Biogeochemical processes in a clay formation in situ experiment: Part E - Equilibrium controls on chemistry of pore water from the Opalinus Clay, Mont Terri Underground Research Laboratory, Switzerland

The chemistry of pore water (particularly pH and ionic strength) is an important property of clay rocks being considered as host rocks for long-term storage of radioactive waste. Pore waters in clay-rich rocks generally cannot be sampled directly. Instead, their chemistry must be found using laboratory-measured properties of core samples and geochemical modelling. Many such measurements have been made on samples from the Opalinus Clay from the Mont Terri Underground Research Laboratory (URL). Several boreholes in that URL yielded water samples against which pore water models have been calibrated. Following a first synthesis report published in 2003, this paper presents the evolution of the modelling approaches developed within Mont Terri URL scientific programs through the last decade (1997-2009). Models are compared to the composition of waters sampled during dedicated borehole experiments. Reanalysis of the models, parameters and database enabled the principal shortcomings of the previous modelling efforts to be overcome. The inability to model the K concentrations correctly with the measured cation exchange properties was found to be due to the use of an inappropriate selectivity coefficient for Na-K exchange; the inability to reproduce the measured carbonate chemistry and pH of the pore waters using mineral-water reactions alone was corrected by considering clay mineral equilibria. Re-examination of the measured Ca/Mg activity ratios and consideration of the mineralogical composition of the Opalinus Clay suggested that Ca/Mg cation exchange rather than dolomite saturation may control the ratio of these ions in solution. This re-examination also suggests that the Ca/Mg ratio decreases with increasing pore-water salinity. Several possible reasons for this are proposed. Moreover, it is demonstrated that feldspar equilibria must not be included in Opalinus Clay modelling because feldspars are present only in very small quantities in the formation and because Na/K ratios measured in pore water samples are inconsistent with feldspar saturation. The principal need to improve future modelling is additional or better data on rock properties, in particular: (i) a more detailed identification of phases in the Opalinus Clay that include redox-sensitive elements together with evaluation of their thermodynamic properties; (ii) an improved understanding of the distribution of celestite throughout the Opalinus Clay for Sr/SO₄ concentrations control; (iii) improvements in analytic and thermodynamic data for Ca-Mg rock cation exchange and mineral chemical properties and (iv) the measurement of composition and stability constants of clay minerals actually present in the formation.     

Analysis of the Excavation Deviations Impact on Geological Radioactive Waste Repository Performance

Numerical simulations of the transport of radionuclide from high-level radioactive waste stored in geological repositories often do not take into account construction defects in the repository. The potential impact of drilling and excavation deviation from the engineer planned design is a priori considered negligible. We conducted computations on repository geometries that contain deviations from horizontal of a few degrees. The analysis of the results shows that the impact of deviation defects varies from 9 to 16%. A perfect control of the galleries and waste repository cell orientations is then of concern for radioactive waste repository construction, failing which numerical simulations must be conducted on the worst geometric configuration or margin errors added. On the other hand, if the orientation control is precise enough, a modification of the repository design including controlled deviations from the horizontal may be of interest.     

Recent advances in offshore geotechnics for deep water oil and gas developments

The paper presents an overview of recent developments in geotechnical analysis and design associated with oil and gas developments in deep water. Typically the seabed in deep water comprises soft, lightly overconsolidated, fine grained sediments, which must support a variety of infrastructure placed on the seabed or anchored to it. A particular challenge is often the mobility of the infrastructure either during installation or during operation, and the consequent disturbance and healing of the seabed soil, leading to changes in seabed topography and strength. Novel aspects of geotechnical engineering for offshore facilities in these conditions are reviewed, including: new equipment and techniques to characterise the seabed; yield function approaches to evaluate the capacity of shallow skirted foundations; novel anchoring systems for moored floating facilities; pipeline and steel catenary riser interaction with the seabed; and submarine slides and their impact on infrastructure. Example results from sophisticated physical and numerical modelling are presented.     

