Tab. 1 Mole % CO2 and 13C values of CO2 at baseline and at the final monitoring event for the eight observation wells

During CO2 storage operations in mature oilfields or saline aquifers it is desirable to trace the movement of injected CO2 for verification and safety purposes. We demonstrate the successful use of carbon isotope abundance ratios for tracing the movement of CO2 injected at the Cardium CO2 Storage Monitoring project in Alberta between 2005 and 2007. Injected CO2 had a d13C value of -4.6±1.1 per mil that was more than 10 per mil higher than the carbon isotope ratios of casing gas CO2 prior to CO2 injection with average d13C values ranging from -15.9 to -23.5 per mil. After commencement of CO2 injection, d13C values of casing gas CO2 increased in all observation wells towards those of the injected CO2 consistent with a two-source end-member mixing model. At four wells located in a NE-SW trend with respect to the injection wells, breakthrough of injected CO2 was registered chemically (>50 mol % CO2) and isotopically 1-6 months after commencement of CO2 injection resulting in cumulative CO2 fluxes exceeding 100000 m**3 during the observation period. At four other wells, casing gas CO2 contents remained below 5 mol % resulting in low cumulative CO2 fluxes (<2000 m**3) throughout the entire observation period, but carbon isotope ratios indicated contributions between <30 and 80% of injected CO2. Therefore, we conclude that monitoring the movement of CO2 in the injection reservoir with geochemical and isotopic techniques is an effective approach to determine plume expansion and to identify potential preferential flow paths provided that the isotopic composition of injected CO2 is constant and distinct from that of baseline CO2.

Paleomegnetic and geochemistry of sediments from the early Aptian Oceanic Anoxic Event

The early Aptian Oceanic Anoxic Event (OAE1a, 120 Ma) represents a geologically brief time interval in the mid-Cretaceous greenhouse world that is characterized by increased organic carbon accumulation in marine sediments, sudden biotic changes, and abrupt carbon-isotope excursions indicative of significant perturbations to global carbon cycling. The brevity of these drastic environmental changes (< 10**6 year) and the typically 10**6 year temporal resolution of the available chronologies, however, represent a critical gap in our knowledge of OAE1a. We have conducted a high-resolution investigation of three widely distributed sections, including the Cismon APTICORE in Italy, Santa Rosa Canyon in northeastern Mexico, and Deep Sea Drilling Project (DSDP) Site 398 off the Iberian margin in the North Atlantic Ocean, which represent a range of depositional environments where condensed and moderately expanded OAE1a intervals are recorded. The objectives of this study are to establish orbital chronologies for these sections and to construct a common, high-resolution timescale for OAE1a. Spectral analyses of the closely-spaced (corresponding to ~5 to 10 kyr) measurements of calcium carbonate content of the APTICORE, magnetic susceptibility (MS) and anhysteretic remanent magnetization (ARM) of the Santa Rosa samples, and MS, ARM and ARM/IRM, where IRM is isothermal remanent magnetization, of Site 398 samples reveal statistically significant cycles. These cycles exhibit periodicity ratios and modulation patterns similar to those of the mid-Cretaceous orbital cycles, suggesting that orbital variations may have modulated depositional processes. Orbital control allows us to estimate the duration of unique, globally identifiable stages of OAE1a. Although OAE1a had a duration of ~1.0 to 1.3 Myr, the initial perturbation represented by the negative carbon-isotope excursion was rapid, lasting for ~27-44 kyr. This estimate could serve as a basis for constraining triggering mechanisms for OAE1a.

Stable isotope and geochemical record of sediments from the Bering Sea

here is controversy over the role of marine methane hydrates in atmospheric methane concentrations and climate change during the last glacial period. In this study of two sediment cores from the southeast Bering Sea (700 m and 1467 m water depth), we identify multiple episodes during the last glacial period of intense methane flux reaching the seafloor. Within the uncertainty of the radiocarbon age model, the episodes are contemporaneous in the two cores and have similar timing and duration as Dansgaard-Oeschger events. The episodes are marked by horizons of sediment containing 13C-depleted authigenic carbonate minerals; 13C-depleted archaeal and bacterial lipids, which resemble those found in ANME-1 type anaerobic methane oxidizing microbial consortia; and changes in the abundance and species distribution of benthic foraminifera. The similar timing and isotopic composition of the authigenic carbonates in the two cores is consistent with a region-wide increase in the upward flux of methane bearing fluids. This study is the first observation outside Santa Barbara Basin of pervasive, repeated methane flux in glacial sediments. However, contrary to the "Clathrate Gun Hypothesis" (Kennett et al., 2003), these coring sites are too deep for methane hydrate destabilization to be the cause, implying that a much larger part of the ocean's sedimentary methane may participate in climate or carbon cycle feedback at millennial timescales. We speculate that pulses of methane in these opal-rich sediments could be caused by the sudden release of overpressure in pore fluids that builds up gradually with silica diagenesis. The release could be triggered by seismic shaking on the Aleutian subduction zone caused by hydrostatic pressure increase associated with sea level rise at the start of interstadials.

