Carbonate properties and oxygen concentrations at time series station DYFAMED

Monthly measurements of pH, alkalinity and oxygen over two years (February 1998-February 2000) at the Dyfamed site in the central zone of the Ligurian-Provençal Basin of the Mediterranean made it possible to assess the vertical distributions (5-2000 m) and the seasonal variations of these properties. Alkalinity varies linearly with salinity between surface water and the Levantine Intermediate Water (marked by a maximum of temperature and salinity). In deep water, total alkalinity is also correlated linearly to salinity, but the slope of the regression line is 15% less. In surface water, the pH at 25°C varies between 7.91 and 8.06 on the total proton scale depending upon the season. The lowest values are observed in winter, the highest in spring and in summer. These variations are primarily due to biological production. The pH goes through a minimum around 150-200 m and a small maximum below the intermediate water. The total dissolved inorganic carbon content (deduced from pH and alkalinity) is variable in surface water (2205-2310 ?mol/kg) and has a maximum in intermediate water, which is related to the salinity maximum. Normalized total inorganic carbon at a constant salinity is strongly negatively correlated with pH at 25°C. The fugacity of CO2, (fCO2) varies between 320 and 430 ?atm in surface water, according to the season. Below the seasonal thermocline, the maximum fCO2 (about 410 ?atm) is located around 150-200 m. The presence of a minimum of oxygen in the intermediate water of this area has been observed for several years, but our measurements made it possible to specify the relationship between oxygen and salinity in deep water. Data from the intense vertical mixing during the winters of 1999 and 2000 were used to calculate the oxygen quantity exchanged with the atmosphere during these periods. The estimated quantity of oxygen entering the Mediterranean Sea exceeds that deduced from exchange coefficients calculated with the formula of Wanninkhof and McGillis. During the vertical mixing in the 1999 winter, fCO2 in surface water was on average below equilibrium with atmospheric fCO2, thus implying that CO2 was entering the sea. However, on this time scale, even with high exchange coefficients, the estimated CO2 uptake had no significant influence on the inorganic carbon content in the water column.

Physical properties, compressional-wave velocity and consolidation characteristics of ODP Holes 133-815B and 133-817B

Sites 815 and 817 were drilled near the Townsville Trough during Leg 133 of the Ocean Drilling Program. The physical properties, compressional-wave velocity, and consolidation characteristics indicate that the periplatform carbonate sediments maintain more water content and lower compressional velocity near the Queensland Plateau than the clayey hemipelagic sediments, which have a clay content of up to 60%. Bulk density, void ratio or porosity, water content, and compressional-wave velocity are shown to have a linear relationship with burial depth. Between 3.5 and 5 Ma (about 100-500 mbsf), these physical properties maintained a constant rate vs. the depth in core because of the fast sedimentation-rate effect at Site 815. However, compressionalwave velocity still increases downward in this section. The clay content in this section causes an increase of bulk modulus and compaction effect. At Site 817, scarce terrigenous mud content and abundant carbonate content (88%-97%) cause a straight line relationship between physical properties and burial depth. During the consolidation test, we show that dominant micritic particles may cause faster acoustic velocity than sediments composed mainly of coccoliths. The bulk modulus ratio increasing rate in the clay-rich carbonate sediments is almost 4.5 times higher than in the clay-free periplatform carbonate sediments.

Consolidation properties and hydraulic conductivities of sediments from ODP Leg 207 sites

The stress history, permeability, and compressibility of sediments from Demerara Rise recovered during Ocean Drilling Program Leg 207 were determined using one-dimensional incremental load consolidation and low-gradient flow pump permeability tests. Relationships among void ratio, effective stress, and hydraulic conductivity are presented for sampled lithologic units and used to reconstruct effective stress, permeability, and in situ void ratio profiles for a transect of three sites across Demerara Rise. Results confirm that a significant erosional event occurred on the northeastern flank of the rise during the late Miocene, resulting in the removal of ~220 m of upper Oligocene-Miocene deposits. Although Neogene and Paleogene sediments tend to be overconsolidated, Cretaceous sediments are normally consolidated to underconsolidated, suggesting the presence of overpressure. A pronounced drop in permeability occurs at the transition from the Cretaceous black shales into the overlying Maastrichtian-upper Paleocene chalks and clays. The development of a hydraulic seal at this boundary may be responsible for overpressure in the Cretaceous deposits, leading to the lower overconsolidation ratios of these sediments. Coupled with large regional variations in sediment thickness (overburden stresses), the higher permeability overpressured Cretaceous sediments represent a regional lateral fluid conduit on Demerara Rise, possibly venting methane-rich fluids where it outcrops on the margin's northeastern flank.

