Geochemistry of pore water and sediments offshore Nicaragua and Costa Rica

Four volcanic ash-bearing marine sediment cores and one ash-free reference core were examined during research cruise RV Meteor 54/2 offshore Nicaragua and Costa Rica to investigate the chemical composition of pore waters related to volcanic ash alteration. Sediments were composed of terrigenous matter derived from the adjacent continent and contained several distinct ash layers. Biogenic opal and carbonate were only minor components. The terrigenous fraction was mainly composed of smectite and other clay minerals while the pore water composition was strongly affected by the anaerobic degradation of particulate organic matter via microbial sulphate reduction. The alteration of volcanic matter showed only a minor effect on major element concentrations in pore waters. This is in contrast to prior studies based on long sediment cores taken during the DSDP, where deep sediments always showed distinct signs of volcanic ash alteration. The missing signal of ash alteration is probably caused by low reaction rates and the high background concentration of major dissolved ions in the seawater-derived pore fluids. Dissolved silica concentrations were, however, significantly enriched in ash-bearing cores and showed no relation to the low but variable contents of biogenic opal. Hence, the data suggest that silica concentrations were enhanced by ash dissolution. Thus, the dissolved silica profile measured in one of the sediment cores was used to derive the in-situ dissolution rate of volcanic glass particles in marine sediments. A non-steady state model was run over a period of 43 kyr applying a constant pH of 7.30 and a dissolved Al concentration of 0.05 ?M. The kinetic constant (AA) was varied systematically to fit the model to the measured dissolved silica-depth profile. The best fit to the data was obtained applying AA = 1.3 * 10**-U9 mol of Si/cm**2/ s. This in-situ rate of ash dissolution at the seafloor is three orders of magnitude smaller than the rate of ash dissolution determined in previous laboratory experiments. Our results therefore imply that field investigations are necessary to accurately predict natural dissolution rates of volcanic glasses in marine sediments.

Bulk geochemistry and grain-size composition of surface sediments from the SW Atlantic

Surface sediments from the South American continental margin surrounding tbe Argentine Basin were studied with respect to bulk geochemistry (Caeo) and C ) and grain-size composition (sand/silt/clay relation and terrigenous silt grain-size distribution). The grain-size distributions of the terrigenous silt fraction were unmixed into three end members (EMs), using an end-member modelling algorithm. Three unimodal EMs appear to satisfactorily explain the variations in the data set of the grain-size distributions ofterrigenous silt. The EMs are related to sediment supply by rivers, downslope transport, winnowing, dispersal and re-deposition by currents. The bulk geochemical composition was used to trace the distribution of prominent water masses within the vertical profile. The sediments of the eastern South American continental margin are generally divided into a coarse-grained and carbonate-depleted southwestern part, and a finer-grained and carbonate-rich northeastern part. The transition of both environments is located at the position of the Brazil Malvinas Confluence (BMC). The sediments below the confluence mixing zone of the Malvinas and Brazil Currents and its extensions are characterised by high concentrations of organic carbon, low carbonate contents and high proportions of the intennediate grain-size end member. Tracing these properties, the BMC emerges as a distinct north-south striking feature centered at 52-54°W crossing the continental margin diagonally. Adjacent to this prominent feature in the southwest, the direct detrital sediment discharge of the Rio de la Plata is clearly recognised by a downslope tongue of sand and high proportions of the coarsest EM. A similar coarse grain-size composition extends further south along the continental slope. However, it displays bener sorting due to intense winnowing by the vigorous Malvinas Current. Fine-grained sedimentary deposition zones are located at the southwestern deeper part of the Rio Grande Rise and the southern abyssal Brazil Basin, both within the AABW domain. Less conspicuous winnowing/accumulation panerns are indicated north of the La Plata within the NADW level according to the continental margin topography. We demonstrate that combined bulk geochemical and grain-size properties of surface sediments, unmixed with an end-member algorithm, provide a powerful tool to reconstruct the complex interplay of sedimentology and oceanography along a time slice.