(Table 1) 40Ar-39Ar incremental heating ages for ODP Hole 163-988A basalt and plagioclase

Results of 40Ar-39Ar Ar dating constrain the age of the submerged volcanic succession, part of the seaward-dipping reflector sequence of the Southeast Greenland volcanic rifted margin, recovered during Leg 163. At the 63ºN drilling transect, the fully normally magnetized volcanic units at Holes 989B (Unit 1) and 990A (Units 1 and 2) are dated at 57.1 ± 1.3 Ma and 55.6 ± 0.6 Ma, respectively. This correlates with a common magnetochron, C25n. The underlying, reversely magnetized lavas at Hole 990A (Units 3-13) yield an average age of 55.8 ± 0.7 Ma and may correlate with C25r. The argon data, however, are also consistent with eruption of the lavas at Site 990 during the very earliest portion of C24. If so, the normally polarized units have to be correlated to a cryptochron (e.g., C24r-11 at ~55.57 Ma). The lavas at Holes 989B and 990A have typical oceanic compositions, implying that final plate separation between Greenland and northwest Europe took place at ~56 Ma. The age for Hole 989B lava is younger than expected from the seismic interpretations, posing questions about the structural evolution of the margin. An age of 49.6 ± 0.2 Ma for the basaltic lava at Site 988 (~66ºN) points to the importance of postbreakup tholeiitic magmatism at the rifted margin. Together with results from Leg 152, a virtually complete time frame for ~12 m.y. of pre-, syn-, and postbreakup volcanism during rifted margin evolution in Southeast Greenland can now be assembled. This time frame includes continental type volcanism at ~61-60 Ma, synbreakup volcanism beginning at ~57 Ma, and postbreakup volcanism at ~49.6 Ma. These discrete time windows coincide with distinct periods of tholeiitic magmatism from the onshore East Greenland Tertiary Igneous Province and is consistent with discrete mantle-melting events triggered by plume arrival (~61-60 Ma) under central Greenland, continental breakup (~57-54 Ma), and passage of the plume axis beneath the East Greenland rifted margin after breakup (~50-49 Ma), respectively.

(Table 1) Physical properties of basalts from DSDP Holes 69-504B and 70-504B

A detailed study of physical properties was made on core samples from Deep Sea Drilling Project Hole 504B. The measured properties are density, porosity, sonic velocity, electrical resistivity, and fluid permeability. Basalts from this young oceanic crust have higher density and sonic velocity than the average DSDP basalts. Porosity (and temperature) dependences of physical properties are given by V = Vo - a-phi; roo = roo-0 exp(E*/RT)phi**-q; k = k0' phi**2q-1; where V is the sonic velocity (km/s), Vo = 6.45 (km/s), a = 0.111 (km/s %), phi is the porosity (%), roo is the electrical resistivity (ohm m), roo-0 = 0.002 (ohm m), E* = 2.7 (Kcal/mol) for fresh basalts, RT has its usual meaning, q = 1.67 ± 0.27, k is the permeability, k0' = (1 to about 10) x 10**-12 (cm**2). Porosity distribution in the crust in this area is estimated by combining the seismic velocity distribution and velocity-porosity relation. Because of the rapid decrease in porosity with depth, resistivity increases and permeability decreases rapidly with depth. The decreasing rate of permeability with increasing depth is approximately given by k(cm**2) = 2 x 10**-10 exp(-z (km)/0.3).

