Origin of nickel in water solution of the chalk aquifer in the north of France and influence of geochemical factors

In the north of France, high registers of nickel are sometimes recorded within the chalk aquifer. In a confined context, the presence of pyrite in the covering clays or in the marcasite nodules encrusted in the clay may constitute a natural source of trace metals. With an objective of sanitary control, the limits of chemical contents regulating the quality of water destined for human consumption have been lowered by the European Framework Directive in the field of water policy (2000/60/EC). As a result, nickel limits have been reduced from 50 to 20 μg/l. The analyses, carried out on three water catchment fields in our area of study, were centred on variable parameters (Eh, O₂(d), pH, Conductivity, T°), major elements (SO₄, NO₃) and metals (Fe, Ni, Mn, Co). The acquired data enabled us to identify from one hand, the conditions which are presented within the site, special thanks to the evolution of nitrate and iron contents and on the other hand, the natural origin (geological) of nickel for two of the three sites studied based essentially on the evaluation of the Nickel/Cobalt ratio. Thus, on the first site, the evolution of nickel content and nitrate content showed the influence of the phenomenon of denitrification on the re-mobilisation of the nickel. Whereas on the second site, a high variation of total iron content and oxygen dissolved in solution highlighted a particular phenomenon of oxidation of the pyrite through molecular oxygen. Finally, the correlation with the sulphates clearly showed behaviour of the nickel, once released, that was entirely dependent on the phenomenon of adsorption on the iron and manganese hydroxides.     

Sub-lethal effects of metal exposure: physiological and behavioural responses of the estuarine bivalve Macoma balthica

Variation in glycogen concentration, condition index (CI) and filtration activity were measured in the bivalve Macoma balthica buried in sediment and experimentally exposed to cadmium (Cd). The stress due to elevated but sub-lethal concentrations (300 ppb Cd) affected the overall fitness of the organism as all parameters monitored responded significantly. Lower concentrations tested (10, 30 and 100 ppb) only induced a significant decrease in filtration activity, which may play a protective role, enabling the organism to slow down its metabolic activity and preserving the integrity of its reserves (reflected by stable CI and glycogen levels). Hence, the various endpoints selected show different thresholds. Our results also demonstrate that under high exposure, small individuals loose proportionally more glycogen per unit of weight than larger ones, thus confirming the higher sensitivity of small individuals to metal contamination. Furthermore, exposure to intermediate concentration (30 ppb) seems to be beneficial to the small individuals as indicated by their high CI values compared to the control. These results showed thus that non-sigmoidal concentration-response relationship and sizes of individuals should be considered in monitoring programmes and risk assessment.     

Significance of vertical flux as a sink for surface water DMSP and as a source for the sediment surface in coastal zones of northern Europe

In April 1997 and 1998 the significance of sedimentation as a sink for epipelagic dimethylsulphoniopropionate (DMSP) production and as a source for marine sediments was reassessed using a newly designed sediment trap. The behaviour of the traps in immersion was monitored continuously and the collection efficiency was evaluated with ²³⁴Th measurements. Net DMS(P) fluxes were corrected for some physical and biological losses during the whole sedimentation process providing reliable estimates of gross DMSP fluxes. It is shown that daily losses by sedimentation account for between 0.1% and 16% of seawater particulate DMSP (DMSPp) standing stocks, and between 3% and 75% of daily DMSPp production. In the Malangen fjord we observed temporal increases of DMSP production and standing stocks which resulted also in increases of DMSP vertical fluxes and DMS(P) concentrations at the sediment surface. This result illustrates how tight the coupling can be between pelagos and benthos, and confirms that DMS(P) concentration in the sediment was a reliable diagnostic indicator of vertical export from overlying waters in Malangen fjord. In Ullsfjord, however, DMS(P) concentrations in the sediment were poorly indicators of Phaeocystis pouchetii export during the early stage of growth of a bloom. The high load of DMS(P) in Balsfjord's sediments could neither be attributed to local vertical sedimentation nor to short-term lateral advection of fresh DMSP-containing phytoplanktonic material, and provides indication that this tracer sometimes also can be misleading. The highest loads of DMS(P) in sediments and the fastest rates of sedimentation occurred in the Southern Bight of the North Sea.     