Physical properties and bulk minerals from IODP Holes 308-U1322B, U1322D and U1324B

How the micro-scale fabric of clay-rich mudstone evolves during consolidation in early burial is critical to how they are interpreted in the deeper portions of sedimentary basins. Core samples from the Integrated Ocean Drilling Program Expedition 308, Ursa Basin, Gulf of Mexico, covering seafloor to 600 meters below sea floor (mbsf) are ideal for studying the micro-scale fabric of mudstones. Mudstones of consistent composition and grain size decrease in porosity from 80% at the seafloor to 37% at 600 mbsf. Argon-ion milling produces flat surfaces to image this pore evolution over a vertical effective stress range of 0.25 (71 mbsf) to 4.05 MPa (597 mbsf). With increasing burial, pores become elongated, mean pore size decreases, and there is preferential loss of the largest pores. There is a small increase in clay mineral preferred orientation as recorded by high resolution X-ray goniometry with burial.

Seismic velocities and elastic properties of gabbroic rocks from ODP Hole 118-735B

The nearly continuous recovery of 0.5 km of generally fresh, layer 3 gabbroic rocks at Hole 735B, especially near the bottom of the section, presents scientists an unusual opportunity to study the detailed elastic properties of the lower oceanic crust. Extending compressional-wave and density shipboard measurements at room pressure, Vp and Vs were measured at pressures from 20 to 200 MPa using the pulse transmission method. All of the rocks exhibit significant increases in velocity with increasing pressure up to about 150 MPa, a feature attributed to the closing of microcrack porosity. Measured velocities reflect the mineralogical makeup and microstructures acquired during the tectonic history of Hole 735B. Most of the undeformed and unaltered gabbros are approximately 65:35 plagioclase/clinopyroxene rocks plus olivine or oxide minerals, and the observed densities and velocities are fully consistent with the Voigt-Reuss-Hill (VRH) averages of the component minerals and their proportions. Depending on their olivine content, the predominant olivine gabbros at 200 MPa have average Vp = 7.1 ± 0.2 km/s, Vs = 3.9 ± 0.1 km/s, and grain densities of 2.95 ± 0.5 g/cm3. The less abundant iron-titanium (Fe-Ti) oxide gabbros average Vp = 6.75 ± 0.15 km/s, Vs = 3.70 ± 0.1 km/s, and grain densities of 3.22 ± 0.05 g/cm3, reflecting the higher densities and lower velocities of oxide minerals compared to olivine. About 30% of the core is plastically deformed, and the densities and directionally averaged velocities of these shear-zone tectonites are generally consistent with those of the gabbros, their protoliths. Three sets of observations indicate that the shear-zone metagabbros are elastically anisotropic: (1) directional variations in Vp, both vertical and horizontal and with respect to foliation and lineation; (2) discrepancies among Vp values for the horizontal cores and the VRH averages of the component minerals and their mineral proportions, suggesting preferred crystallographic orientations of anisotropic minerals; and (3) variations of Vs of up to 7%, with polarization directions parallel and perpendicular to foliation. Optical inspection of thin sections of the same samples indicates that plagioclase feldspar, clinopyroxene, and amphibole typically display crystallographic-preferred orientations, and this, plus the elastic anisotropy of these minerals, suggests that preferred orientations are responsible for much of the observed anisotropy, particularly at high pressure. Alteration tends to be localized to brittle faults and brecciated zones, and typical alteration minerals are amphibole and secondary plagioclase, which do not significantly change the velocity-density relationships.

Physical properties and AMS characteristics of ODP Site 185-1149 sediments

During Ocean Drilling Program Leg 185, we studied progressive changes of microfabrics of unconsolidated pelagic and hemipelagic sediments in Holes 1149A and 1149B in the northwest Pacific at 5818 m water depth. We paid particular attention to the early consolidation and diagenetic processes without tectonic deformation before the Pacific plate subduction at the Izu-Bonin Trench. Shape, size, and arrangement of pores were analyzed by scanning electron microscope (SEM) and were compared to anisotropy of magnetic susceptibility (AMS) data. The microfabric in Unit I is nondirectional fabric and is characterized by large peds of ~10-100 µm diameter, which are made up of clay platelets (mainly illite) and siliceous biogenic fragments. They are ovoid in shape and are mechanically packed by benthic animals. Porosity decreases from 0 to 60 meters below seafloor (mbsf) in Unit I (from 60% to 50%) in association with macropore size decreases. The microfabric of coarser grain particles other than clay in Unit II is characterized by horizontal preferred orientation because of depositional processes in Subunit IIA and burial compaction in Subunit IIB. On the other hand, small peds, which are probably made of fragments of fecal pellets and are composed of smectite and illite (3-30 µm diameter), are characterized by random orientation of clay platelets. The clay platelets in the small peds in Subunit IIA are in low-angle edge-to-face (EF) or face-to-face (FF) contact. These peds are electrostatically connected by long-chained clay platelets, which are interconnected by high-angle EF contact. Breaking of these long chains by overburden pressure diminishes the macropores, and the clay platelets in the peds become FF in contact, resulting in decreases in the volume of the micropores between clay platelets. Thus, porosity in Subunits IIA and IIB decreases remarkably downward. The AMS indicates random fabric and horizontal preferred orientation fabric in Units I and II, respectively. This result corresponds to that of SEM microfabric observations.In Subunit IIB, pressure solutions around radiolarian tests and clinoptilolite veins with normal displacement sense are seen distinctively below ~170 mbsf, probably in correspondence to the transition zone from opal-A to opal-CT.

