Interstitial-water chemistry and stable isotope record of Prydz Bay sediments

Leg 119 of the Ocean Drilling Program (ODP) provided the first opportunity to study the interstitial-water chemistry of the eastern Antarctic continental margin. Five sites were cored in a northwest-southeast transect of Prydz Bay that extended from the top of the continental slope to within 30 km of the coastline. Geological studies of the cores reveal a continental margin that has evolved through terrestrial, glacial, and glacial-marine environments. Chemical and stable isotopic analyses of the interstitial-waters were performed to determine the types of depositional environments and the diagenetic and hydrologic processes that are operating in this unusual marine environment. Highly compacted glacial sediments provide an effective barrier to the vertical diffusion of interstitial-water solutes. Meteoric water from the Antarctic continent appears to be flowing into Prydz Bay sediments through the sequence of terrestrial sediments that lie underneath the glacial sediments. The large amounts of erosion associated with glacial advances appear to have had the effect of limiting the amount of marine organic matter that is incorporated into the sediments on the continental shelf. Although all of the sites cored in Prydz Bay exhibit depletions in dissolved sulfate with increasing depth, the greatest bacterial activity is associated with a thin layer of diatom ooze that coats the seafloor of the inner bay. Results of alkalinity modeling, thermodynamic calculations, and strontium analyses indicate that (1) ocean bottom waters seaward of Site 740 are undersaturated with respect to both calcite and aragonite, (2) interstitial waters at each site become saturated or supersaturated with respect to calcite and aragonite with increasing depth, (3) precipitation of calcium carbonate reduces the alkalinity of the pore waters with increasing depth, and (4) recrystallization of aragonite to calcite accounts for 24% of the pore-water strontium. Weathering of unstable terrestrial debris and cation exchange between clay minerals and pore fluids are the most probable chemical processes affecting interstitial water cation gradients.

Hydrographical and chemical observations during an achor station in the eastern North Atlantic

Serial observations of temperature, salinity, oxygen, alkalinity and pH are presented. They were carried out during an anchor station of R.V. "Meteor" west of Cape Sao Vincente (Portugal) in the area of the maximum Mediterranean water outflow, which follows the continental slope off Portugal. Two observational results are pointed out: The Mediterranean water masses spread out into the Atlantic Ocean, consisting of two distinct layers at depth of 700 m (T=12.0 °C, S=36.15 ?) and 1250 m (T=11.3 °C, S=36.40 ?). The salinity proved to be the most significant indicator of the observed stratification. The values of dissolved oxygen content, alkalinity and pH in the very near bottom layer (1 m above the bottom at depth of 3250 m) are different from the values at depth of 15 m to 100 m above the bottom. As this phenomenon is not observed for the salinity, the changes may be interpreted in terms of chemical and biological processes at the sediment-water interface.

Alkenone composition of water and sediment samples from the Gulf of Lions

A study of the C37 alkenone compositions in suspended particulate matter in the northwestern Mediterranean Sea has shown a correspondence between Uk'37 and sea surface temperature that significantly deviates from the general equation regularly observed in most marine world areas (Müller et al., 1998, doi:10.1016/S0016-7037(98)00097-0). However, the temperatures measured in the core top sediments using the general equation are in agreement with the annual average water column temperatures between 0-40 m depth. These discrepancies suggest that despite the rather constant correlation between UK'37 and seawater temperature throughout the world oceans, specific calibrations should be developed for each new area of application of the C37 alkenones for paleotemperature determination.

Multi-year high-frequency current and water quality in-situ observations at the Guadiana Estuary

High-frequency data collected continuously over a multiyear time frame are required for investigating the various agents that drive ecological and hydrodynamic processes in estuaries. Here, we present water quality and current in-situ observations from a fixed monitoring station operating from 2008 to 2014 in the lower Guadiana Estuary, southern Portugal (37°11.30' N, 7°24.67' W). The data were recorded by a multi-parametric probe providing hourly records (temperature, salinity, chlorophyll, dissolved oxygen, turbidity, and pH) at a water depth of ~1 m, and by a bottom-mounted acoustic Doppler current profiler measuring the pressure, near-bottom temperature, and flow velocity through the water column every 15 min. The time-series data, in particular the probe ones, present substantial gaps arising from equipment failure and maintenance, which are ineluctable with this type of observations in harsh environments. However, prolonged (months-long) periods of multi-parametric observations during contrasted external forcing conditions are available. The raw data are reported together with flags indicating the quality status of each record. River discharge data from two hydrographic stations located near the estuary head are also provided to support data analysis and interpretation.

