Geochemistry of pore water and sediments from ODP Leg 136 sites

During Leg 136 drilling was conducted at two sites in pelagic sediments of the north central Pacific Ocean. In this report, pore-water analyses for major seawater constituents, alkalinity, ammonia, nitrate, phosphate, silica, Ba, Fe, Li, Mn, and Sr are presented. Although concentration gradients are generally weak, resulting from slow sedimentation and concomitant diffusive communication with overlying water, there is evidence of sediment/pore-water interactions, associated sediment diagenesis, and formation of authigenic minerals. Bulk major and trace element compositions of the sediments are consistent with reactions inferred to occur within the sediments and with the lithology and mineralogy. Elemental compositions of the sediments are not strongly affected by diagenesis and are primarily related to the dominant mineralogy. Sediments are typical of deep ocean pelagic settings with a significant contribution from the alteration of volcanic ash and the formation of zeolites. Sedimentary rare earth element patterns also provide evidence of active scavenging processes by Mn and Fe oxide phases in the deeper sediments at Site 842.

Accumulation rates for western Dronning Maud Land from firn cores and snow pits

As a result of intensive field activities carried out by several nations over the past 15 years, a set of accumulation measurements for western Dronning Maud Land, Antarctica, was collected, based on firn-core drilling and snow-pit sampling. This new information was supplemented by earlier data taken from the literature, resulting in 111 accumulation values. Using Geographical Information Systems software, a first region-wide mean annual snow-accumulation field was derived. In order to define suitable interpolation criteria, the accumulation records were analyzed with respect to their spatial autocorrelation and statistical properties. The resulting accumulation pattern resembles well known characteristics such as a relatively wet coastal area with a sharp transition to the dry interior, but also reveals complex topographic effects. Furthermore, this work identifies new high-return shallow drilling sites by uncovering areas of insufficient sampling density.

Concentrations of suspended matter and heavy metals in melted ice- and snow water from the Barents Sea

In September-October 1998, during Cruise 14 of R/V Akademik Fedorov to the Barents Sea, in the region of 82° N between the Spitsbergen and Novaya Zemlya archipelagos samples of snow and ice were collected within four polygons. By means of atomic absorption with an electothermal atomizer (onboard the ship) in filtered (dissolved form) and unfiltered (sum of dissolved and particulate forms) samples of snow melt and ice melt concentrations of Fe, Mn, Cu, Cr, Ni, Co, Pb, and Cd were determined in order to estimate level of potential contamination of snow and ice with these metals. Excluding data on Ni, Cd (and probably Cu) in ice that were regarded to be unsatisfactory because of probable contamination of the ice samples during drilling concentrations of all the elements in snow and ice of the northern part of the Barents Sea appeared to be close to their background values or below. An attempt to identify the main sources of metal supply to snow from the atmosphere by comparison of ratios of metal particulate form to total content in snow of the Barents Sea and the same ratios in snow samples from clean regions of Finland and from contaminated areas of the Kola Peninsula showed that aerosols in the area of the expedition were supplied into the Barents Sea atmosphere from different sources, both natural and anthropogenic.

Chemical element contents and accumulation rates in metalliferous sediments from DSDP Hole 34-319, Bauer Deep, Southeast Pacific

Marked variations in the chemical and mineralogical composition of sediments at Site 319 have occurred during the 15 My history of sedimentation at this site. The change in composition through time parallels the variability observed in surface sediments from various parts of the Nazca Plate and can be related to variations in the proportion of hydrothermal, hydrogenous, detrital and biogenous phases reaching this site at different times. Metal accumulation rates at Site 319 reach a maximum near the basement for most elements, suggesting a strong hydrothermal contribution during the early history of this site. The hydrothermal contribution decreased rapidly as Site 319 moved away from the spreading center, although a subtle increase in this source is detectable about the time spreading began on the East Pacific Rise. The most recent sedimentation exhibits a strong detritalhydrogenous influence. Post-depositional diagenesis of amorphous phases has converted them to ironrich smectite and well-crystallized goethite without significantly altering the bulk composition of the sediment.

