Table 1. Mean geochemical values for Baseline (pre-injection) and Monitor-1 (post-injection) samples, and the percent change between the two weighted means

The Weyburn Oil Field, Saskatchewan is the site of a large (5000 tonnes/day of CO2) CO2-EOR injection project By EnCana Corporation. Pre- and post-injection samples (Baseline and Monitor-1, respectively) of produced fluids from approximately 45 vertical wells were taken and chemically analyzed to determine changes in the fluid chemistry and isotope composition between August 2000 and March 2001. After 6 months of CO2 injection, geochemical parameters including pH, [HCO3], [Ca], [Mg], and ?13CO2(g) point to areas in which injected CO2 dissolution and reservoir carbonate mineral dissolution have occurred. Pre-injection fluid compositions suggest that the reservoir brine in the injection area may be capable of storing as much as 100 million tonnes of dissolved CO2. Modeling of water-rock reactions show that clay minerals and feldspar, although volumetrically insignificant, may be capable of acting as pH buffers, allowing injected CO2 to be stored as bicarbonate in the formation water or as newly precipitated carbonate minerals, given favorable reaction kinetics.

(Table 1) Gravity and pressure within the Sleipner area relative to ones at the reference station in 2002 and 2005

At Sleipner, CO2 is being separated from natural gas and injected into an underground saline aquifer for environmental purposes. Uncertainty in the aquifer temperature leads to uncertainty in the in situ density of CO2. In this study, gravity measurements were made over the injection site in 2002 and 2005 on top of 30 concrete benchmarks on the seafloor in order to constrain the in situ CO2 density. The gravity measurements have a repeatability of 4.3 µGal for 2003 and 3.5 µGal for 2005. The resulting time-lapse uncertainty is 5.3 µGal. Unexpected benchmark motions due to local sediment scouring contribute to the uncertainty. Forward gravity models are calculated based on both 3D seismic data and reservoir simulation models. The time-lapse gravity observations best fit a high temperature forward model based on the time-lapse 3D seismics, suggesting that the average in situ CO2 density is about to 530kg/m**3. Uncertainty in determining the average density is estimated to be ±65 kg/m**3 (95% confidence), however, this does not include uncertainties in the modeling. Additional seismic surveys and future gravity measurements will put better constraints on the CO2 density and continue to map out the CO2 flow.

Results of analysis and model simulation of the bed profiles

Bedforms such as dunes and ripples are ubiquitous in rivers and coastal seas, and commonly described as triangular shapes from which height and length are calculated to estimate hydrodynamic and sediment dynamic parameters. Natural bedforms, however, present a far more complicated morphology; the difference between natural bedform shape and the often assumed triangular shape is usually neglected, and how this may affect the flow is unknown. This study investigates the shapes of natural bedforms and how they influence flow and shear stress, based on four datasets extracted from earlier studies on two rivers (the Rio Paraná in Argentina, and the Lower Rhine in The Netherlands). The most commonly occurring morphological elements are a sinusoidal stoss side made of one segment and a lee side made of two segments, a gently sloping upper lee side and a relatively steep (6 to 21°) slip face. A non-hydrostatic numerical model, set up using Delft3D, served to simulate the flow over fixed bedforms with various morphologies derived from the identified morphological elements. Both shear stress and turbulence increase with increasing slip face angle and are only marginally affected by the dimensions and positions of the upper and lower lee side. The average slip face angle determined from the bed profiles is 14°, over which there is no permanent flow separation. Shear stress and turbulence above natural bedforms are higher than above a flat bed but much lower than over the often assumed 30° lee side angle.

Depth profiles of pore-water and solid-phase constituents, respiration rates and grain size distribution in sediments of the Clarion-Clipperton Fracture Zone

Manganese nodules of the Clarion-Clipperton Fracture Zone (CCFZ) in the NE Pacific Ocean are highly enriched in Ni, Cu, Co, Mo and rare-earth elements, and thus may be the subject of future mining operations. Elucidating the depositional and biogeochemical processes that contribute to nodule formation, as well as the respective redox environment in both, water column and sediment, supports our ability to locate future nodule deposits and evaluates the potential ecological and environmental effects of future deep-sea mining. For these purposes we evaluated the local hydrodynamics and pore-water geochemistry with respect to the nodule coverage at four sites in the eastern CCFZ. Furthermore, we carried out selective leaching experiments at these sites in order to assess the potential mobility of Mn in the solid phase, and compared them with the spatial variations in sedimentation rates. We found that the oxygen penetration depth is 180 - 300 cm at all four sites, while reduction of Mn and NO3- is only significant below the oxygen penetration depth at sites with small or no nodules on the sediment surface. At the site without nodules, potential microbial respiration rates, determined by incubation experiments using 14C-labelled acetate, are slightly higher than at sites with nodules. Leaching experiments showed that surface sediments covered with big or medium-sized nodules are enriched in mobilizable Mn. Our deep oxygen measurements and pore-water data suggest that hydrogenetic and oxic-diagenetic processes control the present-day nodule growth at these sites, since free manganese from deeper sediments is unable to reach the sediment surface. We propose that the observed strong lateral contrasts in nodule size and abundance are sensitive to sedimentation rates, which in turn, are controlled by small-scale variations in seafloor topography and bottom-water current intensity.

