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.     

Heavy metal analyses in the marine environment - approaches to quality control

The validity of analyses of elements in the femto- and picomolar ranges in waters and sediments can be assessed on the basis of several criteria: an evaluation of the chemical technique; the use of primary standards and intercalibration exercises; and chemical and geochemical coherence of the results. Herein are reported analyses of ruthenium, platinum, palladium, rhenium, iridium and gold in oceanic samples. The gold concentrations in surface seawaters, at least 25 times less than those previously reported, are in accord with the concentrations of their periodic table neighbors as well as with crustal and sedimentary contents. The remarkable concentration of rhenium in seawater, in relation to its very low crustal abundance, can be explained by the inertness of the perrhenate ion.     

Variability in concentration of suspensates in an estuarine environment

Three data sets of suspensate concentrations, collected under different sampling plans, were analyzed to develop a minimal sampling period, consistent with a predetermined precision. Individual samples collected during any part of a given day were within ±50% of the daily average. In the main channel of the estuary, a monthly sampling scheme closely approximated a weekly pattern; however, seasonal sampling was unsatisfactory. Outside the main channel, weekly, monthly, and seasonal sampling patterns did not differ greatly. Variability in suspensate concentrations must be considered when calculating sediment flux in estuarine and coastal waters.     

Heave compensation and formation strength evaluation from downhole acceleration measurements while coring

In order to evaluate the efficiency of heave compensation in the Ocean Drilling Program, we developed a device measuring the acceleration of the core barrels. First results show that heave compensation limits bit motion to 10% of the surface heave. We also use the acceleration data to characterize the formation. On rotary corers, acceleration amplitudes decrease with increasing hardness of the formation. Comparison with geophysical logs shows that this relationship can resolve cm-scale features. On piston corers, the maximum acceleration is characteristic of the sediment shear strength. Easy and fast to deploy, this tool allows to characterize formations before any sample analysis.     

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.     

Io's sodium emission cloud and the voyager 1 encounter

Io's neutral sodium emission cloud was monitored during the period of Voyager 1 encounter from two independent ground-based sites. Observations from Table Mountain Observatory verified the continued existence of the “near-Io cloud” (d < 1.5 × 10⁵ km, for 4πI > 1 kR; R denotes Rayleigh) while those from Wise Observatory showed a deficiency in the weaker emission at greater distances from Io. The sodium cloud has been monitored from both observatories for several years. These and other observations demonstrate that the behavior of the cloud is complex since it undergoes a variety of changes, both systematic and secular, which can have both time and spatial dependencies. The cloud also displays some characteristics of stability. Table Mountain images and high-dispersion spectra (resolution $\text{～0.2}\text{A}\text{?}$) indicate that the basic shape and intensity of the “near cloud” have remained relatively constant at least since imaging observations began in 1976. Wise Observatory low-dispersion spectra (resolution $\text{～1}\text{A}\text{?}$) which have been obtained since 1974 demonstrate substantial variability of the size and intensity of the “far cloud” (d ? 1.5 × 10⁵ km) on a time scale of months or less. Corresponding changes in the state of the plasma associated with the Io torus are suggested, with the period of Voyager 1 encounter represented as a time of unusually high plasma temperature and/or density. Dynamic models of the sodium cloud employing Voyager 1 plasma data provide a reasonable fit to the Table Mountain encounter images. The modeling assumptions of anisotropic ejection of neutral sodium atoms from the leading, inner hemisphere of Io with a velocity distribution characteristic of sputtering adequately explain the overall intensity distribution of the “near cloud”. During the Voyager 1 encounter period there appeared a region of enhanced intensity projecting outward from Io's orbit and inclined to the orbital plane. This region is clearly distinguished from the sodium emission normally aligned with the plane of Io's orbit. The process responsible for this phenomenon is not yet understood. Similar but less pronounced features are also present in several Table Mountain images obtained over the past few years.     

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.