Planktonic foraminifera of Oligocene sediments from DSDP Hole 77-538A in the Gulf of Mexico

A relatively extended Oligocene pelagic sequence with good to medium recovery, drilled during DSDP Leg 77 in the Gulf of Mexico, yielded rich and well diversified planktonic foraminiferal faunas. Planktonic foraminifera recorded in Hole 538A span the interval from Zone P19 through P22. Evolutionary lineages were observed among the globoquadrinids, the globigerinitids, and the "Globigerina" ciperoensis and Globigerinoides primordius groups. Quantitative analysis of planktonic foraminiferal assemblages shows that faunas fluctuate in abundance and species diversity throughout the sequence. A few of these fluctuations that could be related to selective dissolution are mainly confined to the early-mid Oligocene. A climatic curve was constructed using as warmer indicators, Turborotalia pseudoampliapertura, Globoquadrina tripartita, Dentoglobigerina globularis, Dentoglobigerina baroemoenensis,. "Globigerina" ciperoensis and Globigerinoides groups, and Cassigerinella chipolensis; and as coller indicators, Catapsydrax spp., Globorotaloides spp., Subbotina angiporoides group, Globigerina s. str., and the tenuitellides. Three major intervals are identifiable in the climatic curve: Interval 1 (lower) up to Zone P20 predominantly cooler: Interval 2 (intermediate) up to the upper part of Zone P21a with warm and cool fluctuations: and lnterval 3 (upper), warmer, with a large positive peak, due to abundant "G." angulisuturalis, at the beginning of Zone P21b with recooling midway in Zone P22. In Intervals 1 and 2 planktonic foraminiferal faunas are dominated by temperate forms. Interpretation of planktonic foraminiferal data suggests that cooler water conditions characterize the early-mid Oligocene: during the mid Oligocene (most of Zone P21a) water masses exhibit peculiar characteristics transitional to the warmer waters prevailing during the late Oligocene. Warmer conditions were not definitely settled in Zone P22, however, as indicated by the cooler episode following the warmest peak. These climatic trends are inconsistent with those inferred from oxygen isotopes except at small scale. In fact, oxygen isotope values for Oligocene Atlantic Ocean are too heavy (thus too cool) in comparison with the high abundance and diversity of warm taxa, expecially in Zone P22. When values are lighter (warmer), as in Zone P19 abundance and diversity of warm indices are too low. To explain such a cool isotope values in presence of highly diversified and abundant warm planktonic foraminifera, we suggest (1) that the oxygen isotope ratio used for estimating Oligocene paleotemperatures might be 1? heavier than Eocene values and further increased for the late Oligocene. This hypothesis implies the presence of a relatively extended ice cap in Antarctica in the early and mid Oligocene, and probably an increase in ice volume during the late Oligocenc: (2) heavier isotope values might be related to an increase in salinity, or (3) by a combination of both ice cap and increase in salinity.

The C37 alkenone record of sea water of time series station DYNAPROC

The concentrations of suspended particulate pigments, C37-C38 alkenones, total organic carbon and nitrogen in the Ligurian Sea (northwestern Mediterranean) have been studied at 5 and 30 m depth during well defined thermocline conditions. An accurate description of the short term changes of these compounds has been achieved by means of four 36-h sampling cycles each encompassing consecutive filtration periods of 4 h. During sampling the thermocline changes were followed closely by simultaneous measurements of water column temperature, salinity and other physical parameters. The analysis of the collected samples indicates that the Haptophyte pigments and alkenones are essentially synthesized at the levels of highest primary production and therefore the C37 alkenone record reflects the seawater temperature at this depth level. The study also shows that part of these alkenones are distributed throughout the water column in association to the suspended particles. This process results in C37 alkenone distributions that, due to their high resistance to chemical and microbial degradation, record the temperature of the highest primary productivity layers even at shallow (e.g., 5 m depth) or deep (e.g., 1100 m depth) waters.