Composition of hardgrounds and of pore-water parameters in ODP Holes 166-1008 and 166-1009

Mineralogic, petrographic, and geochemical analyses of sediments recovered from two Leg 166 Ocean Drilling Program cores on the western slope of Great Bahama Bank (308 m and 437 m water depth) are used to characterize early marine diagenesis of these shallow-water, periplatform carbonates. The most pronounced diagenetic products are well-lithified intervals found almost exclusively in glacial lowstand deposits and interpreted to have formed at or near the seafloor (i.e., hardgrounds). Hardground cements are composed of high-Mg calcite (~14 mol% MgCO3), and exhibit textures typically associated with seafloor cementation. Geochemically, hardgrounds are characterized by increased d18O and Mg contents and decreased d13C, Sr, and Na contents relative to their less lithified counterparts. Despite being deposited in shallow waters that are supersaturated with the common carbonate minerals, it is clear that these sediments are also undergoing shallow subsurface diagenesis. Calculation of saturation states shows that pore waters become undersaturated with aragonite within the upper 10 m at both sites. Dissolution, and likely recrystallization, of metastable carbonates is manifested by increases in interstitial water Sr and Sr/Ca profiles with depth. We infer that the reduction in mineral saturation states and subsequent dissolution are being driven by the oxidation of organic matter in this Fe-poor carbonate system. Precipitation of burial diagenetic phases is indicated by the down-core appearance of dolomite and corresponding decrease in interstitial water Mg, and the presence of low-Mg calcite cements observed in scanning electron microscope photomicrographs.

Maxima of interstitial water and gas parameters in ODP Leg 182 sediments

During the drilling of the southern Australian continental margin (Leg 182 of the Ocean Drilling Program), fluids with unusually high salinities (to 106?) were encountered in Miocene to Pleistocene sediments. At three sites (1127, 1129, and 1131), high contents of H2S (to 15%), CH4 (50%), and CO2 (70%) were also encountered. These levels of H2S are the highest yet reported during the history of either the Deep Sea Drilling Project or the Ocean Drilling Program. The high concentrations of H2S and CH4 are associated with anomalous Na+/Cl- ratios in the pore waters. Although hydrates were not recovered, and despite the shallow water depth of these sites (200-400 m) and relative warm bottom water temperatures (11-14°C), we believe that these sites possess disseminated H2S-dominated hydrates. This contention is supported by calculations using the measured gas concentrations and temperatures of the cores, and depths of recovery. High concentrations of H2S necessary for the formation of hydrates under these conditions were provided by the abundant (SO4)2- caused by the high salinities of the pore fluids, and the high concentrations of organic material. One hypothesis for the origin of these fluids is that they were formed on the adjacent continental shelf during previous lowstands of sea level and were forced into the sediments under the influence of hydrostatic head.

Stable isotope ratios and foraminiferal abundance of sediment cores from the Western Iberian Margin

Rapid climate changes at the onset of the last deglaciation and during Heinrich Event H4 were studied in detail at IMAGES cores MD95-2039 and MD95-2040 from the Western Iberian margin. A major reorganisation of surface water hydrography, benthic foraminiferal community structure, and deepwater isotopic composition commenced already 540 years before the Last Isotopic Maximum (LIM) at 17.43 cal. ka and within 670 years affected all environments. Changes were initiated by meltwater spill in the Nordic Seas and northern North Atlantic that commenced 100 years before concomitant changes were felt off western Iberia. Benthic foraminiferal associations record the drawdown of deepwater oxygenation during meltwater and subsequent Heinrich Events H1 and H4 with a bloom of dysoxic species. At a water depth of 3380 m, benthic oxygen isotopes depict the influence of brines from sea ice formation during ice-rafting pulses and meltwater spill. The brines conceivably were a source of ventilation and provided oxygen to the deeper water masses. Some if not most of the lower deep water came from the South Atlantic. Benthic foraminiferal assemblages display a multi-centennial, approximately 300-year periodicity of oxygen supply at 2470-m water depth. This pattern suggests a probable influence of atmospheric oscillations on the thermohaline convection with frequencies similar to Holocene climate variations. For Heinrich Events H1 and H4, response times of surface water properties off western Iberia to meltwater injection to the Nordic Seas were extremely short, in the range of a few decades only. The ensuing reduction of deepwater ventilation commenced within 500-600 years after the first onset of meltwater spill. These fast temporal responses lend credence to numerical simulations that indicate ocean-climate responses on similar and even faster time scales.

Part of the global DOC versus AOU (dissolved organic carbon/apparent oxygen utilization) data compilation, Arabian Sea

