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.

Geochemistry, lithology, and bulk density of Cricket Flat paleosol samples

The high-resolution marine isotope climate record indicates pronounced global cooling during the Langhian (16-13.8 Ma), beginning with the warm middle Miocene climatic optimum and ending with significant Antarctic ice sheet expansion and the transition to "icehouse" conditions. Terrestrial paleoclimate data from this interval is sparse and sometimes conflicting. In particular, there are gaps in the terrestrial record in the Pacific Northwest during the late Langhian and early Serravallian between about 14.5 and 12.5 Ma. New terrestrial paleoclimate data from this time and region could reconcile these conflicting records. Paleosols are particularly useful for reconstructing paleoenvironment because the rate and style of pedogenesis is primarily a function of surface environmental conditions; however, complete and well-preserved paleosols are uncommon. Most soils form in erosive environments that are not preserved, or in environments such as floodplains that accumulate in small increments; the resulting cumulic soils are usually thin, weakly developed, and subject to diagenetic overprinting from subsequent soils. The paleosol at Cricket Flat in northeastern Oregon is an unusually complete and well-preserved paleosol from a middle Miocene volcanic sequence in the Powder River Volcanic Field. An olivine basalt flow buried the paleosol at approximately 13.8 ± 0.6 Ma, based on three 40Ar/39Ar dates on the basalt. We described the Cricket Flat paleosol and used its physical and chemical profile and micromorphology to assess pedogenesis. The Cricket Flat paleosol is an Ultisol-like paleosol, chemically consistent with a high degree of weathering. Temperature and rainfall proxies suggest that Cricket Flat received 1120 ± 180 mm precipitation y-1 and experienced a mean annual temperature of 14.5 ± 2.1 °C during the formation of the paleosol, significantly warmer and wetter than today. This suggests slower cooling after the middle Miocene climatic optimum than is seen in the existing paleosol record.

Description and chemical and mineral composition of iron oxide samples from two Finnish lakes

Fifteen iron oxide accumulations from the bottoms of two Finnish lakes ("lake ores") were found to contain as much as 50% Fe. Differential X-ray powder diffraction and selective dissolution by oxalate showed that the samples consisted of poorly crystallized goethite and ferrihydrite. The crust ores of one lake had higher ferrihydrite to goethite ratios than the nodular ores of the other lake. The higher ferrihydrite proportion was attributed to a higher rate of Fe2+ supply from the ground water and/or a higher rate of oxidation as a function of water depth and bottom-sediment permeability. Values of Al-for-Fe substitution of the goethites determined from unit-cell dimensions agreed with those obtained from chemical extraction if the unit-cell volume rather than the c dimension was used. In very small goethite crystals a slight expansion of the a unit-cell dimension is probaby compensated by a corresponding contraction of the c dimension, so that a contraction of the c dimension need not necessarily be caused by Al substitution. The goethites of the two lakes differed significantly in their Al-for-Fe substitutions and hence in their unit-cell sizes, OH-bending characteristics, dehydroxylation temperatures, dissolution kinetics, and Mössbauer parameters. The difference in Al substitution (0 vs. 7 mole %) is attributed to the Al-supplying power of the bottom sediments: the silty-clayey sediments in one lake appear to have supplied A1 during goethite formation, whereas the gravelly-sandy sediments in the other lake did not. The compositions of the goethites thus reflect their environments of formation.

Magnetic properties and chemical composition at DSDP Hole 77-538A

Magnetic properties of doleritic and some metamorphic basement rocks underlying Catoche Knoll are studied. Doleritic rocks show a high saturation magnetic moment (2-5 emu/g) compared to metamorphic rocks (0.1-1 emu/g). Magnetic minerals of rocks from this hole show a high stability when heated in vacuo up to 600°C at a fixed rate of heating. Curie temperatures are distributed close to 550°C. These properties differ markedly from those of common submarine basalts observed before. X-ray microprobe analysis techniques were used to determine internal structures of ferromagnetic minerals; in most of ferromagnetic minerals there exist two different types of magnetic phases (i.e., products of high-temperature and low-temperature oxidations). Interpretations on the coexisting, seemingly contradictory, phases can be made based upon present analyses.

