Preliminary Interlaboratory Trial for ISO/DIS 12010: Determination of Short Chain Polychlorinated Alkanes (SCCP) in Water

A first preliminary interlaboratory trial was planned to prepare ISO/DIS 12010: Water quality – determination of short chain polychlorinated alkanes (SCCP) in water – method using GC/MS and electron capture negative ionisation (ECNI). The task was to determine the sum of short chain polychlorinated n‐alkanes with carbon chain lengths of C₁₀–C₁₃ and a chlorine content between 49 and 67% in water by GC‐ECNI‐MS and quantification by multiple linear regression described in ISO/DIS 12010 as the compulsory method. Distributed samples were obtained from a real water extract spiked with a target concentration of 0.4 µg/mL sum of SCCP, i.e. the environmental quality target level according to the Water Framework Directive. The interlaboratory trial included the calibration, a column chromatographic clean up, a concentration step and an integration of chromatographic unresolved humps as well as the quantification with multiple linear regression. Reproducibility standard deviations between 21.5 and 22.9% were achieved by 17 participating laboratories from four countries. The method outlined no significant difference of the results between the standard solution and a real water matrix extract. On the basis of this succeeded preliminary interlaboratory trial the final interlaboratory trial for validation of ISO 12010 was prepared in autumn 2010.     

The Zn abundance and isotopic composition of diatom frustules,a proxy for Zn availability in ocean surface seawater

We have developed cleaning methods for extracting diatomopal from bulk marine sediment samples, for measurement of both zinc (Zn) abundance and isotope composition. This cleaning technique was then applied to a set of Holocene core-top samples from the Southern Ocean. The measured δ⁶⁶Zn (reported relative to the JMC_Lyon standard) and Zn/Si ratios from the Southern Ocean diatom_opal samples range from 0.7 to 1.5‰, and from 14 to 0.9 μmol/mol, respectively. The Zn abundance and isotope composition data show a clear correlation with opal burial rates and other oceanographic parameters. In common with previous work, we interpret the systematic changes in the Zn/Si ratio to be linked to the variability in the concentrations of bioavailable Zn in the ambient surface seawater where the diatom opal is formed. This variability is likely to be primarily controlled by the degree to which Zn is taken up into phytoplankton biomass. The observed systematic pattern in the δ⁶⁶Zn compositions of the diatom_opal core-top samples is, similarly, likely to reflect changes in the δ⁶⁶Zn composition of the ambient Zn in the surface waters above the core-top sites, which is progressively driven towards isotopically heavier values by preferential incorporation of the lighter isotopes into phytoplankton organic material. Thus, the systematic relationship between Zn isotopes and abundance observed in the core-top diatom_opal samples suggests a potential tool for investigating the biogeochemical cycling of Zn in the past surface ocean for down-core diatom_opal material. In this respect, it may be possible to test hypotheses that attribute variations in atmospheric CO₂ on glacial–interglacial timescales to the degree to which trace metals limited primary productivity in HNLC zones.     

Distribution, characterization, and geochemical controls of elements of concern in uranium mine tailings, Key Lake, Saskatchewan, Canada

The distribution of As, Mo, Ni and Se in the aqueous and solid phases of U mine tailings in the Deilmann Tailings Management Facility (DTMF), located at the Key Lake mine in northern Saskatchewan, Canada, was defined using as-discharged tailings samples collected monthly starting in 1996 and core samples collected from the DTMF from 3 locations on 3 occasions between 2004 and 2009. These data indicated that the DTMF can be divided into two geochemical zones; tailings generated from the Deilmann ore body between 1996 and 2000 and tailings from the McArthur River ore body, mined after July 2000. The Deilmann tailings solids are generally characterized by greater elemental concentrations than those in the McArthur River tailings, particularly for As, Co and Ni. These elevated concentrations are attributed to the abundance of Ni–Co–As–S minerals in this ore. The mean aqueous concentrations of As, Mo, Ni, and Se are 3.7, 23.2, 0.14, and 0.02 mg L⁻¹, respectively, in the Deilmann porewaters and 0.20, 4.16, 0.06, and 0.03 mg L⁻¹, respectively, in the McArthur River porewaters. Similarly, the mean As, Mo, Ni, and Se solid phase concentrations are 5.89 × 10³, 69.9, 3.20 × 10³, and 17.4 μg g⁻¹, respectively, for the Deilmann tailings and 440, 13.6, 551, and 3.03 μg g⁻¹ in the McArthur River tailings. Statistically, pH remained unchanged from the time of discharge while Eh values have remained oxic with no significant change between the two tailings types over 15 a of residence time. Results from sequential extractions, thermodynamic modeling, and results of complimentary research indicated that ferrihydrite solubility is the dominant control on aqueous As concentrations and also plays a role in controlling dissolved Mo, Ni and Se.     

