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.

Clay mineralogy and multi-element chemistry of surface sediments on the Aiberian-Arctic Shelf

Clay mineral and bulk chemical (Si, Al, K, Mg, Sr, La, Ce, Nd) analyses of terrigenous surface sediments on the Siberian-Arctic shelf indicate that there are five regions with distinct, or endmember, sedimentary compositions. The formation of these geochemical endmembers is controlled by sediment provenance and grain size sorting. (1) The shale endmember (Al, K and REE rich sediment) is eroded from fine-grained marine sedimentary rocks of the Verkhoyansk Mountains and Kolyma-Omolon superterrain, and discharged to the shelf by the Lena, Yana, Indigirka and Kolyma Rivers. (2) The basalt endmember (Mg rich) originates from NE Siberia's Okhotsk-Chukotsk volcanic belt and Bering Strait inflow, and is prevalent in Chukchi Sea Sediments. Concentrations of the volcanically derived clay mineral smectite are elevated in Chukchi fine-fraction sediments, corroborating the conclusion that Chukchi sediments are volcanic in origin. (3) The mature sandstone endmember (Si rich) is found proximal to Wrangel Island and sections of the Chukchi Sea's Siberian coast and is derived from the sedimentary Chukotka terrain that comprises these landmasses. (4) The immature sandstone endmember (Sr rich) is abundant in the New Siberian Island region and reflects inputs from sedimentary rocks that comprise the islands. (5) The immature sandstone endmember is also prevalent in the western Laptev Sea, where it is eroded from sedimentary deposits blanketing the Siberian platform that are compositionally similar to those on the New Siberian Islands. Western Laptev can be distinguished from New Siberian Island region sediments by their comparatively elevated smectite concentrations and the presence of the basalt endmember, which indicate Siberian platform flood basalts are also a source of western Laptev sediments. In certain locations grain size sorting noticeably affects shelf sediment chemistry. (1) Erosion of fines by currents and sediment ice rafting contributes to the formation of the coarse-grained sandstone endmembers. (2) Bathymetrically controlled grain size sorting, in which fines preferentially accumulate offshore in deeper, less energetic water, helps distribute the fine-grained shale and basalt endmembers. An important implication of these results is that the observed sedimentary geochemical endmembers provide new markers of sediment provenance, which can be used to track sediment transport, ice-rafted debris dispersal or the movement of particle-reactive contaminants.

Fallout and concentration of aerosol-borne radioactivity over the Atlantic (Appendix)

Measurements of atmospheric radioactivity attached to aerosols are described. Fallout was collected in a vessel of large area. Emphasis was on separation of "wet" and "dry" samples. For strontium 90 a ratio of "wet" to "dry" fallout of 5:1 has been found independent of latitude. The total fallout was smaller than comparable values from continents because of very small amounts of rainfall in the equatorial zone. In order to achieve consistency in the global balance a better knowledge not only of radioactivity but also of precipitation over the ocean is required. Fallout of Ra-D clearly shows the ITC as a barrier for the latitudinal movement of near sea-surface air masses. The concentration of short-lived emanation daughters shows large variations according to varying geographic conditions. A variation with time could not be explained. The specific activity of long-lived radioactive substances shows the expected effect of the ITC as well as a seasonal diminuation of average concentration, similar to that measured at Heidelberg.