Mineralogical, sedimentological and paleontological analyses of ODP Hole 127-797B upper Quarternary sediments

Nearly continuous cores of Quaternary fine-grained sediments with distinct dark-light colored cycles were recovered from Sites 794, 795, and 797 in the basinal parts of the Japan Sea during Leg 127. A comparison of gray value (darkness) profiles supplemented by visual inspection of core photographs between sites indicated that most of the dark and light layers were correlatable between sites, and that two of the dark layers lie close to adjacent marker ash layers. These observations indicate that deposition of dark and light layers resulted from basin-wide synchronous events. In order to understand the origin of these dark-light cycles, petrographical, mineralogical, compositional, and paleontological studies were carried out on closely spaced samples from the upper Quaternary sediments recovered from Site 797. Age model was constructed based on comparison between variation in diatom abundance and the standard oxygen isotope curve of Imbrie et al. (1984), the latter was interpolated between the five age controlled levels established at Site 797. The two curves show similar patterns which enabled us to "tune" the sediment ages to the oxygen isotope stages. We have to use variation in diatom abundance as a substitute for oxygen isotope curve since oxygen isotopic data are not available at the studied sites. Bottom water oxygenation conditions were estimated based on two criteria: (1) the degree of lamina preservation and (2) the ratio of Corg to Stot. The surface water productivity was deduced from the Corg and biogenic silica content. Results suggest that the bottom water oxygenation level and the surface water productivity varied significantly in response to the glacial-interglacial cycles. Glacio-eustatic sea-level changes and subsequent changes in water circulation in the Japan Sea appear to have been responsible for these variations and consequent changes in sediment composition throughout the Quaternary.

Coccoliths and carbonate grain-size compositions in sediment samples from the Mid-Atlantic Ridge

This study presents a differentiated carbonate budget for marine surface sediments from the Mid-Atlantic Ridge of the South Atlantic, with results based on carbonate grain-size composition. Upon separation into sand, silt, and clay sub-fractions, the silt grain-size distribution was measured using a SediGraph 5100. We found regionally characteristic grain-size distributions with an overall minimum at 8 µm equivalent spherical diameter (ESD). SEM observations reveal that the coarse particles (>8 µm ESD) are attributed to planktic foraminifers and their fragments, and the fine particles (<8 µm ESD) to coccoliths. On the basis of this division, the regional variation of the contribution of foraminifers and coccoliths to the carbonate budget of the sediments are calculated. Foraminifer carbonate dominates the sediments in mesotropic regions whereas coccoliths contribute most carbonate in oligotrophic regions. The grain size of the coccolith share is constant over water depth, indicating a lower susceptibility for carbonate dissolution compared to foraminifers. Finally, the characteristic grain-size distribution in fine silt (<8 µm ESD) is set into context with the coccolith assemblage counted and biometrically measured using a SEM. The coccoliths present in the silt fraction are predominantly large species (length > 4 µm). Smaller species (length < 4 µm) belong to the clay fraction (<2 µm ESD). The average length of most frequent coccolith species is connected to prominent peaks in grain-size distributions (ESD) with a shape factor. The area below Gaussian distributions fitted to these peaks is suggested as a way to quantitatively estimate the carbonate contribution of single coccolith species more precisely compared to conventional volume estimates. The quantitative division of carbonate into the fraction produced by coccoliths and that secreted by foraminifers enables a more precise estimate for source/sink relations of consumed and released CO2 in the carbon cycle. The allocation of coccolith length and grain size (ESD) suggests size windows for the separation or accumulation of distinct coccolith species in investigations that depend on non to slightly-mixed signals (e.g., isotopic studies).

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.

Terrestrial organic matter in marine sediments of the Central Equatorial Atlantic