XCO2 and XCH4 total column measurement during POLARSTERN cruise PS83 (ANT-XXIX/10), north-south gradient

A portable Fourier transform spectrometer (FTS), model EM27/SUN, was deployed onboard the research vessel Polarstern to measure the column-average dry air mole fractions of carbon dioxide (XCO2) and methane (XCH4) by means of direct sunlight absorption spectrometry. We report on technical developments as well as data calibration and reduction measures required to achieve the targeted accuracy of fractions of a percent in retrieved XCO2 and XCH4 while operating the instrument under field conditions onboard the moving platform during a 6-week cruise on the Atlantic from Cape Town (South Africa, 34° S, 18° E; 5 March 2014) to Bremerhaven (Germany, 54° N, 19° E; 14 April 2014). We demonstrate that our solar tracker typically achieved a tracking precision of better than 0.05° toward the center of the sun throughout the ship cruise which facilitates accurate XCO2 and XCH4 retrievals even under harsh ambient wind conditions. We define several quality filters that screen spectra, e.g., when the field of view was partially obstructed by ship structures or when the lines-of-sight crossed the ship exhaust plume. The measurements in clean oceanic air, can be used to characterize a spurious air-mass dependency. After the campaign, deployment of the spectrometer alongside the TCCON (Total Carbon Column Observing Network) instrument at Karlsruhe, Germany, allowed for determining a calibration factor that makes the entire campaign record traceable to World Meteorological Organization (WMO) standards. Comparisons to observations of the GOSAT satellite and concentration fields modeled by the European Centre for Medium-Range Weather Forecasts (ECMWF) Copernicus Atmosphere Monitoring Service (CAMS) demonstrate that the observational setup is well suited to provide validation opportunities above the ocean and along interhemispheric transects.

Organic compounds in sediments and pore waters of ODP Sites 117-723 and 117-724

Total organic carbon, amino compounds, and carbohydrates were measured in pore waters and sediments of Pliocene to Pleistocene age from Sites 723 and 724 (ODP Leg 117) to evaluate (1) relationships between organic matter in the sediment and in the pore water, (2) the imprint of lithological variations on the abundance and contribution of organic substances, (3) degradation of amino compounds and carbohydrates with time and/or depth, and (4) the dependence of the ammonia concentration in the pore water on the degradation of amino compounds in the sediment. Total organic carbon concentrations (TOC) of the investigated sediment samples range from 0.9% to 8.7%, and total nitrogen concentrations (TN) from 0.1% to 0.5%. Up to 4.9% of the TOC is contributed by hydrolyzable amino acids (THAA) which are present in amounts between 1.1 and 21.3 µmol/g dry sediment and decrease strongly downhole. Hydrolyzable carbohydrates (THCHO) were found in concentrations from 1.3 to 6.6 ?mol/g sediment constituting between 0.1% and 2.0% of the TOC. Differences between the distribution patterns of monomers in Sites 723 and 724 indicate higher terrigenous influence for Site 724 and, furthermore, enhanced input of organic matter that is relatively resistant to microbial degradation. Lithologically distinct facies close to the Pliocene/Pleistocene boundary yield different organic matter compositions. Laminated horizons seem to correspond with enhanced amounts of biogenic siliceous material and minor microbiological degradation. Total amounts of dissolved organic carbon (DOC) in pore waters vary between 11 and 131 mg/L. Concentrations of DOC as well as of dissolved amino compounds and carbohydrates appear to be related to microbial activity and/or associated redox zones and not so much to the abundance of organic matter in the sediments. Distributions of amino acids and monosaccharides in pore waters show a general enrichment in relatively stable components in comparison to those of the sediments. Nevertheless, the same trend appears between amino acids present in the sediments from Sites 723 and 724 as well as between amino acids in pore waters from these two sites, indicating a direct relation between the dissolved and the sedimentary organic fractions. Different ammonia concentrations in the pore waters of Sites 723 and 724 seem to be related to enhanced release of ammonia from degradation of amino compounds in Site 723.