Late Neogene sediment composition and accumulation rates of ODP Hole 120-751A

Through scanning electron microscope analysis of sediment microfabric, we have evaluated variations in high-resolution shipboard physical properties (index properties and shear strength), sediment components (smear slide determinations), and shore-based calcium carbonate and biogenic silica data from Site 751 (Kerguelen Plateau). The stratigraphic section at this site records a change in biogenic ooze composition from predominantly calcareous (nannofossil) to siliceous (diatom) ooze from ~23 Ma to the present, reflecting expansion of Antarctic water masses during the late Neogene. The profound change in physical properties and sediment character at 40.1 mbsf (~5-6 Ma) evidently records the northward movement of the Polar Front and a change in absolute accumulation rates of sediment at this site. Trends in geotechnical properties with depth at Site 751 allowed us to subdivide the sedimentary column into a number of geotechnical units that reflect changes in depositional and postdepositional processes with time. Geotechnical properties are sensitive to changing sedimentary inputs of primarily siliceous and calcareous microfossils. This allows us to study the physical nature of biostratigraphically-identified hiatuses and variations in environmental conditions linked to the migration of the Polar Front across this region. The analysis of geotechnical properties permits a more detailed division of the sedimentary column than is possible from shipboard lithologic descriptions alone. Our study of the sedimentary microfabric indicates that randomly oriented, elongate pennate diatom valves compose the sediments with highest porosity and water content values, and the lowest density values (wet bulk, dry bulk, and grain density). Conversely, sediments composed of nannofossils and disassociated nannofossil crystallites and little or no siliceous remains have the lowest porosity and water content values, and the highest density values. Samples of mixed siliceous/calcareous composition have intermediate physical property values, but these vary according to the nature of the sedimentary matrix and the state of preservation of individual skeletal elements.

Geochemistry of DSDP Hole 83-504B minerals

Leg 83 of the Deep Sea Drilling Project has deepened Hole 504B to over 1 km into basement, 1350 m below the seafloor (BSF). The hole previously extended through 274.5 m of sediment and 561.5 m of pillow basalts altered at low temperature (< 100°C), to 836 m BSF. Leg 83 drilling penetrated an additional 10 m of pillows, a 209-m transition zone, and 295 m into a sheeted dike complex. Leg 83 basalts (836-1350 m BSF) generally contain superimposed greenschist and zeolite-facies mineral parageneses. Alteration of pillows and dikes from 836 to 898 m BSF occurred under reducing conditions at low water/rock ratios, and at temperatures probably greater than 100°C. Evolution of fluid composition resulted in the formation of (1) clay minerals, followed by (2) zeolites, anhydrite, and calcite. Alteration of basalts in the transition zone and dike sections (898-1350 m BSF) occurred in three basic stages, defined by the opening of fractures and the formation of characteristic secondary minerals. (1) Chlorite, actinolite, pyrite, albite, sphene, and minor quartz formed in veins and host basalts from partially reacted seawater (Mg-bearing, locally metal-and Si-enriched) at temperatures of at least 200-250°C. (2) Quartz, epidote, and sulfides formed in veins at temperatures of up to 380°C, from more evolved (Mg-depleted, metal-, Si-, and 18O-enriched) fluids. (3) The last stage is characterized by zeolite formation: (a) analcite and stilbite formed locally, possibly at temperatures less than 200°C followed by (b) formation of laumontite, heulàndite, scolecite, calcite, and prehnite from solutions depleted in Mg and enriched in Ca and 18O, at temperatures of up to 250°C. The presence of small amounts of anhydrite locally may be due to ingress of relatively unaltered seawater into the system during Stage 3. Alteration was controlled by the permeability of the crust and is characterized by generally incomplete recrystallization and replacement reactions among secondary minerals. Secondary mineralogy in the host basalts is strongly controlled by primary mineralogy. The alteration of Leg 83 basalts can be interpreted in terms of an evolving hydrothermal system, with (a) changes in solution composition because of reaction of seawater fluids with basalts at high temperatures; (b) variations in permeability caused by several stages of sealing and reopening of cracks; and (c) a general cooling of the system, caused either by the cooling of a magma chamber beneath the spreading center and/or the movement of the crust away from the heat source. The relationship of the high-temperature alteration in the transition zone and dike sections to the low-temperature alteration in the overlying pillow section remains uncertain.