Terrestrial organic matter (OM) in pelagic sediments is discussed with regard to depositional processes and land-sea interactions in the modern and past glacial/interglacial Equatorial Atlantic. Special emphasis is placed on a critical evaluation of different analytical approaches (C/N, Rock-Eval Pyrolysis, stable carbon isotopes, palynology, organic petrology, and selected biomarkers) which are currently used for the qualitative and quantitative assessment of terrigenous organic carbon. If binary mixing equations are used to calculate terrestrial and marine proportions of organic carbon, we consider the definition of endmember values to be most critical since these values may be biased by a great number of independent controls. A combination of geochemical methods including optical studies (organic petrology and palynology) is therefore suggested to evaluate each individual proxy. Organic geochemical analyses performed on sediments from the modern and Late Quaternary Equatorial Atlantic evidence fluctuations in eolian supply of terrigenous OM related to changes in intensity of the trade winds. Quantification of this organic fraction leads to differing proportions depending on the approach applied, i.e. the organic carbon isotopic composition or maceral analyses. Modern distribution of terrigenous OM reveals a decrease in supply towards the basin contributing less than a fifth of the total OM in pelagic areas. Organic geochemical data indicate that sedimentation in the modern northeastern Brasil Basin is affected by lateral advection of reworked OM probably from southern source areas. Glacial/interglacial deposits from the pelagic Equatorial Atlantic (ODP Site 663), covering isotopic stages 12 and 11, reveal that deposition of terrigenous OM was higher under past glacial conditions, in correspondence to generally enhanced dust fluxes. Proportions of terrigenous OM, however, never exceed 50% of the total OM according to maceral analyses. Other estimates, recently proposed by Verardo and Ruddiman (1996), are considered to be too high probably for analytical reasons. Palynological records in the Equatorial Atlantic parallel dust records. Increased portions of grass pollen suggest the admixture of C4-plant material under modern and past glacial conditions. It is therefore assumed, as one possible interpetation, that C4-plant debris has an effect on sedimentary d13Corg and might explain differences between isotopic and microscopic quantitative estimates. Using the difference between these two records, we calculate that maximum supply of C4-material remains below 20% of the total OM for the deep modern and past glacial/interglacial Equatorial Atlantic.

Methane discharge in sediments of the Dvurechenskii mud volcano

During the MARGASCH cruise M52/1 in 2001 with RV Meteor we sampled surface sediments from three stations in the crater of the Dvurechenskii mud volcano (DMV, located in the Sorokin Trough of the Black Sea) and one reference station situated 15 km to the northeast of the DMV. We analysed the pore water for sulphide, methane, alkalinity, sulphate, and chloride concentrations and determined the concentrations of particulate organic carbon, carbonate and sulphur in surface sediments. Rates of anaerobic oxidation of methane (AOM) were determined using a radiotracer (14CH4) incubation method. Numerical transport-reaction models were applied to derive the velocity of upward fluid flow through the quiescently dewatering DMV, to calculate rates of AOM in surface sediments, and to determine methane fluxes into the overlying water column. According to the model, AOM consumes 79% of the average methane flux from depth (8.9 x 10**+ 6 mol a**-1), such that the resulting dissolved methane emission from the volcano into the overlying bottom water can be determined as 1.9 x 10**+ 6 mol a**-1. If it is assumed that all submarine mud volcanoes (SMVs) in the Black Sea are at an activity level like the DMV, the resulting seepage represents less than 0.1% of the total methane flux into this anoxic marginal sea. The new data from the DMV and previously published studies indicate that an average SMV emits about 2.0 x 10**+ 6 mol a**-1 into the ocean via quiescent dewatering. The global flux of dissolved methane from SMVs into the ocean is estimated to fall into the order of 10**+10 mol a**-1. Additional methane fluxes arise during periods of active mud expulsion and gas bubbling occurring episodically at the DMV and other SMVs.

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.

Carbonate sedimentology of the Propeller Mound, Northeast Atlantic

High resolution studies from the Propeller Mound, a cold-water coral carbonate mound in the NE Atlantic, show that this mound consists of >50% carbonate justifying the name "carbonate mound". Through the last ~300,000 years approximately one third of the carbonate has been contributed by cold-water corals, namely Lophelia pertusa and Madrepora oculata. This coral bound contribution to the carbonate budget of Propeller Mound is probably accompanied by an unknown portion of sediments buffered from suspension by the corals. However, extended hiatuses in Propeller Mound sequences only allow the calculation of a net carbonate accumulation. Thus, net carbonate accumulation for the last 175 kyr accounts for only <0.3 g/cm2/kyr, which is even less than for the off-mound sediments. These data imply that Propeller Mound faces burial by hemipelagic sediments as has happened to numerous buried carbonate mounds found slightly to the north of the investigated area.

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.

Lead in bottom sediments, nodules, and sulfides from the Black Sea

A study of lead distribution in recent, ancient Black Sea and Neweuxinian bottom sediment shows similar vertical distributions of the element in the oxygen and hydrogen sulfide zones of the sea; i.e. hydrogen sulfide contamination does not affect lead contents in bottom sediments of the sea. Lead distribution in sediment mass of the Black Sea reflects dependence of accumulation of the element on the hydrodynamic regime of the sea and forms of its migration. It is noted that absence of lead accumulation in Black Sea nodules results from specific nodule formation and from geochemical activity of the element. A large role of diagenetic sulfide formation in lead geochemistry is shown. Degree of lead accumulation in iron sulfides depends on conditions of sedimentation and on physical and chemical parameters in the sea.

