Composition of soil samples from injection location

CO2 leakage from subsurface storage sites is one of the main concerns connected with the CCS technology. As CO2 leakages into near surface formations appear to be very unlikely within pilot CCS projects, the aim of this work is to emulate a leakage by injecting CO2 into a near surface aquifer. The two main questions pursued by the injection test are (1) to investigate the impact of CO2 on the hydrogeochemistry of the groundwater as a base for groundwater risk assessment and (2) to develop and apply monitoring methods and monitoring concepts for detecting CO2 leakages in shallow aquifers. The presented injection test is planned within the second half of 2010, as a joint project of the University of Kiel (Germany), the Helmholtz-Centre for Environmental Research (Leipzig, Germany) and the Engineering Company GICON (Dresden, Germany). The test site has been investigated in detail using geophysical methods as well as direct-push soundings, groundwater well installation and soil and groundwater analyses. The present paper presents briefly the geological and hydrogeological conditions at the test site as well as the planned injection test design and monitoring concept.

Chemical element contents and accumulation rates in metalliferous sediments from DSDP Hole 34-319, Bauer Deep, Southeast Pacific

Marked variations in the chemical and mineralogical composition of sediments at Site 319 have occurred during the 15 My history of sedimentation at this site. The change in composition through time parallels the variability observed in surface sediments from various parts of the Nazca Plate and can be related to variations in the proportion of hydrothermal, hydrogenous, detrital and biogenous phases reaching this site at different times. Metal accumulation rates at Site 319 reach a maximum near the basement for most elements, suggesting a strong hydrothermal contribution during the early history of this site. The hydrothermal contribution decreased rapidly as Site 319 moved away from the spreading center, although a subtle increase in this source is detectable about the time spreading began on the East Pacific Rise. The most recent sedimentation exhibits a strong detritalhydrogenous influence. Post-depositional diagenesis of amorphous phases has converted them to ironrich smectite and well-crystallized goethite without significantly altering the bulk composition of the sediment.

Geochemistry at DSDP Hole 76-534A

At Site 534 in the Blake-Bahama Basin, western North Atlantic, an interval of 68 m of Maestrichtian (Upper Cretaceous) and upper middle to upper Eocene sediments consists of terrigenous siltstones, mudstones, and varicolored zeolitic claystones; minor recovery of micritic limestones, porcellanites, and quartzitic chert was made at this site as well. Comparisons with other Deep Sea Drilling Project (DSDP) sites in the western North Atlantic suggest that the following formations are present in this interval: Hatteras (Maestrichtian), Plantagenet (Maestrichtian and upper Eocene), Bermuda Rise (upper middle to upper Eocene), and the basal Blake Ridge Formation (upper middle to upper Eocene). Recognition of a Tertiary interval of the Plantagenet allows that formation to be divided into lower and upper informal units. Condensation makes this formal lithostratigraphic subdivision difficult. Together the formations record marked net condensed sedimentation (average rate ca. 2.5 m/m.y.) in strongly oxidizing bottom waters. From sedimentary structures and petrography, it is inferred that the terrigenous siltstones and micritic limestones were redeposited from the continental margin by turbidity currents. Chemical data plus petrography confirm relatively high plankton productivity during the upper Eocene. Much of the nonrecovered Eocene interval may represent chert and porcellanite. Fragments recovered were formed by replacement of relatively porous calciturbidites by opal-CT and quartz. Radiolarians in interbedded claystones rich in clinoptilolite show extensive dissolution. Relative to typical hemipelagic sediments, the claystones are enriched in many metals (Cu, Ni, Zn, Pb), particularly within manganese micronodules. The metal accumulation is related to a 30-m.y. period of slow net sediment accumulation, rather than to hydrothermal enrichment or to upward mobilization of metals from the underlying reduced Hatteras black shale facies. Elsewhere in the Blake-Bahama Basin, at Site 391, 22 km to the northwest, upper Eocene facies are missing, reportedly due to deep seafloor erosion of up to 800 m of the sedimentary succession. By contrast, the discovery that this interval is preserved at nearby Site 534 points to much less extensive seafloor erosion, possibly mostly in the Oligocene, which is missing at both DSDP Sites.

Chemical composition of DSDP cherts and associated host sediments

Chert and associated host sediments from Monterey Formation and Deep Sea Drilling Project (DSDP) sequences were analyzed in order to assess chemical behavior during diagenesis of biogenic sediments. The primary compositional contrast between chert and host sediment is a greater absolute SiO2 concentration in chert, often with final SiO2 >=98 wt%. This contrast in SiO2 (and Si/Al) potentially reflects precursor sediment heterogeneity, diagenetic chemical fractionation, or both. SiO2 concentrations and Si/Al ratios in chert are far greater than in modern siliceous oozes, however and often exceed values in acid-cleaned diatom tests. Compositional contrasts between chert and host sediment are also orders-of-magnitude greater than between multiple samples of the host sediment. Calculations based on the initial composition of adjacent host, observed porosity reductions from host to chert and a postulated influx of pure SiO2, construct a chert composition which is essentially identical to observed SiO2 values in chert. Thus, precursor heterogeneity does not seem to be the dominant factor influencing the current chert composition for the key elements of interest. In order to assess the extent of chemical fractionation during diagenesis, we approximate the precursor composition by analyzing host sediments adjacent to the chert. The SiO2 concentration contrast seems caused by biogenic SiO2 dissolution and transport from the local adjacent host sediment and subsequent SiO2 reprecipitation in the chert. Along with SiO2, other elements are often added (with respect to Al) to Monterey and DSDP chert during silicification, although absolute concentrations decrease. The two Monterey quartz chert nodules investigated, in contrast to the opal-CT and quartz chert lenses, formed primarily by extreme removal of carbonate and phosphate, thereby increasing relative SiO2 concentrations. DSDP chert formed by both carbonate/phosphate dissolution and SiO2 addition from the host. Manganese is fractionated during chert formation, resulting in MnO/Al2O3 ratios that no longer record the depositional signal of the precursor sediment. REE data indicate only subtle diagenetic fractionation across the rare earth series. Ce/Ce* values do not change significantly during diagenesis of either Monterey or DSDP chert. Eu/Eu* decreases slightly during formation of DSDP chert. Normative La/Yb is affected only minimally as well. During formation of one Monterey opal-CT chert lens, REE/Al ratios show subtle distribution changes at Gd and to a lesser extent near Nd and Ho. REE compositional contrasts between diagenetic states of siliceous sediment and chert are of a vastly smaller scale than has been noted between different depositional environments of marine sediment, indicating that the paleoenvironmental REE signature is not obscured by diagenetic overprinting.