Physical properties of sediments at DSDP Holes 78-541 and 78-543

Sediment cored within the Barbados subduction complex at Sites 541 and 542 are underconsolidated. Underconsolidation and changes in physical properties of the cored section can be related to excess pore water pressure that equals the lithostatic load at Site 542 and to major thrust faulting observed at Site 541. Apparently, the pore fluids within the subduction complex are absorbing the tectonic shock of underthrusting. Sediment sampled from the reference Site 543 on the adjacent Atlantic Plate are also underconsolidated. However, underconsolidation in Hole 543 is apparently due to the movement of excess nitrogen gas observed deeper in the hole. Excess gas was not observed at Sites 541 and 542.

Igneous geochemistry of OP Leg 126 samples

Major element, trace element, and radiogenic isotope compositions of samples collected from Ocean Drilling Program Leg 126 in the Izu-Bonin forearc basin are presented. Lavas from the center of the basin (Site 793) are high-MgO, low-Ti, two-pyroxene basaltic andesites, and represent the products of synrift volcanism in the forearc region. These synrift lavas share many of the geochemical and petrographic characteristics of boninites. In terms of their element abundances, ratios, and isotope systematics they are intermediate between low-Ti arc tholeiites from the active arc and boninites of the outer-arc high. These features suggest a systematic geochemical gradation between volcanics related to trench distance and a variably depleted source. A basement high drilled on the western flank of the basin (Site 792) comprises a series of plagioclase-rich two-pyroxene andesites with calc-alkaline affinities. These lavas are similar to calc-alkaline volcanics from Japan, but have lower contents of Ti, Zr, and low-field-strength elements (LFSE). Lavas from Site 793 show inter-element variations between Zr, Ti, Sr, Ni, and Cr that are consistent with those predicted during crystallization and melting processes. In comparison, concentrations of P, Y, LFSE, and the rare-earth elements (REE) are anomalous. These elements have been redistributed within the lava pile, concentrating particularly in sections of massive and pillowed flows. Relative movement of these two-element groupings can be related to the alteration of interstitial basaltic andesite glass to a clay mineral assemblage by a post-eruptive process. Fluid-rock interaction has produced similar effects in the basement lavas of Site 792. In this sequence, andesites and dacites have undergone a volume change related to silica mobility. As a result of this process, some lithologies have the major element characteristics of basaltic andesite and rhyolite, but can be related to andesitic or dacitic precursors by silica removal or addition.

(Table 1) n-alkane distribution, and stable carbon and deuterium isotope ratios of DSDP Hole 10-94

Hydrology, source region, and timing of precipitation are important controls on the climate of the Great Plains of North America and the composition of terrestrial ecosystems. Moisture delivered to the Great Plains varies seasonally and predominately derives from the Gulf of Mexico/Atlantic Ocean with minor contributions from the Pacific Ocean and Arctic region. For this work, we evaluate long-term relationships for the past ~ 35 million years between North American hydrology, climate, and floral change, using isotopic records and average carbon chain lengths of higher plant n-alkanes from Gulf of Mexico sediments (DSDP Site 94). We find that carbon isotope values (d13C) of n-alkanes, corrected for variations in the d13C value of atmospheric CO2, provide minor evidence for contributions of C4 plants prior to the Middle Miocene. A sharp spike in C4 input is identified during the Middle Miocene Climatic Optimum, and the influence of C4 plants steadily increased during the Late Miocene into the Pleistocene - consistent with other North American records. Chain-length distributions of n-alkanes, indicative of the composition of higher plant communities, remained remarkably constant from 33 to 4 Ma. However, a trend toward longer chain lengths occurred during the past 4 million years, concurrent with an increase in d13C values, indicating increased C4 plant influence and potentially aridity. The hydrogen isotope values (dD) of n-alkanes are relatively invariant between 33 and 9 Ma, and then become substantially more negative (75 per mil) from 9 to 2 Ma. Changes in the plant community and temperature of precipitation can solely account for the observed variations in dD from 33 to 5 Ma, but cannot account for Plio-Pleistocene dD variations and imply substantial changes in the source region of precipitation and seasonality of moisture delivery. We posit that hydrological changes were linked to tectonic and oceanographic processes including the shoaling and closure of the Panamanian Seaway, amplification of North Atlantic Deep Water Production and an associated increase of meridional winds. The southerly movement of the Intertropical Convergence Zone near 4 Ma allowed for the development of a near-modern pressure/storm track system, driving increased aridity and changes in seasonality within the North American interior.