Age models and stable isotope ratios from the Mid-Miocene

Mid-Miocene pelagic sedimentary sections can be correlated using intermediate and high resolution oxygen and carbon isotopic records of benthic foraminifera. Precision of a few tens of thousands of years is readily achievable at sites with high sedimentation rates, for example, Deep Sea Drilling Project sites 289 and 574. The mid-Miocene carbon isotope records are characterized by an interval of high d13C values between 17 and 13.5 Ma (the Monterey Excursion of Vincent and Berger 1985) upon which are superimposed a series of periodic or quasi-periodic fluctuations in d13C values. These fluctuations have a period of approximately 440 kyr, suggestive of the 413 kyr cycle predicted by Milankovitch theory. Vincent and Berger proposed that the Monterey Excursion was the result of increased organic carbon burial in continental margins sediments. The increased d13C values (called 13C maxima) superimposed on the generally high mid-Miocene signal coincide with increases in d18O values suggesting that periods of cooling and/or ice buildup were associated with exceptionally rapid burial of organic carbon and lowered atmospheric CO2 levels. It is likely that during the Monterey Excursion the ocean/atmosphere system became progressively more sensitive to small changes in insolation, ultimately leading to major cooling of deep water and expansion of continental ice. We have assigned an absolute chronology, based on biostratigraphic and magneto-biostratigraphic datum levels, to the isotope stratigraphy and have used that chronology to correlate unconformities, seismic reflectors, carbonate minima, and dissolution intervals. Intervals of sediment containing 13C maxima are usually better preserved than the overlying and underlying sediments, indicating that the d13C values of TCO2 in deep water and the corrosiveness of seawater are inversely correlated. This again suggests that the 13C maxima were associated with rapid burial of organic carbon and reduced levels of atmospheric CO2. The absolute chronology we have assigned to the isotopic record indicates that the major mid-Miocene deepwater cooling/ice volume expansion took 2 m.y. and was not abrupt as had been reported previously. The cooling appears abrupt at many sites because the interval is characterized by a number of dissolution intervals. The cooling was not monotonic, and the 2 m.y. interval included an episode of especially rapid cooling as well as a brief return to warmer conditions before the final phase of the cooling period. The increase in d18O values of benthic foraminifera between 14.9 and 12.9 Ma was greatest at deeper water sites and at sites closest to Antarctica. The data suggest that the d18O value of seawater increased by no more than about 1.1 per mil during this interval and that the remainder of the change in benthic d18O values resulted from cooling in Antarctic regions of deepwater formation. Equatorial planktonic foraminifera from sites 237 and 289 exhibit a series of 0.4 per mil steplike increases in d13C values. Only one of these increases in planktonic d13C is correlated with any of the features in the mid-Miocene benthic carbon isotope record.

Seismic properties of sheeted dikes from ODP Hole 111-504B

Seismic velocities have been measured at confining pressures to 600 MPa for eight samples of sheeted dike rock obtained from Hole 504B during Leg ODP 111. The compressional- and shear-wave velocities are, in general, higher than the velocities measured in overlying dike rocks obtained from the hole during DSDP Leg 83. The velocity gradients observed in Layer 2C result from decreasing porosity with depth and increasing metamorphic grade. The laboratory-measured velocities of the Leg 111 dike rocks are similar to those of dike rocks reported for the Bay of Islands, Samail, and Troodos ophiolites.

Thermal conductivity at DSDP Leg 60 Holes

A total of 1547 thermal conductivity values were determined by both the NP (needle probe method) and the QTM (quick thermal conductivity meter) on 1319 samples recovered during DSDP Leg 60. The NP method is primarily for the measurement of soft sedimentary samples, and the result is free from the effect of porewater evaporation. Measurement by the QTM method is faster and is applicable to all types of samples-namely, sediments (soft, semilithified, and lithified) and basement rocks. Data from the deep holes at Sites 453, 458, and 459 show that the thermal conductivity increases with depth, the rate of increase ranging from (0.18 mcal/cm s °C)/100 m at Site 459 to (0.72 mcal/cm s °C)/100 m at Site 456. A positive correlation between the sedimentary accumulation rate and the rate of thermal conductivity increase with depth indicates that both compaction and lithification are important factors. Drilled pillow basalts show nearly uniform thermal conductivity. At She 454 the thermal conductivity of one basaltic flow unit was higher near the center of the unit and lower toward the margin, reflecting variable vesicularity. Hydrothermally altered basalts at Site 456 showed higher thermal conductivity than fresh basalt because secondary calcite, quartz, and pyrite are generally more thermally conductive than fresh basalt. The average thermal conductivity in the top 50 meters of sediments correlates inversely with water depth because of dissolution of calcite, a mineral with high thermal conductivity, from the sediments as the water depth exceeds the lysocline and the carbonate compensation depth. Differences between the Mariana Trench data and the Mariana Basin and Trough data may reflect different abundances of terrigenous material in the sediment. There are remarkable correlations between thermal conductivity and other physical properties. The relationship between thermal conductivity and compressional wave velocity can be used to infer the ocean crustal thermal conductivity from the seismic velocity structure.