Corrected index properties for ODP Leg 127 and 128 sites

During Legs 127 and 128, we found a systematic error in the index property measurements, in that the wet bulk density, grain density, and porosity did not satisfy well-established interrelationships. We have found that an almost constant difference exists between the weight of water lost during drying and the volume of water lost. This discrepancy is independent of volume or water content of the sample. The water losses should be equal because the density of water is close to 1.0 g/cm**3. The pycnometer wet volume measurement has been identified as the source of the systematic error. The wet volume on average is 0.2 cm**3 too low. For the rare cases when the water content is negligible, there is no offset. The source of the wet volume error results from the partial vapor pressure of water in the pycnometer cell. Newly corrected tables of index properties measured during Legs 127 and 128 are included. The corrected index properties are internally consistent. The data are in better agreement with theoretical models that relate the index properties to other physical properties, such as thermal conductivity and acoustic velocity. In future, a standard volume sampler should be used, or the wet volume should be calculated from the dry volume and the water loss by weight.

Investigations on sediment coring site PS1823 in the Riiser-Larsen Sea, Southern Ocean

Physical and sedimentological investigations were carried out on a 14 m long gravity core and a 0.5 m long box core from 4440 m water depth off Queen Maud Land, East-Antarctica. Strongly bioturbated hemipelagic muds of predominantly terrigenous origin and a very small biogenic part build up the 'Normal-Facies'. Several sandy to silty layers are inserted in the 'Normal-Facies'. These layers are seperated by lithology, structure and the investigated parameters of this study and are interpreted as turbidites. The source area for the turbidity currents is supposed to be at the uppermost continental margin, close to the shelf break and there is evidenee for this gravity transport within the erosive Ritscher-Canyon, which extends close to the core position. The distribution of biogenic components indicates an age of 1.3 million years or more, with an average sedimentation rate of about 1 cm/1000 years. Early diagenetic proeesses caused water loss by compaction, errosion and dissolution of biogenic components and precipitation and recrystallization of manganese micronodules. Cyclic fluctuations of the sediment-parameters within the 'Normal-Facies' enable the distinction of a 'Glazial'- and an 'Interglazial'-Facies. The 'Glazial'-Facies reflects glacial sedimentary conditions and shows a dark olive gray colour, high susceptibility, low silt/clay-ratios, only a few biogenic components and the regular occurence of interrelated turbidite layers. In contrast, the 'Interglazial'-Facies is dominated by a light olive or olive-brown colour, low susceptibility, high silt/clay-ratios and an increased number of biogenic components. This facies corresponds to interglacial conditions. Three main processes are supposed to have been responsible for the observed facies changes: (1) the bottom water mass circulation, (2) the gravity transport by turbidity currents and (3) the biogenic surface production. These processes are related to the quaternary climatic changes. The extension of the ice shelves directed the gravity transport to the deep sea and the formation of Antarctic Bottom Water, which in turn influenced the silt/clay-ratios in the sediment record. Fluctuations in sea ice coverage controlled the biogenic surface production.

He isotope, U/Th isotope, Calcium carbonate, biogenic opal, rare earth element concentrations, and grain size distribution measured on core-top sediments during SONNE cruise SO202 (INOPEX)