Isotopic composition of the fine fraction of ODP Site 114-704

Ocean Drilling Program Site 704 in the subantarctic South Atlantic was drilled to investigate the response of the Southern Ocean to climatic and Oceanographic developments during the late Neogene. Stable oxygen and carbon isotopes of fine-fraction (<63 µm) carbonate were analyzed to supplement similar analyses of benthic and planktonic foraminifers. The fine fraction is generally composed primarily of coccoliths, and isotopic analyses of the fine fraction were made to complement the foraminiferal analyses. The isotopic curves thus generated suggest paleoceanographic changes not recognizable by the use of benthic and planktonic foraminifers alone. The global Chron 6 carbon isotope shift, found at 253-244 mbsf (6.39-6.0 Ma) at Site 704 in the planktonic and benthic record, is seen in the fine-fraction d13C record as a gradual decrease from 255 mbsf (6.44 Ma) to 210 mbsf (4.24 Ma). At 170 mbsf, mean d18O values of Neogloboquadrina pachyderma increase by 0.6 per mil-0.7 per mil (Hodell and Ciesielski, 1991, doi:10.2973/odp.proc.sr.114.150.1991), reflecting decreased temperature and increased continental ice volume. Accumulation rates increase by 3.3 times above this depth (which corresponds to an age of 2.5 Ma), suggesting increased upwelling and biologic productivity. Carbon isotopic values of fine-fraction carbonate decrease by about 1.5 per mil at 2.6 Ma; however, no change is recorded in the d13C of N. pachyderma. The fine-fraction d13C shift slightly precedes an average l per mil decrease in d13C in benthic foraminifers. The cause of the benthic d13C shift (most likely due to a change in deep water circulation; Hodell and Ciesielski, 1991) is probably not directly related to the fine-fraction shift. The fine-fraction shift is most likely caused by (1) a change in the upwelling to productivity ratio at this site, with increased upwelling bringing lighter carbon to surface waters, more productivity, and higher sedimentation rates and (2) a change in the particle composition of the fine fraction. The increased upwelling is probably due to a northward migration of the Antarctic Polar Front to a position nearer Site 704.

Mineralogical and grain size analysis of ODP Hole 119-745B from the Southern Ocean

The upper Miocene to Pleistocene sediments recovered at ODP Sites 745 and 746 in the Australian-Antarctic Basin are characterized by cyclic facies changes. Sedimentological investigations of a detailed Quaternary section reveal that facies A is dominated by a high content of siliceous microfossils, a relatively low terrigenous sediment content, an ice-rafted component, low concentrations of fine sediment particles, and a relatively high smectite content. This facies corresponds to interglacial sedimentary conditions. Facies B, in contrast, is characteristic of glacial conditions and is dominated by a large amount of terrigenous material and a smaller opaline component. There is also a prominent ice-rafted component. The microfossils commonly are reworked and broken. The clay mineral assemblages show higher proportions of glacially derived illite and chlorite. A combination of four different processes, attributed to glacial-interglacial cycles, was responsible for the cyclic facies changes during Quaternary time: transport by gravity, ice, and current and changes in primary productivity. Of great importance was the movement of the grounding line of the ice shelves, which directly influenced the intensity of ice rafting and of gravitational sediment transport to the deep sea. The extension of the ice shelves was also responsible for the generation of cold and erosive Antarctic Bottom Water, which controlled the grain-size distribution, particularly of the fine fraction, in the investigated area.