The effect of methanogenesis on the geochemistry of low temperature water–Fe0–basalt reactions

Hydrogen gas produced in the subsurface from the hydration of mafic rocks is known to be a major energy source for chemolithotrophic life in extreme environments such as hydrothermal vents. The possibility that in situ anaerobic microorganisms present in the deep subsurface are sustained by low temperature H₂-generating water–rock reactions taking place around them is being investigated. Whether the growth and activity of H₂-utilizing microbes directly influences aqueous geochemistry, rates of mineral dissolution, and the chemical composition of the alteration products is also being quantitatively evaluated.To explore how microorganisms are affected by water–rock reactions, and how their activity may in turn affect reaction progress, laboratory experiments have been conducted to monitor the growth of a methanogenic Archaea in the presence of H_2(g) produced from low temperature water–Fe⁰–basalt reactions. In these systems, the conversion of Fe(II) to Fe(III) and subsequent hydrolysis of water is responsible for the production of H_2(g). To characterize key components of the geochemical system, time series measurements of H₂ and CH₄ gas concentrations, Fe and Si aqueous concentrations, and spatially resolved synchrotron-based analyses of microscale Fe distribution and speciation were conducted. Culture experiments were compared with an abiotic control to document changes in the geochemistry both in the presence and absence of the methanogen.In the control abiotic batch experiment, H₂ was continuously produced, until the headspace became saturated, while in the biotic experiments, microbial consumption of H₂ for methanogenesis draws H₂ down and produces CH₄. Purging the headspace gas reinitiates H₂ and CH₄ production in abiotic and culture experiments, respectively. Mass balance analysis of the amount of CH₄ produced suggests that the total H₂ production in microbial experiments does not exceed the abiotic experiment. Soluble Si concentrations, while buffered to relatively constant values, were higher in culture experiments than the abiotic control.Iron_(aq) concentrations appear to respond to perturbations of H₂ and CH₄ gas concentrations in both culture experiments and the abiotic control. A pulse of Fe preceded the rise in either H₂ or CH₄ production, and as the gas concentrations increased the Fe_(aq) decreased. Iron-bearing mineral assemblages change with increasing reaction time and mineral assemblages vary between culture experiments and the abiotic control. These geochemical trends suggest that there are different reaction paths between the culture experiments and the abiotic control.The hydration of mafic rocks is a common geologic reaction and one that has taken place on Earth for the majority of its history and is postulated to occur on Mars. These reactions are important because of their effect on the rheology and geochemistry of the ocean crust. While most often studied at temperatures of ～250 °C, this work suggests that at lower temperatures microorganisms may have a profound effect on what has long been thought to be solely an abiotic reaction, and may produce diagnostic mineral assemblages that will be preserved in the geological record.     

Rainfall-induced landslide event of May 2010 in the eastern part of the Czech Republic

More than 150 landslides originated in the eastern part of the Czech Republic (region of the Flysch Outer Western Carpathians—hereinafter, OWC) due to soil saturation caused by antecedent precipitation and long lasting and intensive rainfalls on 16–18 May 2010 (>300 mm as measured by some stations). As a consequence, a multitude of small failures originated 88% of which was smaller than 10⁴ m². Most landslides are characterised as shallow (<10 m) or middle–deep (10–30 m) incipient (rather short travel) landslides, debris slides and soil slips spatially clustered to a geological domain underlain by rather weak thin-bedded flysch and unconsolidated Quaternary deposits. An exception to this is represented by a kilometre-long rockslide (∼2–3 mil m³) affecting tectonically weakened and weathered claystone/mudstone-dominated flysch on the southern slope of Mt. Girová (the Beskydy Mountains). The rockslide is one of the largest long runout landslides in the territory of the Czech Republic activated over the past few decades as it reaches the dimensions of the largest documented Holocene long runout landslides in the Czech part of the OWC. A majority of the May 2010 landslide events developed inside older (Holocene or historic) landslide terrains, which points to their spatial persistency and recurrent nature. In spite of the fact that the May 2010 landslide event was not as destructive as some previous landslide activisation in the OWC region (e.g. July 1997 event), it left many slope failures at the initial stage of their potential future reactivation.     

The Middle Miocene to Recent Davis Strait Drift Complex: implications for Arctic�CAtlantic water exchange

A large-scale contourite drift complex has been recognised on multi-channel 2D reflection seismic data acquired in the south-eastern Davis Strait and adjacent Labrador Sea slope offshore West Greenland between 63°?C66°N. Based on well-tie data, the drift complex developed from the Middle Miocene to the Recent. It has been mapped in a wide variety of water depths ranging from about 700?m, at a NNW-ESE-elongated crest located above structural highs in the Davis Strait, to more than 2,000?m beyond the slope to the Labrador Sea. The overall drift geometry has been described by subdivision into two first-order seismic units, enabling the generation of time-isochore maps. The reflection patterns demonstrating current-related deposition are illustrated by seismic examples. The time-isochores of the two first-order seismic units show lateral changes in their depocentres: the lower unit is absent in a zone slightly displaced south-westwards of the present-day crest, indicating changes in the prevailing deepwater current system during the Early Pliocene. The observations can be explained by two alternative palaeoceanographic scenarios: (1) either the present-day oceanographic setting with Arctic?CAtlantic water exchange across the Davis Strait was largely established by the mid-Miocene, with only minor adjustments during the Early Pliocene caused by tectonic movements, or (2) it became established during the Early Pliocene as a consequence of enhanced northward flow across the Davis Strait due to lowering of the sill depth.     

