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.

Diatoms, total organic carbon, and total nitrogen of sediment core Dethlingen, Germany

To provide insights into the long-term evolution of aquatic ecosystems without human interference, we here evaluate a decadal- to centennial-scale-resolution diatom record spanning about 12 ka of the Holsteinian interglacial (Marine Isotope Stage 11c). Using a partially varved sediment core from the Dethlingen palaeolake (northern Germany), which has previously been studied for palynological and microfacies signals, we document the co-evolution of the aquatic and surrounding terrestrial environment. The diatom record is dominated by the genera Stephanodiscus, Aulacoseira, Ulnaria and Fragilaria. Based on the diatom assemblages and physical sediment properties, the evolution of the Dethlingen palaeolake can be subdivided into three major phases. During the oldest phase (lasting ~1900 varve years), the lake was ~10-15 m deep and characterized by anoxic bottom-water conditions and a high nutrient content. The following ~5600 years exhibited water depths >20 m, maximum diatom and Pediastrum productivity, and a peak in allochtonous nutrient input. During this phase, water-column mixing became more vigorous, resulting in a breakdown of anoxia. The youngest lake phase (~4000-5000 years) was characterized by decreasing water depth, turbulent water conditions and decreased nutrient loading. Based on our palaeolimnological data, we conclude that the evolution of the Dethlingen palaeolake during the Holsteinian interglacial responded closely to (i) changes within the catchment area (as documented by vegetation and sedimentation) related to the transition from closed forests growing on nutrient-rich soils (mesocratic forest phase) to open forests developing on poor soils (oligocratic forest phase), and (ii) short-term climate variability as reflected in centennial-scale climate perturbations.

(Table 1) Geochemistry of feldspars at DSDP Holes 62-464 and 62-465A

Labradorite is the principal feldspar in tholeiitic basalt from Deep Sea Drilling Project Site 464, on northern Hess Rise. Andesine and oligoclase constitute most primary feldspar in the reportedly trachytic rocks from southern Hess Rise at Site 465. Secondary sanidine(?) has replaced the primary phases at Site 465. The secondary potassium feldspar probably resulted from reaction of trachyte with potassium-bearing hydrothermal fluids or sea water.

Reefs shift from net accretion to net erosion along a natural environmental gradient

Coral reefs persist in an accretion-erosion balance and ocean acidification resulting from anthropogenic CO2 emissions threatens to shift this balance in favor of net reef erosion. Corals and calcifying algae, largely responsible for reef accretion, are vulnerable to environmental changes associated with ocean acidification, but the direct effects of lower pH on reef erosion has received less attention, particularly in the context of known drivers of bioerosion and natural variability. This study examines the balance between reef accretion and erosion along a well-characterized natural environmental gradient in Kane'ohe Bay, Hawai'i using experimental blocks of coral skeleton. Comparing before and after micro-computed tomography (µCT) scans to quantify net accretion and erosion, we show that, at the small spatial scale of this study (tens of meters), pH was a better predictor of the accretion-erosion balance than environmental drivers suggested by prior studies, including resource availability, temperature, distance from shore, or depth. In addition, this study highlights the fine-scale variation of pH in coastal systems and the importance of microhabitat variation for reef accretion and erosion processes. We demonstrate significant changes in both the mean and variance of pH on the order of meters, providing a local perspective on global increases in pCO2. Our findings suggest that increases in reef erosion, combined with expected decreases in calcification, will accelerate the shift of coral reefs to an erosion-dominated system in a high-CO2 world. This shift will make reefs increasingly susceptible to storm damage and sea-level rise, threatening the maintenance of the ecosystem services that coral reefs provide.

Minerals and geochemistry at DSDP Hole 62-466

Alkali-basalt clasts in Upper Cretaceous sediments from Site 466 on southern Hess Rise suggest that parts of Hess Rise were constructed by off-ridge volcanic activity. Apparently, tectonic adjustments at Hess Rise occurred during the Late Cretaceous (Campanian-Maastrichtian), when parts of the original volcanic pedestal were uplifted and provided source rocks for the clasts. Synchronous volcanism may have occurred. Causes for the Late Cretaceous tectonic adjustments (and volcanism?) are not known, but they may be related to intraplate movement along the Mendocino Fracture Zone.