Chemical and isotope compositions of main phases of metalliferous sediments from holes of DSDP Leg 92

The carbonate-free metalliferous fraction of thirty-nine sediment samples from four DSDP Leg 92 sites has been analyzed for 12 elements, and a subset of 16 samples analyzed for Pb isotopic composition. The main geochemical features of this component are as follows: i) very high concentrations of Fe and Mn, typically 25-39% and 5-14%, respectively; ii) Al and Ca contents generally less than 2% and 5%, respectively; iii) high Cu (1000-2000 ppm), and Zn and Ni (500-1000 ppm) values; and iv) Co and Pb concentrations of 100-250 ppm. In terms of element partitioning within the metalliferous fraction, amorphous to poorly crystallized oxide-oxyhydroxides removed by the second leach carry virtually all of the Mn, and about 90% of the Ca, Sr and Ni. The well-crystallized goethite-rich material removed by the third leach carries the majority of Fe, Cu, and Pb. These relations hold for sediments as young as ~1-2 Ma, indicating early partitioning of hydrothermal Fe and Mn into separate phases. Calculated mass accumulation rates (MAR) for Fe, Mn, Cu, Pb, Zn and Ni in the bulk sediment show the same overall trends at three of the sites, with greatest MAR values near the basement, and a general decrease in MAR values towards the tops of the holes (for sediments deposited above the lysocline). These relations strongly support the concept of a declining hydrothermal contribution of these elements away from a ridge axis. Nevertheless, MAR values for these metals up to ~200 km from the ridge axis are orders of magnitude higher than on abyssal seafloor plains where there is no hydrothermal influence. Mn/Fe ratios throughout the sediment column at two sites indicate that the composition of the hydrothermal precipitates changed during transport through seawater, becoming significantly depleted in Mn beyond ~200-300 km from the axis, but maintaining roughly the same proportion of Fe. Most of the Pb isotope data for the Leg 92 metalliferous sediments form approximately linear arrays in the conventional isotopic plots, extending from the middle of the field for mid-ocean ridge basalts toward the field for Mn nodules. The array of data lying between these two end-members is most readily interpreted in terms of simple linear mixing of Pb derived from basaltic and seawater end-member sources. The least radiogenic sediments reflect the average Pb isotope composition of discharging hydrothermal solutions and ocean-ridge basalt at the EPR over the ~4-8 Ma B.P. interval. Pb in sediments deposited up to 250 km from the axis can be almost entirely of basaltic-hydrothermal origin. Lateral transport of some basaltic Pb by ocean currents appears to extend to distances of at least 1000 km west of the East Pacific Rise.

Mg/Ca of planktonic foraminifera from tropical Pacific surface sediments

Mg/Ca in planktonic foraminifers carries two main signals: calcification temperature and postdepositional test dissolution. Shell dissolution thus distorts water temperature reconstructions made with Mg/Ca in foraminifers. This problem could be resolved by quantifying the impact of carbonate dissolution on Mg/Ca with an independent, temperature-insensitive deep-sea calcite dissolution proxy, such as the Globorotalia menardii fragmentation index (MFI). To test the validity of this approach, we measured Mg/Ca in the tests of several planktonic foraminifers and MFI in core tops collected over a wide geographic region of the tropical Pacific and covering a wide range of deep-sea calcite dissolution and seawater temperature. We confirm that Mg/Ca from different species have different susceptibility to temperature and dissolution. Mg/Ca in surface-dwelling Globigerina bulloides is controlled by calcification temperature and is largely unaffected by carbonate dissolution estimated from MFI. In contrast, Mg/Ca in deeper dwelling G. menardii is minimally sensitive to temperature and dominantly affected by dissolution. Mg/Ca in Neogloboquadrina dutertrei and Pulleniatina obliquiloculata are significantly affected by both temperature and dissolution, and MFI can be effectively used to correct temperature estimates from these species for calcite dissolution. Additional variables besides temperature and dissolution appear to control Mg/Ca in Globorotalia tumida, and their identification is a prerequisite for interpreting elemental shell composition in this species. Combining down-core measurements of Mg/Ca in multiple foraminifer species with MFI provides a powerful tool for reconstructing past changes in the upper water column temperature structure in the tropical Pacific.