Properties and faunal abundances of level sea ice and sea-ice ridges in the Chukchi/Beaufort Seas and Canada Basin

The abundances and distribution of metazoan within-ice meiofauna (13 stations) and under-ice fauna (12 stations) were investigated in level sea ice and sea-ice ridges in the Chukchi/Beaufort Seas and Canada Basin in June/July 2005 using a combination of ice coring and SCUBA diving. Ice meiofauna abundance was estimated based on live counts in the bottom 30 cm of level sea ice based on triplicate ice core sampling at each location, and in individual ice chunks from ridges at four locations. Under-ice amphipods were counted in situ in replicate (N=24-65 per station) 0.25 m**2 quadrats using SCUBA to a maximum water depth of 12 m. In level sea ice, the most abundant ice meiofauna groups were Turbellaria (46%), Nematoda (35%), and Harpacticoida (19%), with overall low abundances per station that ranged from 0.0 to 10.9 ind/l (median 0.8 ind/l). In level ice, low ice algal pigment concentrations (<0.1-15.8 µg Chl a /l), low brine salinities (1.8-21.7) and flushing from the melting sea ice likely explain the low ice meiofauna concentrations. Higher abundances of Turbellaria, Nematoda and Harpacticoida also were observed in pressure ridges (0-200 ind/l, median 40 ind/l), although values were highly variable and only medians of Turbellaria were significantly higher in ridge ice than in level ice. Median abundances of under-ice amphipods at all ice types (level ice, various ice ridge structures) ranged from 8 to 114 ind/m**2 per station and mainly consisted of Apherusa glacialis (87%), Onisimus spp. (7%) and Gammarus wilkitzkii (6%). Highest amphipod abundances were observed in pressure ridges at depths >3 m where abundances were up to 42-fold higher compared with level ice. We propose that the summer ice melt impacted meiofauna and under-ice amphipod abundance and distribution through (a) flushing, and (b) enhanced salinity stress at thinner level sea ice (less than 3 m thickness). We further suggest that pressure ridges, which extend into deeper, high-salinity water, become accumulation regions for ice meiofauna and under-ice amphipods in summer. Pressure ridges thus might be crucial for faunal survival during periods of enhanced summer ice melt. Previous estimates of Arctic sea ice meiofauna and under-ice amphipods on regional and pan-Arctic scales likely underestimate abundances at least in summer because they typically do not include pressure ridges.

Table 1. Pressure, temperature and isotope ratios between H2O and CO2 for all experiments

Traditionally, the application of stable isotopes in Carbon Capture and Storage (CCS) projects has focused on d13C values of CO2 to trace the migration of injected CO2 in the subsurface. More recently the use of d18O values of both CO2 and reservoir fluids has been proposed as a method for quantifying in situ CO2 reservoir saturations due to O isotope exchange between CO2 and H2O and subsequent changes in d18OH2O values in the presence of high concentrations of CO2. To verify that O isotope exchange between CO2 and H2O reaches equilibrium within days, and that d18OH2O values indeed change predictably due to the presence of CO2, a laboratory study was conducted during which the isotope composition of H2O, CO2, and dissolved inorganic C (DIC) was determined at representative reservoir conditions (50°C and up to 19 MPa) and varying CO2 pressures. Conditions typical for the Pembina Cardium CO2 Monitoring Pilot in Alberta (Canada) were chosen for the experiments. Results obtained showed that d18O values of CO2 were on average 36.4±2.2 per mil (1 sigma, n=15) higher than those of water at all pressures up to and including reservoir pressure (19 MPa), in excellent agreement with the theoretically predicted isotope enrichment factor of 35.5 per mil for the experimental temperatures of 50°C. By using 18O enriched water for the experiments it was demonstrated that changes in the d18O values of water were predictably related to the fraction of O in the system sourced from CO2 in excellent agreement with theoretical predictions. Since the fraction of O sourced from CO2 is related to the total volumetric saturation of CO2 and water as a fraction of the total volume of the system, it is concluded that changes in d18O values of reservoir fluids can be used to calculate reservoir saturations of CO2 in CCS settings given that the d18O values of CO2 and water are sufficiently distinct.