Sr-Nd isotopic analyses of sand-sized sediment from the San Francisco Bay coastal system

A diverse suite of geochemical tracers, including 87Sr/86Sr and 143Nd/144Nd isotope ratios, the rare earth elements (REEs), and select trace elements were used to determine sand-sized sediment provenance and transport pathways within the San Francisco Bay coastal system. This study complements a large interdisciplinary effort (Barnard et al., 2012) that seeks to better understand recent geomorphic change in a highly urbanized and dynamic estuarine-coastal setting. Sand-sized sediment provenance in this geologically complex system is important to estuarine resource managers and was assessed by examining the geographic distribution of this suite of geochemical tracers from the primary sources (fluvial and rock) throughout the bay, adjacent coast, and beaches. Due to their intrinsic geochemical nature, 143Nd/144Nd isotopic ratios provide the most resolved picture of where sediment in this system is likely sourced and how it moves through this estuarine system into the Pacific Ocean. For example, Nd isotopes confirm that the predominant source of sand-sized sediment to Suisun Bay, San Pablo Bay, and Central Bay is the Sierra Nevada Batholith via the Sacramento River, with lesser contributions from the Napa and San Joaquin Rivers. Isotopic ratios also reveal hot-spots of local sediment accumulation, such as the basalt and chert deposits around the Golden Gate Bridge and the high magnetite deposits of Ocean Beach. Sand-sized sediment that exits San Francisco Bay accumulates on the ebb-tidal delta and is in part conveyed southward by long-shore currents. Broadly, the geochemical tracers reveal a complex story of multiple sediment sources, dynamic intra-bay sediment mixing and reworking, and eventual dilution and transport by energetic marine processes. Combined geochemical results provide information on sediment movement into and through San Francisco Bay and further our understanding of how sustained anthropogenic activities which limit sediment inputs to the system (e.g., dike and dam construction) as well as those which directly remove sediments from within the Bay, such as aggregate mining and dredging, can have long-lasting effects.

Bird count in Mastbos forest (Breda, Netherlands) in the years 1950 to 1981

Notes from Henrik de Nie: The project started as a phenological study in cooperation with the (Dutch) meteorological institute (KNMI) to register the time of arrival of Fitis and Tjiftaf. During 1951 to 1969 he went every day to the wood (except 1966, in this year his wife died). Thereafter he went no more daily, but because he knew the wood very well and he was free to choice the day on which he did a survey, therefore he choose days with relatively good weather. He did not observe very common bird species, maybe because they are dependent on nest boxes and he did not want to be dependent on the management of the nest box-people (in fact I forgot precisely his arguments, and now I cannot ask him this): Common Starling; Eurasian Tree Sparrow (not common); Great Tit; Eurasian Blue Tit Pieter mentioned 14 species that scored many zero values or only one observation: Stock Dove; Common Cuckoo; Lesser Spotted Woodpecker; Eurasian Golden Oriole; Eurasian Nuthatch; Short-toed Treecreeper; Common Nightingale; Marsh Warbler; Lesser Whitethroat; Goldcrest; Common Firecrest (after 1970 he had difficulties in hearing these two species); Spotted Flycatcher; Eurasian Bullfinch; Black Woodpecker He also mentioned species that he found much fewer as: European Greenfinch; European Pied Flycatcher; Long-eared Owl; Red Crossbill; Sedge Warbler; Icterine Warbler; Eurasian Woodcock; Eurasian Siskin; European Green Woodpecker; Great Spotted Woodpecker; Eurasian Hobby; Western Barn Owl; Woodlark; Common Wood Pigeon; Little Owl; European Crested Tit; Hawfinch. But for these species I think that observations are strongly dependent on the number of visits to the wood. Also here, many zeros and few 1 x during the whole series of visits.

Climate reconstruction and oxygen isotope composition of sediment core Dethlingen, Germany

To gain insights into the mechanisms of abrupt climate change within interglacials, we have examined the characteristics and spatial extent of a prominent, climatically induced vegetation setback during the Holsteinian interglacial (Marine Isotope Stage 11c). Based on analyses of pollen and varves of lake sediments from Dethlingen (northern Germany), this climatic oscillation, here termed the "Older Holsteinian Oscillation" (OHO), lasted 220 years. It can be subdivided into a 90-year-long decline of temperate tree taxa associated with an expansion of Pinus and herbs, and a 130-year-long recovery phase marked by the expansion of Betula and Alnus, and the subsequent recovery of temperate trees. The climate-induced nature of the OHO is corroborated by changes in diatom assemblages and ?18O measured on biogenic silica indicating an impact on the aquatic ecosystem of the Dethlingen paleolake. The OHO is widely documented in pollen records from Europe north of 50° latitude and is characterized by boreal climate conditions with cold winters from the British Isles to Poland, with a gradient of decreasing temperature and moisture availability, and increased continentality towards eastern Europe. This pattern points to a weakened influence of the westerlies and/or a stronger influence of the Siberian High. A comparison of the OHO with the 8.2 ka event of the Holocene reveals close similarities regarding the imprint on terrestrial ecosystems and the interglacial boundary conditions. Hence, in analogy to the 8.2 ka event, a transient, meltwater-induced slowdown of the North Atlantic Deep Water formation appears as a plausible trigger mechanism for the OHO. If correct, meltwater release into the North Atlantic may be a more common agent of abrupt climate change during interglacials than previously thought. We conclude that meltwater-induced climate setbacks during interglacials preferentially occurred when low rates of summer insolation increase during the preceding terminations facilitated the persistence of large-scale continental ice-sheets well into the interglacials.