Eolian dust is a significant source of iron and other nutrients that are essential for the health of marine ecosystems and potentially a controlling factor of the high nutrient-low chlorophyll status of the Subarctic North Pacific. We map the spatial distribution of dust input using three different geochemical tracers of eolian dust, 4He, 232Th and rare earth elements, in combination with grain size distribution data, from a set of core-top sediments covering the entire Subarctic North Pacific. Using the suite of geochemical proxies to fingerprint different lithogenic components, we deconvolve eolian dust input from other lithogenic inputs such as volcanic ash, ice-rafted debris, riverine and hemipelagic input. While the open ocean sites far away from the volcanic arcs are dominantly composed of pure eolian dust, lithogenic components other than eolian dust play a more crucial role along the arcs. In sites dominated by dust, eolian dust input appears to be characterized by a nearly uniform grain size mode at ~4 µm. Applying the 230Th-normalization technique, our proxies yield a consistent pattern of uniform dust fluxes of 1-2 g/m**2/yr across the Subarctic North Pacific. Elevated eolian dust fluxes of 2-4 g/m**2/yr characterize the westernmost region off Japan and the southern Kurile Islands south of 45° N and west of 165° E along the main pathway of the westerly winds. The core-top based dust flux reconstruction is consistent with recent estimates based on dissolved thorium isotope concentrations in seawater from the Subarctic North Pacific. The dust flux pattern compares well with state-of-the-art dust model predictions in the western and central Subarctic North Pacific, but we find that dust fluxes are higher than modeled fluxes by 0.5-1 g/m**2/yr in the northwest, northeast and eastern Subarctic North Pacific. Our results provide an important benchmark for biogeochemical models and a robust approach for downcore studies testing dust-induced iron fertilization of past changes in biological productivity in the Subarctic North Pacific.

(Table 12-4, page 360) Percentage loss of water from manganese nodules (on a wet basis) at different temperatures

This chapter discusses the formation and distribution of some metals in ocean-floor manganese nodules in the light of the observed data in the literature and thermodynamic and kinetic considerations of the oxidation of metal ions in the oceanic environment. There are, in general, two major schools of thought on the mechanism of incorporation of the minor elements such as nickel, copper, and cobalt with the major elements such as manganese and iron. One is the lattice substitution mechanism and the other the adsorption mechanism. If the mechanism is lattice substitution, extraction of the metal ions is not possible unless the lattice of the major elements is first broken and exchanged with other ions from the bulk solution. Consequently, the leaching behavior of minor elements should display a very close relationship with that of major elements.

Daily polynya area and ice production in the North Water polynya region

The North Water (NOW) Polynya is a regularly-forming area of open-water and thin-ice, located between northwestern Greenland and Ellesmere Island (Canada) at the northern tip of Baffin Bay. Due to its large spatial extent, it is of high importance for a variety of physical and biological processes, especially in wintertime. Here, we present a long-term remote sensing study for the winter seasons 1978/1979 to 2014/2015. Polynya characteristics are inferred from (1) sea ice concentrations and brightness temperatures from passive microwave satellite sensors (Advanced Microwave Scanning Radiometer (AMSR-E and AMSR2), Scanning Multichannel Microwave Radiometer (SMMR), Special Sensor Microwave Imager/Sounder (SSM/I-SSMIS)) and (2) thin-ice thickness distributions, which are calculated using MODIS ice-surface temperatures and European Center for Medium-Range Weather Forecasts (ECMWF) atmospheric reanalysis data in a 1D thermodynamic energy-balance model. Daily ice production rates are retrieved for each winter season from 2002/2003 to 2014/2015, assuming that all heat loss at the ice surface is balanced by ice growth. Two different cloud-cover correction schemes are applied on daily polynya area and ice production values to account for cloud gaps in the MODIS composites. Our results indicate that the NOW polynya experienced significant seasonal changes over the last three decades considering the overall frequency of polynya occurrences, as well as their spatial extent. In the 1980s, there were prolonged periods of a more or less closed ice cover in northern Baffin Bay in winter. This changed towards an average opening on more than 85% of the days between November and March during the last decade. Noticeably, the sea ice cover in the NOW polynya region shows signs of a later-appearing fall freeze-up, starting in the late 1990s. Different methods to obtain daily polynya area using passive microwave AMSR-E/AMSR2 data and SSM/I-SSMIS data were applied. A comparison with MODIS data (thin-ice thickness < 20 cm) shows that the wintertime polynya area estimates derived by MODIS are about 30 to 40% higher than those derived using the polynya signature simulation method (PSSM) with AMSR-E data. In turn, the difference in polynya area between PSSM and a sea ice concentration (SIC) threshold of 70% is fairly low (approximately 10%) when applied to AMSR-E data. For the coarse-resolution SSM/I-SSMIS data, this difference is much larger, particularly in November and December. Instead of a sea ice concentration threshold, the PSSM method should be used for SSM/I-SSMIS data. Depending on the type of cloud-cover correction, the calculated ice production based on MODIS data reaches an average value of 264.4 ± 65.1 km**3 to 275.7 ± 67.4 km**3 (2002/2003 to 2014/2015) and shows a high interannual variability. Our achieved long-term results underline the major importance of the NOW polynya considering its influence on Arctic ice production and associated atmosphere/ocean processes.