Composition and age of rocks from the King's Trough and Palmer Ridge

This paper presents results of studies of rocks sampled during Cruise 19 of R/V Akademik Mstislav Keldysh with the Mir submersibles in the Atlantic Ocean (slopes of the King's Trough and Palmer Ridge). Based on these materials and published data two stages of magmatism and evolution in the region are distinguished: 1) formation of a mid-ocean ridge in the rift zone (68-32 Ma); 2) development of intraplate volcanism during movement of the plate over a "hot spot" (32-0 Ma).

Composition and origin of sediments at DSDP Site 54-424

The sediments recovered on Deep Sea Drilling Project Leg 54 appear to be mixtures of the normal pelagic sediments of the area and hydrothermally produced manganese and iron phases. The latter are mineralogically and chemically very similar to phases recovered from surficial sampling of the mounds. The hydrothermal nontronite which is approximately 15 meters thick in the three holes is essentially free of carbonate or detrital contaminants. The basal sediments are similar to the carbonate oozes presently being deposited in the region, but are enriched in Mn and Fe. This enrichment appears to be the result of hydrothermal deposition that took place at or near the spreading center and may not be associated with the mounds formation. Three different hypotheses for the formation of the nontronite layer and the mounds deposits are considered. An initial deposition of a widespread nontronite layer and subsequent diapiric-like movement of the layer into carbonates could account for the observed stratigraphy; however, if this be correct, analogous deposits should be present in other DSDP sites. The second hypothesis - replacement of the normal sediments by nontronite - may be feasible, but the high purity of the nontronite requires dissolution and removal of refractory elements. The third hypothesis, metal deposition in an advancing oxidation gradient, is compatible with submersible observations of the mounds; however, it can account only for the high purity of the nontronite by very rapid deposition of the hydrothermal phases.

Age determination of corals from the North Atlantic and the Tasman Sea

During the past 40,000 years, global climate has moved into and out of a full glacial period, with the deglaciation marked by several millennial-scale rapid climate change events. Here we investigate the ecological response of deep-sea coral communities to both glaciation and these rapid climate change events. We find that the deep-sea coral populations of Desmophyllum dianthus in both the North Atlantic and the Tasmanian seamounts expand at times of rapid climate change. However, during the more stable Last Glacial Maximum, the coral population globally retreats to a more restricted depth range. Holocene populations show regional patterns that provide some insight into what causes these dramatic changes in population structure. The most important factors are likely responses to climatically driven changes in productivity, [O2] and [CO3]2-.

Siliceous components of Pliocene-Holocene sediments of the South Atlantic

The Pliocene-Holocene sediments recovered on ODP Leg 114 from Holes 699A, 701C, and 704B are the subject of a detailed investigation to interpret changes in the Oceanographic environment of the South Atlantic in the vicinity of the Polar Front Zone (PFZ). The cores sample sediments at shallow (Hole 704B, 2532 m), intermediate (Hole 699A, 3716 m), and basinal (Hole 701C, 4647 m) depths. Sites 699 and 704 come under the influence of the Antarctic Circumpolar Current (ACC) and Circumpolar Deep Water. It is possible that the upper reaches of Antarctic Bottom Water (AABW) may also affect Hole 699A. Site 701 is influenced by AABW. Closely spaced samples were analyzed for grain-size distribution, sand fraction components, biosiliceous microfossils, organic carbon, and water content. PFZ migrations are traced using changes in bulk sedimentaccumulation rates and the abundance of the diatoms Actiniscus ssp. and Genus et species indet. 1 Fenner (1991), as well as changes in sediment grain size and composition. Diatomaceous sediments of Gilbert age in Hole 699A indicate that the PFZ was positioned over this site, but during the Gauss it migrated north, bringing in less productive Antarctic Surface Water. All cores document a very gradual southerly movement of the PFZ throughout the Matuyama (with some sharp fluctuations of the northen PFZ border over Site 704 between 1.45 and 1.83 m.y.). This regressive shift culminated in the late Matuyama. The latest Matuyama to earliest Brunhes record in Hole 699A has been removed by a hiatus lasting from 1.0 to 0.6 m.y., which was probably caused by intensification of the deep-reaching ACC. The corresponding interval in Hole 704B, the shallowest core, contains evidence of winnowing. Sharp fluctuations of large amplitude and high frequency in the lithology of the sediments from Hole 704B in the eastern South Atlantic, starting at about 0.75 m.y. and characterizing the whole Brunhes Epoch, record the rapid movement of the northern border of the PFZ over the site. These reflect strong glacial/interglacial alternations in climate. To a lesser extent, lithologic fluctuations in Hole 701C reflect the same phenomenon, whereas in Hole 699A the lithology does not vary as dramatically.