Measurement and modeling of bed shear stress under solitary waves

Direct measurements of bed shear stresses (using a shear cell apparatus) generated by non-breaking solitary waves are presented. The measurements were carried out over a smooth bed in laminar and transitional flow regimes (~ 10⁴ < R_e < ~ 10⁵). Measurements were carried out where the wave height to water depth (h/d) ratio varied between 0.12 and 0.68; maximum near bed velocity varied between 0.16 m/s and 0.51 m/s and the maximum total shear stress (sum of skin shear stress and Froude–Krylov force) varied between 0.386 Pa and 2.06 Pa. The total stress is important in determining the stability of submarine sediment and in sheet flow regimes. Analytical modeling was carried out to predict total and skin shear stresses using convolution integration methods forced with the free stream velocity and incorporating a range of eddy viscosity models. Wave friction factors were estimated from skin shear stress at different instances over the wave (viz., time of maximum positive total shear stress, maximum skin shear stress and at the time of maximum velocity) using both the maximum velocity and the instantaneous velocity at that phase of the wave cycle. Similarly, force coefficients obtained from total stress were estimated at time of maximum positive and negative total stress and at maximum velocity. Maximum positive total shear stress was approximately 1.5 times larger than minimum negative total stress. Modeled and measured positive bed shear stresses are well correlated using the best convolution model, but the model underestimates the data by about 4%. Friction factors are dependent on the choice of normalizing using the maximum velocity, as is conventional, or the instantaneous velocity. These differ because the stress is not in phase with the velocity in general. Friction factors are consistent with previous data for monochromatic waves, and vary inversely with the square-root of the Reynolds number. The total shear stress leads the free stream fluid velocity by approximately 50°, whereas the skin friction shear stress leads by about 30°, which is similar to that reported by earlier researchers.     

Timing and mechanisms controlling evaporite diapirism on Ellef Ringnes Island,Canadian Arctic Archipelago

The Permo‐Carboniferous to Eocene Sverdrup Basin in Canada's Arctic Archipelago is strongly influenced by evaporite diapirism. However, salt structures within the basin have not been extensively investigated recently due to their remote location. This study includes the interpretation of legacy seismic reflection and borehole data to characterize the geometry of selected evaporite domes, and 1D backstripping of wells to investigate tectonic and sedimentary influences on diapirism. Extensional rift‐structures appear to have played a significant role in the formation of evaporite domes by triggering and directing salt movement. Diapirism was initiated by at least the Middle Triassic and continued to develop during the Mesozoic. Differential loading of salt on opposing east–west dome margins led to their present day asymmetric geometries. Diapir growth rates in the Mesozoic were closely linked to the rate of sedimentation and influenced by regional tectonism.     

Determination of the Jenkinson and Collison’s weather types for the western Mediterranean basin over the 1948-2009 period. Temporal analysis

We determined the weather type, according to the Jenkinson and Collison procedure, of the 22 646 days in the 1948-2009 period for the western Mediterranean basin. The analysis is based upon the surface pressure values of the NCEP/NCAR reanalysis, for a grid of nine points with extreme vertices at 45º N, 5º W and 35º N, 15º E, which provides a broad synoptic catalogue for this region. We analyzed the trends of the types and their different groupings during the same period. The most frequent type is U (undetermined), with an annual average of approximately 100 days (99.4, 27.2%), followed by type A (anticyclone), with 75.5 days/ year (20.7%), and C (depression), with 67.8 days/year (18.6%). The high frequency of type U is due to the habitual pressure of baric fields with a low gradient over Mediterranean waters in the warm half of the year. According to their directions, the types from the west are the most frequent and those from the south, the least. The monthly regime of the most frequent types and groupings is quite regular; type C groups, as well as advective and cyclonic curvature groups, present summertime minima and maxima in the cold half of the year, whereas the opposite occurs with types U and A. The main statistically significant annual trends in the 1948-2009 period involve a decrease in type A (–4.19 days/decade, that is, –29.0%) and an increase in type U, the cyclonic types and those presenting an easterly component. On comparing the 31-yr sub-periods 1948-1978 and 1979-2009, the tendencies of A and U were confirmed, and increases can generally be seen in the types presenting an easterly component and a decrease in those with a westerly component. The variation in type A ranged from 2490 days in the first sub-period to 2192 in the second one (p = 0.000), mainly concentrated in summer and autumn. This evident reduction of type A coincides, paradoxically, with an increase in the sea surface pressure variable (+0.31 hPa/decade) throughout the 62 years of analysis. The negative trend found in type A differs from the results of some studies. The different analysis periods, the different scales or areas of study and the variety of methods used to determine the weather types can account for the fact that these results are discordant. Moreover, warming over the last few decades in the waters of the western Mediterranean basin, as well as the clearly cyclogenetic character of the gulfs of Lion and Genoa, might account for the decrease in type A and the increase in the cyclonic curvature types.