Concentrations of total organic carbon (TOC) were determined on samples collected during six cruises in the northern Arabian Sea during the 1995 US JGOFS Arabian Sea Process Study. Total organic carbon concentrations and integrated stocks in the upper ocean varied both spatially and seasonally. Highest mixed-layer TOC concentrations (80-100 µM C) were observed near the coast when upwelling was not active, while upwelling tended to reduce local concentrations. In the open ocean, highest mixed-layer TOC concentrations (80-95 µM C) developed in winter (period of the NE Monsoon) and remained through mid summer (early to mid-SW Monsoon). Lowest open ocean mixed-layer concentrations (65-75 µM C) occurred late in the summer (late SW Monsoon) and during the Fall Intermonsoon period. The changes in TOC concentrations resulted in seasonal variations in mean TOC stocks (upper 150 m) of 1.5-2 mole C/m**2, with the lowest stocks found late in the summer during the SW Monsoon-Fall Intermonsoon transition. The seasonal accumulation of TOC north of 15°N was 31-41 x 10**12 g C, mostly taking place over the period of the NE Monsoon, and equivalent to 6-8% of annual primary production estimated for that region in the mid-1970s. A net TOC production rate of 12 mmole C/m**2/d over the period of the NE Monsoon represented ~80% of net community production. Net TOC production was nil during the SW Monsoon, so vertical export would have dominated the export terms over that period. Total organic carbon concentrations varied in vertical profiles with the vertical layering of the water masses, with the Persian Gulf Water TOC concentrations showing a clear signal. Deep water (>2000 m) TOC concentrations were uniform across the basin and over the period of the cruises, averaging 42.3±1.4 µM C.

Interstitial-water chemistry of ODP Leg 113 sites

Variations in the distribution of major elements and stable oxygen isotopes in ODP Leg 113 pore water are not related to lithology and thus appear to be controlled by minor constituents. Petrographic observations and geochemical considerations indicate that alteration of calc-alkalic volcanic material dispersed in the sediment is an important process. A diagenetic reaction is constructed that involves transformation of volcanic glass into smectite, zeolite (represented by phillipsite), chert, and iron sulfide. Mass balance calculations reveal that alteration of less than 10% (volume) of volcanogenic material may account for the observed depletion of magnesium, potassium, and 18O and enrichment of calcium. Alteration of this amount of volcanic glass produces less than 4% (volume) of smectite and zeolite. Hence, mass balance is obtained without having to invoke unreasonable large amounts of volcanic matter or interactions between seawater and basement.

Hydrochemistry measured on water bottle samples during the METEOR International Indian Ocean Expedition 1964/65

The present volume gives the observed physical and chemical data obtained by R.V. "Meteor" in the Indian Ocean during cruise 1964/65. The tables are based on the computations made by the National Oceanographic Data Center (NODC) in Washington. In addition to the normally communicated data, the tables contain four chemical parameters: alkalinity, ammonia, fluoride, and calcium.

Part of the global DOC versus AOU (dissolved organic carbon/apparent oxygen utilization) data compilation, BATS

The contributions of total organic carbon and nitrogen to elemental cycling in the surface layer of the Sargasso Sea are evaluated using a 5-yr time-series data set (1994-1998). Surface-layer total organic carbon (TOC) and total organic nitrogen (TON) concentrations ranged from 60 to 70 µM C and 4 to 5.5 µM N seasonally, resulting in a mean C : N molar ratio of 14.4±2.2. The highest surface concentrations varied little during individual summer periods, indicating that net TOC production ceased during the highly oligotrophic summer season. Winter overturn and mixing of the water column were both the cause of concentration reductions and the trigger for net TOC production each year following nutrient entrainment and subsequent new production. The net production of TOC varied with the maximum in the winter mixed-layer depth (MLD), with greater mixing supporting the greatest net production of TOC. In winter 1995, the TOC stock increased by 1.4 mol C/m**2 in response to maximum mixing depths of 260 m. In subsequent years experiencing shallower maxima in MLD (<220 m), TOC stocks increased <0.7 mol C/m**2. Overturn of the water column served to export TOC to depth (>100 m), with the amount exported dependent on the depth of mixing (total export ranged from 0.4 to 1.4 mol C/m**2/yr). The exported TOC was comprised both of material resident in the surface layer during late summer (resident TOC) and material newly produced during the spring bloom period (fresh TOC). Export of resident TOC ranged from 0.5 to 0.8 mol C/m**2/yr, covarying with the maximum winter MLD. Export of fresh TOC varied from nil to 0.8 mol C/m**2/yr. Fresh TOC was exported only after a threshold maximum winter MLD of ~200 m was reached. In years with shallower mixing, fresh TOC export and net TOC production in the surface layer were greatly reduced. The decay rates of the exported TOC also covaried with maximum MLD. The year with deepest mixing resulted in the highest export and the highest decay rate (0.003 1/d) while shallow and low export resulted in low decay rates (0.0002 1/d), likely a consequence of the quality of material exported. The exported TOC supported oxygen utilization at dC : dO2 molar ratios ranging from 0.17 when TOC export was low to 0.47 when it was high. We estimate that exported TOC drove 15-41% of the annual oxygen utilization rates in the 100-400 m depth range. Finally, there was a lack of variability in the surface-layer TON signal during summer. The lack of a summer signal for net TON production suggests a small role for N2 fixation at the site. We hypothesize that if N2 fixation is responsible for elevated N : P ratios in the main thermocline of the Sargasso Sea, then the process must take place south of Bermuda and the signal transported north with the Gulf Stream system.