Mercury content and isotopic composition of teeth, and sex and age of skulls of polar bears collected in Svalbard

We examined the use of mercury (Hg) and nitrogen and carbon stable isotopes in teeth of polar bear (Ursus maritimus) from Svalbard as biotracers of temporal changes in Hg pollution exposure between 1964 and 2003. Teeth were regarded as a good matrix of the Hg exposure, and in total 87 teeth of polar bears were analysed. Dental Hg levels ranged from 0.6 to 72.3 ng/g dry weight and increased with age during the first 10 years of life. A decreasing time trend in Hg concentrations was observed over the recent four decades while no temporal changes were found in the stable isotope ratios of nitrogen (d15N) and carbon (d13C). This suggests that the decrease of Hg concentrations over time was more likely due to a lower environmental Hg exposure in this region rather than a shift in the feeding habits of Svalbard polar bears.

Distribution of biological, anthropogenic, and volcanic constituents in the San Francisco Bay Coastal System

Although conventional sediment parameters (mean grain size, sorting, and skewness) and provenance have typically been used to infer sediment transport pathways, most freshwater, brackish, and marine environments are also characterized by abundant sediment constituents of biological, and possibly anthropogenic and volcanic, origin that can provide additional insight into local sedimentary processes. The biota will be spatially distributed according to its response to environmental parameters such as water temperature, salinity, dissolved oxygen, organic carbon content, grain size, and intensity of currents and tidal flow, whereas the presence of anthropogenic and volcanic constituents will reflect proximity to source areas and whether they are fluvially- or aerially-transported. Because each of these constituents have a unique environmental signature, they are a more precise proxy for that source area than the conventional sedimentary process indicators. This San Francisco Bay Coastal System study demonstrates that by applying a multi-proxy approach, the primary sites of sediment transport can be identified. Many of these sites are far from where the constituents originated, showing that sediment transport is widespread in the region. Although not often used, identifying and interpreting the distribution of naturally-occurring and allochthonous biologic, anthropogenic, and volcanic sediment constituents is a powerful tool to aid in the investigation of sediment transport pathways in other coastal systems.

Methane and sulfide fluxes in permanent anoxia: in situ studies at the Dvurechenskii mud volcano (Sorokin Trough, Black Sea)

The Dvurechenskii mud volcano (DMV), located in permanently anoxic waters at 2060 m depth (Sorokin Trough, Black Sea), was visited during the M72/2 cruise with the RV Meteor to investigate the methane and sulfide release from mud volcanoes into the Black Sea hydrosphere. We studied benthic fluxes of methane and sulfide, and the factors controlling transport, consumption and production of both compounds within the sediment. The pie shaped mud volcano showed temperature anomalies as well as solute and gas fluxes indicating high fluid flow at a small elevation north of the geographical center. The anaerobic oxidation of methane (AOM) coupled to sulfate reduction (SR) was excluded from this zone due to fluid-flow induced sulfate limitation and a fresh mud flow and consequently methane escaped into the water column with a rate of 0.46 mol/m**2/d. In the outer center of the mud volcano fluid flow and total methane flux were decreased, correlating with an increase in sulfate penetration into the sediment, and with higher SR and AOM rates. Here between 50-70% of the methane flux (0.07-0.1 mol/m**2/d) was consumed within the upper 10 cm of the sediment. Also at the edge of the mud volcano fluid flow and rates of methane and sulfate turnover were substantial. The overall amount of dissolved methane released from the mud volcano into the water column was significant with a discharge of 1.4x10**7 mol/yr. The DMV maintains also high areal rates of methane-fueled sulfide production of on average 0.05 mol/m**2/d. However, we concluded that sulfide and methane emission into the hydrosphere from deep water mud volcanoes does not significantly contribute to the sulfide and methane inventory of the Black Sea.