Planktic and benthic 14C reservoir ages, calibrated by a suite of 14C plateaus in the glacial-to-deglacial Suigetsu atmospheric 14C record

We here present a compilation of planktic and benthic 14C reservoir ages for the Last Glacial Maximum (LGM) and early deglacial from 11 key sites of global ocean circulation in the Atlantic and Indo-Pacific Ocean. The ages were obtained by 14C plateau tuning, a robust technique to derive both an absolute chronology for marine sediment records and a high-resolution record of changing reservoir/ventilation ages (Delta14C values) for surface and deep waters by comparing the suite of planktic 14C plateaus of a sediment record with that of the atmospheric 14C record (Sarnthein et al., 2007, doi:10.1029/173GM13). Results published thus far used as atmospheric 14C reference U/Th-dated corals, the Cariaco planktic record, and speleothems (Fairbanks et al., 2005, doi:10.1016/j.quascirev.2005.04.007; Hughen et al., 2006, doi:10.1016/j.quascirev.2006.03.014; Beck et al., 2001, doi:10.1023/A:1008175728826). We have now used the varve-counted atmospheric 14C record of Lake Suigetsu terrestrial macrofossils (Ramsey et al., 2012, doi:10.1126/science.1226660) to recalibrate the boundary ages and reservoir ages of the seven published records directly to an atmospheric 14C record. In addition, the results for four new cores and further planktic results for four published records are given. Main conclusions from the new compilation are: (1) The Suigetsu atmospheric 14C record on its varve counted time scale reflects all 14C plateaus, their internal structures and relative length previously identified, but implies a rise in the average 14C plateau age by 200-700 14C yr during LGM and early deglacial times. (2) Based on different 14C ages of coeval atmospheric and planktic 14C plateaus, marine surface water Delta14C may have temporarily dropped to an equivalent of ~0 yr in low-latitude lagoon waters, but reached >2500 14C yr both in stratified subpolar waters and in upwelled waters such as in the South China Sea. These values differ significantly from a widely assumed constant global planktic Delta14C value of 400 yr. (3) Suites of deglacial planktic Delta14C values are closely reproducible in 14C records measured at neighboring core sites. (4) Apparent deep-water 14C ventilation ages (equivalents of benthic Delta14C), deduced from the sum of planktic Delta14C and coeval benthic-planktic 14C differences, vary from 500 up to >5000 yr in LGM and deglacial ocean basins.

Seawater carbonate chemistry, nutrients and growth rate during experiments with coral Astrangia poculata and field observations, 2010

Zooxanthellate colonies of the scleractinian coral Astrangia poculata were grown under combinations of ambient and elevated nutrients (5 µM NO, 0.3 µM PO4, and 2nM Fe) and CO2 (780 ppmv) treatments for a period of 6 months. Coral calcification rates, estimated from buoyant weights, were not significantly affected by moderately elevated nutrients at ambient CO2 and were negatively affected by elevated CO2 at ambient nutrient levels. However, calcification by corals reared under elevated nutrients combined with elevated CO2 was not significantly different from that of corals reared under ambient conditions, suggesting that CO2 enrichment can lead to nutrient limitation in zooxanthellate corals. A conceptual model is proposed to explain how nutrients and CO2 interact to control zooxanthellate coral calcification. Nutrient limited corals are unable to utilize an increase in dissolved inorganic carbon (DIC) as nutrients are already limiting growth, thus the effect of elevated CO2 on saturation state drives the calcification response. Under nutrient replete conditions, corals may have the ability to utilize more DIC, thus the calcification response to CO2 becomes the product of a negative effect on saturation state and a positive effect on gross carbon fixation, depending upon which dominates, the calcification response can be either positive or negative. This may help explain how the range of coral responses found in different studies of ocean acidification can be obtained.

Seawater carbonate chemistry, nutrients and growth rate during experiments with coral Astrangia poculata, 2010

Zooxanthellate colonies of the scleractinian coral Astrangia poculata were grown under combinations of ambient and elevated nutrients (5 µM NO, 0.3 µM PO4, and 2nM Fe) and CO2 (780 ppmv) treatments for a period of 6 months. Coral calcification rates, estimated from buoyant weights, were not significantly affected by moderately elevated nutrients at ambient CO2 and were negatively affected by elevated CO2 at ambient nutrient levels. However, calcification by corals reared under elevated nutrients combined with elevated CO2 was not significantly different from that of corals reared under ambient conditions, suggesting that CO2 enrichment can lead to nutrient limitation in zooxanthellate corals. A conceptual model is proposed to explain how nutrients and CO2 interact to control zooxanthellate coral calcification. Nutrient limited corals are unable to utilize an increase in dissolved inorganic carbon (DIC) as nutrients are already limiting growth, thus the effect of elevated CO2 on saturation state drives the calcification response. Under nutrient replete conditions, corals may have the ability to utilize more DIC, thus the calcification response to CO2 becomes the product of a negative effect on saturation state and a positive effect on gross carbon fixation, depending upon which dominates, the calcification response can be either positive or negative. This may help explain how the range of coral responses found in different studies of ocean acidification can be obtained.