Glacial-interglacial record of ODP Site 181-1119 in the Canterbury Bright, Southwest Pacific Ocean

Ocean Drilling Program (ODP) Site 1119 is located at water depth 395 m near the subtropical front (STF; here represented by the Southland Front), just downslope from the shelf edge of eastern South Island, New Zealand. The upper 86.19 metres composite depth (mcd) of Site 1119 sediment was deposited at an average sedimentation rate of 34 cm/kyr during Marine Isotope Stages (MIS) 1-8 (0-252 ka), and is underlain across a ~25 kyr intra-MIS 8 unconformity by MIS 8.5-11 (277-367 ka) and older sediment deposited at ~14 cm/kyr. A time scale is assigned to Site 1119 using radiocarbon dates for the period back to ~39 ka, and, prior to then, by matching its climatic record with that of the Vostok ice core, which it closely resembles. Four palaeoceanographic proxy measures for surface water masses vary together with the sandy-muddy, glacial-interglacial (G/I) cyclicity at the site. Interglacial intervals are characterised by heavy delta13C, high colour reflectance (a proxy for carbonate content), low Q-ray (a proxy for clay content) and light delta18O; conversely, glacial intervals exhibit light delta13C, low reflectance, high Q-ray and heavy delta18O signatures. Early interglacial intervals are represented by silty clays with 10-105-cm-thick beds of sharp-based (Chondrites-burrowed), shelly, graded, fine sand. The sands are rich in foraminifera, and were deposited distant from the shoreline under the influence of longitudinal flow in relatively deep water. Glacial intervals comprise mostly micaceous silty clay, though with some thin (2-10 cm thick) sands present also at peak cold periods, and contain the cold-water scallop Zygochlamys delicatula. Interglacial sandy intervals are characterised by relatively low sedimentation rates of 5-32 cm/kyr; cold climate intervals MIS 10, 6 and 2 have successively higher sedimentation rates of 45, 69 and 140 cm/kyr. Counter-intuitively,and forced by the bathymetric control of a laterally-moving shoreline during G/I and I/G transitions, the 1119 core records a southeasterly (seaward) movement of the STF during early glacial periods, accompanied by the incursion of subtropical water (STW) above the site, and northwesterly (landward) movement during late glacial and interglacial times, resulting in a dominant influence then of subantarctic surface water (SAW). The history of passage of these different water masses at the site is clearly delineated by their characteristic delta13C values. The intervals of thin, graded sands-muds which occur within MIS 2-3, 6, 7.4 and 10 indicate the onset at times of peak cold of intermittent bottom currents caused by strengthened and expanded frontal flows along the STF, which at such times lay near Site 1119 in close proximity to seaward-encroaching subantarctic waters within the Bounty gyre. In common with other nearby Southern Hemisphere records, the cold period which represents the last glacial maximum lasted between ~23-18 ka at Site 1119, during which time the STF and Subantarctic Front (SAF) probably merged into a single intense frontal zone around the head of the adjacent Bounty Trough.