Interstitial-water geochemistry of Kerguelen Plateau sediments

This report synthesizes all of the interstitial-water chemistry studies associated with the Kerguelen Plateau phase of ODP Leg 119. Sediments were cored at six sites (49°24'S to 59°36'S) in water depths ranging from 564 to 4082 m. A total of 77 interstitial-water samples was recovered as part of the routine sampling protocol. In addition, a novel, highresolution pore-water sampling program was tested during Leg 119 that enabled us to pinpoint reaction zones and extend our data base to deeper, drier levels that were heretofore inaccessible. Data collected include interstitial-water sodium, potassium, calcium, magnesium, pH, alkalinity, sulfate, ammonia, phosphate, aqueous silica, salinity, chloride, oxidation-reduction potentials, and sediment chemistry. The northern sector (Sites 736 and 737) is characterized by the highest sedimentation rates (up to 140 m/m.y.) and thermal gradients (70°-98°C/km) encountered on the Kerguelen Plateau during Leg 119. Site 737 represents the most reactive sediment column cored on the Kerguelen Plateau. Major cation fluxes at Site 737 are the strongest measured during Leg 119. High dissolved calcium concentrations (141.5 mM) were encountered near the bottom of Hole 737B. Elevated temperatures promote silica diagenesis and the alteration of volcanic material below 300 mbsf, and a diagenetic front was discovered near 370 mbsf at Site 737. The southern portion of the Kerguelen Plateau (Sites 738 and 744) records the lowest sedimentation rates (less than 5 m/m.y.) and thermal gradients (43°C/km) of the three study areas. Major cation fluxes at the southern sites are the lowest that we measured on the Kerguelen Plateau. High-resolution sampling provided evidence for significant silica release to the pore waters during the weathering of basement basalt. The relatively low thermal gradient does not appear to be sufficient for the formation of the opal-CT and quartz chert beds and nodules that were encountered below 120 mbsf at Site 738. Sediment-accumulation rates on the Eastern Kerguelen Sediment Ridge (Sites 745 and 746) are intermediate to those of the northern and southern sites. Deposition below the regional CCD accounts for the nearly carbonate-free, siliceous sediments. Despite their low organic carbon contents (mean = 0.15%), sediments on the Eastern Kerguelen Sediment Ridge exhibit the highest pore-water alkalinity (6.77 mM), ammonium (0.50 mM), and phosphate (23 µM) concentrations measured on the Kerguelen Plateau. Major cation fluxes are intermediate to those calculated for the northern and southern sites. The Eastern Kerguelen Sediment Ridge interstitial waters are unusual, however, in that the downward flux of magnesium is greater than the upward flux of calcium.

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.

Interstitial water chemistry of ODP Leg 103 sites

Interstitial waters were squeezed from strata recovered at Sites 637-641 of ODP Leg 103 on the Galicia margin, along the northwestern Iberian continental margin in the northeast Atlantic. Chemical profiles of Site 638 show the most complexity, which appears to be related to an unconformity in the strata between Cretaceous and Neogene sediments and to rapid deposition of Cretaceous syn-rift sediments upon pre-rift strata. Analyses of waters from all of the Leg 103 sites show generally antithetical trends for calcium and magnesium; calcium increases with depth as magnesium decreases. No calcium-magnesium 'crossover' profiles are observed in these data. Data from Site 637 show an unusual pattern; calcium increases with increasing depth, but magnesium remains relatively constant. Sulfate is either stable or shows an overall decrease with depth, and boron profiles show some structure. At all but one site (Site 638), strontium profiles do not show marked depth structure. The structure of alkalinity and silica profiles is highly site dependent. Bromide profiles are, in general, constant. In nearly every case, observed bromide concentrations are near average seawater values. Relatively low concentrations of iron and manganese are common within the upper 10 m of the sediment sequence and typically are near detection limits at deeper depths

(Table 1) Trace element/Ca ratios of Orbulina universa shells from late Neogene Mediterranean samples