Th sorption and export models in the water column: A review

Over the past few decades, the radioisotope pair of ²³⁸U / ²³⁴Th has been widely and increasingly used to describe particle dynamics and particle export fluxes in a variety of aquatic systems. The present paper is one of five review articles dedicated to ²³⁴Th. It is focused on the models associated with ²³⁴Th whereas the companion papers (same issue) are focused on present and future methodologies and techniques (Rutgers van der Loeff et al.), C / ²³⁴Th ratios (Buesseler et al.), ²³⁴Th speciation (Santschi et al.) and present and future applications of ²³⁴Th [Waples, J.T., Benitez-Nelson, C.R., Savoye, N., Rutgers van der Loeff, M., Baskaran, M., Gustafsson, Ö., this issue. An Introduction to the application and future use of ²³⁴Th in aquatic systems. Marine Chemistry, FATE special issue]. In this paper, we review current ²³⁴Th scavenging models and discuss the relative importance of the non-steady state and physical terms associated with the most commonly used model to estimate ²³⁴Th flux. Based on this discussion we recommend that for future work the use of models should be accompanied by a discussion of the effect that model and data uncertainty have on the model results. We also suggest that future field work incorporate repeat occupations of sample sites on time scales of 1–4 weeks in order to evaluate steady state versus non-steady state estimates of ²³⁴Th export, especially during high flux events (> ca. 800 dpm m^− 2 d^− 1). Finally, knowledge of the physical oceanography of the study area is essential, particularly in ocean margins and in areas of established upwelling (e.g., Equatorial Pacific). These suggestions will greatly enhance the application of ²³⁴Th as a tracer of particle dynamics and flux in more complicated regimes.     

Synthetic zeolites formed from expanded perlite: Type,formation conditions and properties

Summary The starting material used was expanded perlite with a grain size < 40 m (74.5 wt.% SiO₂; 12.5 wt.% Al₂O₃). This material is a waste product obtained during the production of expanded perlite. The experiments were carried out with KOH solutions, mixtures of KOH and NaOH solutions (1:1) as well as NaOH solutions in the concentration range 0.5 N to 6.0 N at temperatures of between 100° and 140°C and with reaction periods of 2 hours to 13 days in closed system. In the experiments with KOH containing solutions zeolite ZK-19 (phillipsite), W (merlinoite), G (chabazite) and F (edingtonite) formed. Without addition of aluminium high percentages of zeolite ZK-19 (80–100 wt.%) and zeolite W (90–100 wt.%) were obtained. The addition of aluminium rendered possibly the formation of 90 to 100 wt.% of zeolite G and 85 to 100 wt.% of zeolite F, respectively. In the experiments with NaOH solutions analcime, zeolite Na-Pc (gismondine), zeolite HS (sodalite hydrate) and zeolite A formed. High percentages of zeolite Na-Pc (90–100 wt.%), zeolite HS (up to 100 wt.%) and analcime (up to 100 wt.%) were synthesized without addition of aluminium. The formation of high percentages of zeolite A (95–100 wt.%), however, needs the addition of aluminium, NaCI and seed crystals. The temperature stability of the zeolites decreases in the following sequence: K-F > K-W K-ZK-19 (Na), K-W Na, K-F G_si-rich (Na), K-ZK-19 >> Na-Pc G_si-poor. Zeolite A has a very good temperature stability up to temperatures of } 550 °C similar to that of zeolite K-W. At higher temperatures, however, its stability is very poor. The NH₄ ⁺-exchange capacities (meq/g) of the different zeolites amount to the following values: ZK-19:2.8 - 3.2; W:3.0 - 3.2; G:2.3 - 3.6; A:3.1 - 3.2; Na-Pc:3.5 - 3.6; F : 3.9 - 4.8.

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Zeolithsynthese aus Blähperlit—Art, Bildungsbedingungen und Eigenschaften

Zusammenfassung Ausgangsmaterial der experimentellen Untersuchungen war Blähperlit mit einer Korngröße < 40 ,m (74,5 Gew.-% SiO₂; 12,5 Gew.-% Al₂O₃). Dieses Material ist ein Abfallprodukt, das bei der Produktion von Blähperlit anfällt. Die Experimente wurden mit KOH-Lösungen, Lösungsgemischen aus KOH und NaOH (1:1) sowie mit NaOH-Losungen im Konzentrationsbereich 0,5 n-6,0 n bei Temperaturen von 100° – 140°C und über Reaktionszeiten von 2 Stunden bis zu 13 Tagen im geschlossenen System durchgeführt. In den Experimenten mit KOH-hältigen Lösungen bildeten sich die Zeolithe ZK-19 (Phillipsit), W (Merlinoit), G (Chabasit) und F (Edingtonit). Hohe Prozentgehalte an Zeolith ZK-19 (80 – 100 Gew.-%) und Zeolith W (90–100 Gew.-%) entstehen nur ohne Zugabe von Aluminium. Die Bildung von 90–100 Gew.-% Zeolith G bzw. 85–100 Gew. % Zeolith F ist dagegen durch die Zugabe von Aluminium möglich. In den Experimenten mit NaOH-Lösungen bildeten sich die Zeolithe Analcim, Na-Pc (Gismondin), HS (Sodalithhydrat) und Zeolith A. Hohe Prozentanteile an Zeolith Na-Pc (90–100 Gew.-%), HS (bis zu 100 Gew. %) und Analcim (bis zu 100 Gew.-%) wurden ohne Aluminium-Zugabe synthetisiert. Die Bildung von hohen Gehalten an Zeolith A (95–100 Gew. %) ist jedoch nur unter Zugabe von Aluminium, NaCl und Kristallkeimen möglich.Die Temperaturbeständigkeit der Zeolithe nimmt in der folgenden Reihenfolge ab: K-F > K-W - K-ZK-19 (Na), K-W Na, K-F G_si-reich (Na), K-ZK-19 >> Na-Pc G_si-am. Zeolith A weist bis zu Temperaturen von etwa 550°C eine gute Temperaturbeständigkeit auf, die in etwa der von Zeolith K-W entspricht. Bei höheren Temperaturen ist die Beständigkeit jedoch sehr gering.Die NH⁴⁺-Austauschkapazitäten (mÄqu/g) der verschiedenen Zeolithe erreichen folgende Werte: ZK-19:2,8 - 3,2; W:3,0 - 3,2; G:2,3 - 3,6; A:3,1 - 3,2; Na-Pc:3,5 -3,6; F:3,9 - 4,8.

