional environment types.

Utility of thallium and geochemical analysis of Mariana arc sediments from ODP Hole 129-801A and 129-801B

We provide the first exploration of thallium (Tl) abundances and stable isotope compositions as potential tracers during arc lava genesis. We present a case study of lavas from the Central Island Province (CIP) of the Mariana arc, supplemented by representative sedimentary and altered oceanic crust (AOC) inputs from ODP Leg 129 Hole 801 outboard of the Mariana trench. Given the large Tl concentration contrast between the mantle and subduction inputs coupled with previously published distinctive Tl isotope signatures of sediment and AOC, the Tl isotope system has great potential to distinguish different inputs to arc lavas. Furthermore, CIP lavas have well-established inter island variability, providing excellent context for the examination of Tl as a new stable isotope tracer. In contrast to previous work (Nielsen et al., 2006b), we do not observe Tl enrichment or light epsilon 205Tl (where epsilon 205Tl is the deviation in parts per 10,000 of a sample 205Tl/203Tl ratio compared to NIST SRM 997 Tl standard) in the Jurassic-aged altered mafic ocean crust subducting outboard of the Marianas (epsilon 205Tl = - 4.4 to 0). The lack of a distinctive epsilon 205Tl signature may be related to secular changes in ocean chemistry. Sediments representative of the major lithologies from ODP Hole Leg 129 801 have 1-2 orders of magnitude of Tl enrichment compared to the CIP lavas, but do not record heavy signatures (epsilon 205Tl = - 3.0 to + 0.4), as previously found in similar sediment types (epsilon 205Tl > + 2.5; Rehkämper et al., 2004). We find a restricted range of epsilon 205Tl = - 1.8 to - 0.4 in CIP lavas, which overlaps with MORB. One lava from Guguan falls outside this range with epsilon 205Tl = + 1.2. Coupled Cs, Tl and Pb systematics of Guguan lavas suggests that this heavy Tl isotope composition may be due to preferential degassing of isotopically light Tl. In general, the low Tl concentrations and limited isotopic range in the CIP lavas is likely due to the unexpectedly narrow range of epsilon 205Tl found in Mariana subduction inputs, coupled with volcaniclastic, rather than pelagic sediment as the dominant source of Tl. Much work remains to better understand the controls on Tl processing through a subduction zone. For example, Tl could be retained in residual phengite, offering the potential exploration of Cs/Tl ratios as a slab thermometer. However, data for Tl partitioning in phengite (and other micas) is required before developing this application further. Establishing a database of Tl concentrations and stable isotopes in subduction zone lavas with different thermal parameters and sedimentary inputs is required for the future use of Tl as a subduction zone tracer.