Plutonium and americium concentrations in sea water and in sinking particles

Vertical fluxes of 239+240Pu and 241Am and temporal changes in their inventories in the northwestern Mediterranean Sea have been examined through high-resolution water column sampling coupled with direct measurements of the vertical flux of particle-bound transuranics using time-series sediment traps. Water column profiles of both radionuclides showed well-defined sub-surface maxima (2391240Pu between 100-400 m; 241Am at 100-200 m and 800 m), the depths of which are a result of the different biogeochemical scavenging behavior of the two radionuclides. Comparison of deep water column (0-2,000 m) transuranic inventories with those derived from earlier measurements demonstrate that the total 2391240Pu inventory had not substantially changed between 1976-1990 whereas 241Am had decreased by approximately 24%. Enhanced scavenging of 241Am and a resultant, more rapid removal from the water column relative to 239+240Pu was also supported by the observation of elevated Am/Pu activity ratios in sinking particles collected in sediment traps at depth. Direct measurements of the downward flux of particulate 239+240Pu and 241Am compared with transuranic removal rates derived from observed total water column inventory differences over time, show that particles sinking out of deep waters (1,000-2,000 m) could account for 26-72% of the computed total annual 239+240Pu loss and virtually all of the 241Am removal from the water column. Upper water column (0-200 m) residence times based on direct flux measurements ranged from 20-30 yr for 239+240Pu and 5-10 yr for 241Am. The observation that 241Am/239+240Pu activity ratios in unfiltered Mediterranean seawater are six times lower than those in the north Pacific suggests the existence of a specific mechanism for enhanced scavenging and removal of 241Am from the generally oligotrophic waters of the open Mediterranean. It is proposed that atmospheric inputs of aluminosilicate particles transported by Saharan dust events which frequently occur in the Mediterranean region could enhance the geochemical scavenging and resultant removal of 241Am to the sediments.

Major ion concentrations and chlorine isotope composition of water-soluble chloride and structurally bound chloride in DSDP/ODP serpentinized ultramafic rocks

Eight DSDP/ODP cores were analyzed for major ion concentrations and d37Cl values of water-soluble chloride (d37Clwsc) and structurally bound chloride (d37Clsbc) in serpentinized ultramafic rocks. This diverse set of cores spans a wide range in age, temperature of serpentinization, tectonic setting, and geographic location of drilled serpentinized oceanic crust. Three of the cores were sampled at closely spaced intervals to investigate downhole variation in Cl concentration and chlorine isotope composition. The average total Cl content of all 86 samples is 0.26±0.16 wt.% (0.19±0.10 wt.% as water-soluble Cl (Xwsc) and 0.09±0.09 wt.% as structurally bound Cl (Xsbc)). Structurally bound Cl concentration nearly doubles with depth in all cores; there is no consistent trend in water-soluble Cl content among the cores. Chlorine isotope fractionation between the structurally bound Cl**- site and the water-soluble Cl**- site varies from -1.08? to +1.16?, averaging to +0.21?. Samples with negative fractionations may be related to reequilibration of the water-soluble chloride with seawater post-serpentinite formation. Six of the cores have positive bulk d37Cl values (+0.05? to +0.36?); the other two cores (173-1068A (Leg-Hole) and 84-570) have negative bulk d37Cl values (-1.26? and -0.54?). The cores with negative d37Cl values also have variable Cl**-/SO4**2- ratios, in contrast to all other cores. The isotopically positive cores (153-920D and 147-895E) show no isotopic variation with depth; the isotopically negative core (173-1068A) decreases by ~1? with depth for both the water-soluble and structurally bound Cl fractions. Non-zero bulk d37Cl values indicate Cl in serpentinites was incorporated during original hydration and is not an artifact of seawater infiltration during drilling. Cores with positive d37Cl values are most likely explained by open system fractionation during hydrothermal alteration, with preferential incorporation of 37Cl from seawater into the serpentinite and loss of residual light Cl back to the ocean. Fluid / rock ratios were probably low as evidenced by the presence of water-soluble salts. The two isotopically negative cores are characterized by a thick overlying sedimentary package that was in place prior to serpentinization. We believe the low d37Cl values of these cores are a result of hydration of ultramafic rock by infiltrating aqueous pore fluids from the overlying sediments. The resulting serpentinites inherit the characteristic negative d37Cl values of the pore waters. Chlorine stable isotopes can be used to identify the source of the serpentinizing fluid and ultimately discern chemical and tectonic processes involved in serpentinization.