A western boundary current east of New Caledonia: Observed characteristics

Waters from the South Equatorial Current (SEC), the northern branch of the South Pacific subtropical gyre, are a major supply of heat to the equatorial warm pool, and have an important contribution to climate variability and ENSO which motivated the Southwest Pacific Ocean and Climate Experiment (SPICE, CLIVAR/WCRP). Initially a broad westward current extending from the equator to 30°S, the SEC splits upon arriving at the major islands and archipelagoes of Fiji (18°S, 180°E), Vanuatu (16°S, 168°E), and New Caledonia (22°S, 165°E), resulting in a complex system of western boundary currents and zonal jets that feed the Coral and Solomon Seas. We focus here on the formation of one specific jet feeding the Coral Sea, the North Caledonian Jet (NCJ). Using a combination of recent oceanographic cruises, we describe the ocean circulation to the northeast of New Caledonia, where the SEC forms a western boundary current that ultimately becomes the NCJ. This current, which we document for the first time and propose to refer to as the East Caledonian Current (ECC), has its core located 10-100 km off the east coast of New Caledonia, and extends vertically to at least 1000 m depth. Water mass properties show continuous westward transports through the ECC, from the SEC to the NCJ in both the South Pacific Tropical Waters in the thermocline and Antarctic Intermediate Waters near 700 m depth. The ECC extends about 100 km horizontally; its average 0-1000 m transport was estimated at 14.5±3 Sv off the north tip of the New Caledonian reef, with a maximum of 20 Sv in May 2010. South of that the upstream branch of the ECC east of the Loyalty is close to 8 Sv suggesting an important additional contribution from central Pacific waters carried by the SEC at 16°S and diverted to our region through the western boundary current system east of Vanuatu.     

Statistical distribution of rainy events characteristics and instantaneous hyetographs generation (Merguellil watershed in central Tunisia)

In semi-arid regions, variability of rainfall inputs is high at different time and space scales. Thus, intense and highly variable hydro-meteorological events, which generate both potential resource and hazards, are of major interest. The Merguellil watershed is characterized by a large majority of rainfall in the form of storms, particularly violent in spring and autumn. Storms of summer are short and violent and can be the origin of important floods. Due to the strong rainfall variability, precipitation and hydrological regime are very irregular. This is what led us to think of a detailed study of rainy events. It was founded that two statistical distributions of parameters characterizing events are dominated (log normal, exponential).Thus, our objective consists in studying, in its globality, the collected pluviographic data in order to make a synthesis and analysis which should make it possible the generation of fictitious events to better control the rainfall risk and to study the response of the watershed faces to several types of rainfall. As result, we obtained hyetographs of the height studied rain gauges. These hyetographs show several types of events that are well in conformity with the observed reality. This generation is an advantageous tool in terms of both its robustness and its performance. Its relevance is based on the analysis of the fine time structure of recorded rainfall events. It can be made over several years, and would permit us to avoid being constrained by sample size. Generating rainfall events provides extensive time-related rainfall data that are consistent at all time steps, and can be seen as solution, even partially, of data lack in hydrological study.     

Multixenobiotic resistance, acetyl-choline esterase activity and total oxyradical scavenging capacity of the Arctic spider crab, Hyasaraneus, following exposure to bisphenol A, tetra bromo diphenyl ether and diallyl phthalate

The Arctic has become a sink for persistent organic pollutants (POPs) originating from lower latitudes, and relatively high levels have been found in different biota. Recent studies have identified detrimental effects on wildlife including endocrine disruption, impairment of enzyme activity, and reduced immune function. The Arctic spider crab, Hyas araneus, shown interesting potential for its use as sentinel organism in polar ecosystems. This study investigated the effect of 2,2',4,4'-tetra bromo diphenyl ether (BPDE), bisphenol A (BPA), and diallyl phthalte (DPA) on H. araneus in a three weeks exposure study. Expression of multixenibiotic resistance (MXR) proteins has been studied using the C219 monoclonal antibody which allows identifying an immunoreactive protein of 40 kDa in the digestive gland while no such protein could be observed in the gills. Expression of this protein was increased by exposure to DPA (+75%; p<0.05, n=10). All compounds significantly affected muscle acetylcholine esterase (AChE) activity (p<0.05, n=10) with 50 microg/L DPA having the strongest effect by lowering the value to 37% of control. The total oxyradical scavenging capacity measured in the digestive gland toward peroxyl, hydroxyl and peroxynitrite was also significantly reduced indicating a decreased resistance to oxidative stress generated by DPA (p<0.05, n=5). These results thus suggest the potential detrimental effects of DPA even at concentration as low as 50 microg/L on H. araneus.     