Trace element concentrations and Li isotope composition in DSDP and ODP sediments from island arcs

We have studied the sedimentary and basaltic inputs of lithium to subduction zones. Various sediments from DSDP and ODP drill cores in front of the Mariana, South Sandwich, Banda, East Sunda and Lesser Antilles island arcs have been analysed and show highly variable Li contents and d7Li values. The sediment piles in front of the Mariana and South Sandwich arcs largely consist of pelagic sediments (clays and oozes). The pelagic clays have high Li contents (up to 57.3 ppm) and Li isotope compositions ranging from +1.3? to +4.1?. The oozes have lower Li contents (7.3-16 ppm) with d7Li values of the diatom oozes from the South Sandwich lower (+2.8? to +3.2?) than those of the radiolarian oozes from the Mariana arc (+8.1? to +14.5?). Mariana sediment also contains a significant portion of volcanogenic material, which is characterised by a moderate Li content (14 ppm) and a relatively heavy isotope composition (+6.4?). Sediments from the Banda and Lesser Antilles contain considerable amounts of continental detritus, and have high Li contents (up to 74.3 ppm) and low d7Li values (around 0?), caused by weathering of continental bedrock. East Sunda sediments largely consist of calcareous oozes. These carbonate sediments display intermediate to high Li contents (2.4-41.9 ppm) and highly variable d7Li values (-1.6? to +12.8?). Basaltic oceanic crust samples from worldwide DSDP and ODP drill cores are characterised by enrichment of Li compared to fresh MORB (6.6-33.1 vs. 3.6-7.5 ppm, respectively), and show a large range in Li isotope compositions (+1.7? to +11.8?). The elemental and isotopic enrichment of Li in altered basalts is due to the uptake of isotopically heavy seawater Li during weathering. However, old oceanic crust samples from Sites 417/418 exhibit lighter Li isotope compositions compared to young basaltic crust samples from Sites 332B and 504B. This lighter Li isotope signature in old crust is unexpected and further research is needed to explore this issue.

Geochemistry and petrology of ODP Site 136-843 basalts

About 13 m of Cretaceous, tholeiitic basalt, ranging from normal (N-MORB) to transitional (T-MORB) mid-ocean-ridge basalts, was recovered at Ocean Drilling Program Site 843 west of the island of Hawaii. These moderately fractionated, aphyric lavas are probably representative of the oceanic basement on which the Hawaiian Islands were built. Whole-rock samples from parts of the cores exhibiting only slight, low-temperature, seawater alteration were analyzed for major element, trace element, and isotopic composition. The basalts are characterized by enrichment in the high field strength elements relative to N-MORB, by a distinct positive Eu anomaly, and by Ba/Nb and La/Nb ratios that are much lower than those of other crustal or mantle-derived rocks, but their isotope ratios are similar to those of present-day N-MORB from the East Pacific Rise. Hole 843A lavas are isotopically indistinguishable from Hole 843B lavas and are probably derived from the same source at a lower degree of partial melting, as indicated by lower Y/Nb and Zr/Nb ratios and by higher concentrations of light and middle rare earth elements and other incompatible elements relative to Hole 843B lavas. Petrographic and trace-element evidence indicates that the Eu anomaly was the result of neither plagioclase assimilation nor seawater alteration. The Eu anomaly and the enrichments in Ta, Nb, and possibly U and K relative to N-MORB apparently are characteristic of the mantle source. Age-corrected Nd and Sr isotopic ratios indicate that the source for the lavas recovered at ODP Site 843 was similar to the source for Southeast Pacific MORB. An enriched component within the Cretaceous mantle source of these basalts is suggested by their initial 208Pb/204Pb-206Pb/204Pb and epsilon-Nd-206Pb/204Pb ratios. The Sr-Pb isotopic trend of Hawaiian post-shield and post-erosional lavas cannot be explained by assimilation of oceanic crust with the isotopic composition of the Site 843 basalts.

Composition of hydrothermal manganese oxide deposits from Galapagos mounds, DSDP Leg 70, Hole 509B

During DSDP Leg 70, a 1.60 m thick manganese oxide layer was sampled in hole 509B. This deposit is formed of alternating layers of hard plates of pure todorokite, about 2 mm thick, and of a more powdery material deeply impregnated with manganese oxide, about 3 mm thick. A SEM study of the plates and the associated powder shows that the powdery material is a transformation of a pre-existing sediment, while the plates are a direct precipitation from a hydrothermal solution. The uranium series disequilibrium method was used to determine the ages of the plates. They are found to be in good chronological sequence and in accordance with the sedimentation rate of the area (4.9 cm/10^3 years) which implies that they have been formed at the sediment-seawater interface during a pulsed injection of hydrothermal solution. The powder presents systematically an "older age" which is explained by a slowing down of the injection while the normal sediment settles; the older age is due to the 230Th excess of the sediment.