Interstitial water and sediment chemistry at DSDP Sites 87-582 and 87-584

Two trenches off Japan were explored during DSDP Leg 87. One is the Nankai Trough and the other is the Japan Trench; Site 582 is located on the floor of the former and Site 584 is situated on the deep-sea terrace of the latter. Cores from Site 582 and 584 consist mainly of hemipelagic sediments and diatomaceous silts and mudstone, respectively. In this report we analyze the chemistry of the interstitial water and sediments, as well as the sediment mineralogy. Sulfate reduction is accompanied by the production of secondary pyrite, which is rich in the sediment at both sites. Dissolved Ca concentration is relatively low and changes only slightly at both sites, probably because of the formation of carbonate with high alkalinity. Concentrations of dissolved Mg decrease with depth at Site 584. The dissolved Mg depletion probably results from the formation of Mg-rich carbonate and/or ion exchange and reaction between interstitial water and clay minerals. Higher Si/Al values are due to biogenic opal in the sediments and roughly correlate with higher values of interstitial water SiO2. Increases in dissolved Li concentrations may be related to its release from clay minerals, to advection that results from dewatering, and/or to fluid transport.

Composition of sediment pore water and isotopes in carbonate and benthic foraminifera at DSDP Holes 68-501, 69-505 and Site 69-504

Two sites on the southern flank of the Costa Rica Rift were drilled on DSDP Legs 68 and 69, one on crust 3.9 m.y. old and the other on crust 5.9 m.y. old. The basement of the younger site is effectively cooled by the circulation of seawater. The basement of the older site has been sealed by sediment, and an interval in the uppermost 560 meters of basement recently reheated to temperatures of 60 to 120°C. Although the thickness of the sediments at the two sites is similar (150-240 m versus 270 m), the much rougher basement topography at the younger Site 505 produces occasional basement outcrops, through which 80 to 90% of the total heat loss apparently occurs by advection of warm seawater. This seawater has been heated only slightly, however; the temperature at the base of the sediments is only 9°C. Changes in its composition due to reaction with the basement basalts are negligible, as indicated by profiles of sediment pore water chemistry. Bacterial sulfate reduction in the sediments produces a decrease in SO4 (and Ca) and an increase in alkalinity (and Sr and NH3) as depth increases to an intermediate level, but at deeper levels these trends reverse, and all of these species plus Mg, K, Na, and chlorinity approach seawater values near basement. Si, however, is higher, and Li may be lower. At the older site, Site 501/504, where heat loss is entirely by conduction, the temperature at the sediment/basement contact is 59°C. Sediment pore water chemistry is heavily affected by reaction with the basaltic basement, as indicated by large decreases in d18O, Mg, alkalinity, Na, and K and an increase in Ca with increasing depth. The size of the changes in d18O, Mg, alkalinity, Ca, Sr, and SO4 varies laterally over 500 meters, indicating lateral gradients in pore water chemistry that are nearly as large as the vertical gradients. The lateral gradients are believed to result from similar lateral gradients in the composition of the basement formation water, which propagate upward through the sediments by diffusion. A model of the d18O profile suggests that the basement at Site 501/504 was sealed off from advection about 1 m.y. ago, so that reaction rates began to dominate the basement pore water chemistry. A limestone-chert diagenetic front began to move upward through the lower sediments less than 200,000 yr. ago.