External controls on the distribution,fabrics and mineralization of modern microbial mats in a coastal hypersaline lagoon,Cayo Coco (Cuba)

Active, carbonate‐mineralizing microbial mats flourish in a tropical, highly evaporative, marine‐fed lagoonal network to the south of Cayo Coco Island (Cuba). Hypersaline conditions support the development of a complex sedimentary microbial ecosystem with diverse morphologies, a variable intensity of mineralization and a potential for preservation. In this study, the role of intrinsic (i.e. microbial) and extrinsic (i.e. physicochemical) controls on microbial mat development, mineralization and preservation was investigated. The network consists of lagoons, forming in the interdune depressions of a Pleistocene aeolian substratum; they developed due to a progressive increase in sea‐level since the Holocene. The hydrological budget in the Cayo Coco lagoonal network changes from west to east, increasing the salinity. This change progressively excludes grazers and increases the saturation index of carbonate minerals, favouring the development and mineralization of microbial mats in the easternmost lagoons. Detailed mapping of the easternmost lagoon shows four zones with different flooding regimes. The microbial activity in the mats was recorded using light–dark shifts in conjunction with microelectrode O₂ and HS^? profiles. High rates of O₂ production and consumption, in addition to substantial amounts of exopolymeric substances, are indicative of a potentially strong intrinsic control on mineralization. Seasonal, climate‐driven water fluctuations are key for mat development, mineralization, morphology and distribution. Microbial mats show no mineralization in the permanently submersed zone, and moderate mineralization in zones with alternating immersion and exposure. It is suggested that mineralization is also driven by water‐level fluctuations and evaporation. Mineralized mats are laminated and consist of alternating trapping and binding of grains and microbially induced magnesium calcite and dolomite precipitation. The macrofabrics of the mats evolve from early colonizing Flat mats to complex Cerebroid or Terrace structures. The macrofabrics are influenced by the hydrodynamic regime: wind‐driven waves inducing relief terraces in windward areas and flat morphologies on the leeward side of the lagoon. Other external drivers include: (i) storm events that either promote (for example, by bioclasts covering) or prevent (for example, by causing erosion) microbial mat preservation; and (ii) subsurface degassing, through mangrove roots and desiccation cracks covered by Flat mats (i.e. forming Hemispheroids and Cerebroidal structures). These findings provide in‐depth insights into understanding fossil microbialite morphologies that formed in lagoonal settings.     

A Compilation of Silicon,Rare Earth Element and Twenty‐One other Trace Element Concentrations in the Natural River Water Reference Material SLRS‐5 (NRC‐CNRC)

The natural river water certified reference material SLRS‐5 (NRC‐CNRC) was routinely analysed in this study for major and trace elements by ten French laboratories. Most of the measurements were made using ICP‐MS. Because no certified values are assigned by NRC‐CNRC for silicon and 35 trace element concentrations (rare earth elements, Ag, B, Bi, Cs, Ga, Ge, Li, Nb, P, Rb, Rh, Re, S, Sc, Sn, Th, Ti, Tl, W, Y and Zr), or for isotopic ratios, we provide a compilation of the concentrations and related uncertainties obtained by the participating laboratories. Strontium isotopic ratios are also given.     

Interannual predictability of Arctic sea ice in a global climate model: regional contrasts and temporal evolution

The predictability of the Arctic sea ice is investigated at the interannual time scale using decadal experiments performed within the framework of the fifth phase of the Coupled Model Intercomparison Project with the CNRM-CM5.1 coupled atmosphere–ocean global climate model. The predictability of summer Arctic sea ice extent is found to be weak and not to exceed 2 years. In contrast, robust prognostic potential predictability (PPP) up to several years is found for winter sea ice extent and volume. This predictability is regionally contrasted. The marginal seas in the Atlantic sector and the central Arctic show the highest potential predictability, while the marginal seas in the Pacific sector are barely predictable. The PPP is shown to decrease drastically in the more recent period. Regarding sea ice extent, this decrease is explained by a strong reduction of its natural variability in the Greenland–Iceland–Norwegian Seas due to the quasi-disappearance of the marginal ice zone in the center of the Greenland Sea. In contrast, the decrease of predictability of sea ice volume arises from the combined effect of a reduction of its natural variability and an increase in its chaotic nature. The latter is attributed to a thinning of sea ice cover over the whole Arctic, making it more sensitive to atmospheric fluctuations. In contrast to the PPP assessment, the prediction skill as measured by the anomaly correlation coefficient is found to be mostly due to external forcing. Yet, in agreement with the PPP assessment, a weak added value of the initialization is found in the Atlantic sector. Nevertheless, the trend-independent component of this skill is not statistically significant beyond the forecast range of 3 months. These contrasted findings regarding potential predictability and prediction skill arising from the initialization suggest that substantial improvements can be made in order to enhance the prediction skill.