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With 2 Figures     

Combining ordination techniques and geostatistics to determine the patterns of diatom distributions at Lake Lama, Central Siberia

The patterns of spatial variation of diatom assemblages from surface sediments in Lake Lama were quantified using a combined approach of ordination and geostatistics. The aims were (i) to estimate the amount of variation between diatom assemblages within the lake, (ii) to model the spatial variability of the diatom assemblages and their diversity, and (iii) to map the diatom distributions in the lake. A correspondence analysis (CA) separated the diatom assemblages into a planktonic and a periphytic group. Rheophilic taxa were found within the periphytic group. Variogram analysis showed that only the sample scores of the first CA axis and the Shannon diversity index were spatially structured. The range of spatial correlation was estimated to be 55 km for both variables. The diversity and, to a lesser extent, the sample scores had considerable small-scale variability of about 20 and 3%, respectively. Estimates of the first component of the CA and the Shannon index were derived using block-kriging. The maps of the estimates provided a basis for partitioning Lake Lama according to the spatial structures into an eastern and a western basin, a north–south connection between the basins, and a north–south directed tip at the far eastern end. It was shown that variation in diatom assemblages is mainly spatially structured at the catchment scale and that there is a considerable amount of variation at smaller scales. According to the modeled spatial distribution, the assemblages are most likely affected by the lake size, morphology, and the water and nutrient input introduced by rivers. This has to be taken into account when paleolimnological interpretations are drawn from records of complex lake systems like Lake Lama.     

Generalized Coarse Graining Procedures for Flow in Porous Media

This paper focuses on heterogeneous soil conductivities and on the impact their resolution has on a solution of the piezometric head equation: owing to spatial variations of the conductivity, the flow properties at larger scales differ from those found for experiments performed at smaller scales. The method of coarse graining is proposed in order to upscale the piezometric head equation on arbitrary intermediate scales. At intermediate scales large scale fluctuations of the conductivities are resolved, whereas small scale fluctuations are smoothed by a partialy spatial filtering procedure. The filtering procedure is performed in Fourier space with the aid of a low-frequency cut-off function. We derive the partially upscaled head equations. In these equations, the impact of the small scale variability is modeled by scale dependent effective conductivities which are determined by additional differential equations. Explicit results for the scale dependent conductivity values are presented in lowest order perturbation theory. The perturbation theory contributions are summed up with using a renormalisation group analysis yielding explicit results for the effective conductivity in isotropic media. Therefore, the results are also valid for highly heterogeneous media. The results are compared with numerical simulations performed by Dykaar and Kitanidis (1992). The method of coarse graining combined by a renormalisation group analysis offers a tool to derive exact and explicit expressions for resolution dependent conductivity values. It is, e.g., relevant for the interpretation of measurement data on different scales and for reduction of grid-block resolution in numerical modeling. This revised version was published online in July 2006 with corrections to the Cover Date.     

Palaeoecology and Archaeology of the Kärlich–Seeufer Open-Air Site (Middle Pleistocene) in the Central Rhineland, Germany

The Kärlich–Seeufer archaeological site in Germany's central Rhineland was excavated between 1980 and 1992. The site provides evidence for hominid activity during a Middle Pleistocene interglaciation known up to now only from the Kärlich clay pit and therefore defined as the Kärlich Interglaciation, which is considered to be post-Cromer IV and pre-Holstein (sensu stricto) in age. The site is characterized by Acheulean artifacts, a fauna dominated byElephas (Palaeoloxodon) antiquus,and a unique and outstanding preservation of wooden and other palaeobotanical remains. Assuming all finds are associated, the site previously was interpreted as an elephant hunting camp with a wooden structure, together with wood and bone implements preservedin situ.Recent analysis of the same features has shown that the site can also be interpreted as a reworked archaeological sample. Hominid occupation occurred in the vicinity of a small lake with prevailing meso-oligotrophic conditions. Expanding boreal forests and fen vegetation characterized the landscape.