A Mediterranean composite sedimentary record was analyzed for Ba/Ca ratios on carbonate shells of Orbulina universa planktonic foraminifer (Ba/Ca)carb providing the opportunity to study and assess the extent of freshwater inputs on the basin and possible impacts on its dynamics during the Tortonian to Recent period. A number of scanning electron microscope analyses and auxiliary trace element measurements (Mn, Sr, and Mg), obtained from the same samples, exclude important diagenetic effects on the studied biogenic carbonates and corroborate the reliability of (Ba/Ca)carb ratios in foraminifera calcite as indicators of seawater source components during the studied interval. A long-term trend with (Ba/Ca)carb values shifting from ~7 to 3 µmol/mol from the base of the Tortonian to the top of the Messinian is observed. The interval of the late Messinian salinity crisis, where biogenic carbonates are missing or strongly diagenized, represents a crucial passage not monitored in our record. At the base of the Pliocene, up to about 4.7 Ma, the (Ba/Ca)carb record shows a decreasing trend from ~4 µmol/mol stabilizing itself to an about constant value of 0.9 ± 0.3 µmol/mol for the whole Plio-Pleistocene interval. These results suggest a dramatic change in the continental runoff values, up to ~3-16 times higher during part of the late Neogene (Tortonian-early Pliocene), with a possible profound modification in the physical dynamics of the Mediterranean basin. First-order mass balance equations used to estimate barium and salinity budgets in the Mediterranean Sea during the late Miocene-early Pliocene interval support the hypothesis of an active connection of the basin with the Paratethys region and of a definitive restriction at the base of the Pliocene after about 0.7 Ma from the well-known Messinian Lagomare phase. They also open intriguing scenarios on possible circulation shifts during the Neogene.

Geochemistry of pore water and sediments from Exmouth Plateau

During Leg 122, a transect was drilled across the Wombat Plateau, a marginal spur of the Exmouth Plateau, complemented by two sites on the Exmouth Plateau proper. In this report, pore-water analyses for major seawater constituents, alkalinity, Ba, Fe, Mn, Li, Sr, Rb, and silica are presented. Large gradients in the pore-water profiles provide evidence of complex sediment/pore-water interactions associated with carbonate and silica diagenesis and the formation of authigenic minerals. Diffusion affects pore-water profiles but differs considerably from site to site. Advection of freshwater, probably of continental origin, helps maintain negative Cl and salinity gradients deep within the sediments of the Exmouth Plateau.

Physicochemical and photosynthetic characteristics of water samples obtained during a CCGS Amundsen cruise in 2008

During summer 2008, as part of the Circumpolar Flaw Lead system study, we measured phytoplankton photosynthetic parameters to understand regional patterns in primary productivity, including the degree and timescale of photoacclimation and how variability in environmental conditions influences this response. Photosynthesis-irradiance measurements were taken at 15 sites primarily from the depth of the subsurface chlorophyll a (Chl a) maximum (SCM) within the Beaufort Sea flaw lead polynya. The physiological response of phytoplankton to a range of light levels was used to assess maximum rates of carbon (C) fixation (P*m), photosynthetic efficiency (alpha*), photoacclimation (Ek), and photoinhibition (beta*). SCM samples taken along a transect from under ice into open water exhibited a >3-fold increase in alpha* and P*m, showing these parameters can vary substantially over relatively small spatial scales, primarily in response to changes in the ambient light field. Algae were able to maintain relatively high rates of C fixation despite low light at the SCM, particularly in the large (>5 µm) size fraction at open water sites. This may substantially impact biogenic C drawdown if species composition shifts in response to future climate change. Our results suggest that phytoplankton in this region are well acclimated to existing environmental conditions, including sea ice cover, low light, and nutrient pulses. Furthermore, this photoacclimatory response can be rapid and keep pace with a developing SCM, as phytoplankton maintain photosynthetic rates and efficiencies in a narrow ''shade-acclimated'' range.

Chemistry of pore water and solids, formation factors and salt-corrected porosities of DSDP Site 68-503

Recent discoveries relating to the circulation of fluids within the oceanic crust include the finding of both important fluxes of elements and isotopes into the oceans by ridge-crest hydrothermal convection and important fluxes of heat out of the oceanic crust by convection at ridge crests and at some distance from ridge crests. In the present chapter, I present isotopic, chemical, and physical data from sediments and pore waters of Deep Sea Drilling Project (DSDP) Holes 503A and 503B. These results are modeled in terms of pore-water diffusion, advection, and production to ascertain the relative contribution of these processes at this location, 7.5 m.y. removed from ridge-crest hydrothermal activity. The observations made here contribute to the understanding of chemical and heat transport in oceanic crust of moderate age.