Leaching of lead metallurgical slags and pollutant mobility far from equilibrium conditions

Lead metallurgical slags are partially vitrified materials containing residual amounts of Zn, Pb, Cr, Cd and As. These hazardous materials are generally buried on heaps exposed to weathering. In this study, leaching behavior of lead blast furnace slags has been tested using pure water and open flow experiments. It appears that in such far from equilibrium and slightly acidic conditions, the main phase to be altered is the vitreous phase. As for lunar, basaltic and nuclear glasses, alkalis/proton exchanges prevail and lead to the formation of a non-protective altered layer enriched in Si, Fe and Al. The composition of the altered layer is quite constant except for Si whose concentration decreases towards the leachate interface. Owing to their sizes, micrometric Pb droplets are not always totally dissolved at the slag surface. Nevertheless, nanometric Pb droplets are instantaneously dissolved while a surrounding altered layer is formed. This leads to high Pb releases in open flow systems. Leachate chemistry and dissolution rates of the vitreous phase are closely comparable to previous leaching tests with basaltic and nuclear glasses in conditions far from equilibrium. Moreover, this study confirms that Fe is a stable element in such conditions.     

Recursive algorithms for the computation of the potential harmonic coefficients of a constant density polyhedron

The gravitational potential of a constant density general polyhedron can be expressed both in terms of a closed analytical expression and as a series expansion involving the corresponding spherical harmonic coefficients. The latter can be obtained from two independent algorithms, which differ not only in their algorithmic architecture but in their efficiency and overall performance, especially when computing the coefficients of higher degree and order. In the present paper a comparative study of all these three approaches is carried out focusing on the numerical implementation of the recursive relations appearing in the two algorithms for the computation of the polyhedral potential harmonic coefficients. The performed numerical investigations show that the linear algorithm proposed by Jamet and Thomas (Proceedings of the second international GOCE user workshop, ‘GOCE, The Geoid and Oceanography’, ESA-ESRIN, Frascati, Italy, 8–10 March 2004, ESA SP-569, 2004), but so far not implemented, achieves a reasonable accuracy at a computational expense that opens to practical applications, for instance in the field of satellite gravimetry/gradiometry interpretation. The convergence behavior of the linear recursion algorithm is studied thoroughly and a computational procedure is proposed that enables the stable computation of potential harmonic coefficients up to degree 60 when referring to an arbitrarily shaped polyhedral body.     

Seasonal succession of cyanoprokaryotes in a hypereutrophic oligo-mesohaline lagoon from the South of France

The Bolmon lagoon (South of France) is an oligo-mesohaline coastal lagoon that has undergone intense eutrophication in the past decades, resulting from a strong concentration of human activities in its drainage basin. Consequently, it exhibits some characteristics typical of an advanced trophic state; namely, the disappearance of submerged vegetation, the permanently intense phytoplankton growth and the recurrence of cyanoprokaryote blooms. As cyanoprokaryote dominance in south-temperate saline lagoons is little reported, we carried out this study in order to understand the seasonal variations in the phytoplankton composition and biomass, and to analyse the influence of environmental parameters such as salinity, nutrients and climate on the seasonal succession of species. In this lagoon, the phytoplankton was permanently dominated by cyanoprokaryotes, probably because of high availability of nutrients, low light penetration in the water column and frequent turbulent mixing induced by wind. The two most abundant species Planktothrix agardhii (in winter–spring) and Pseudanabaena limnetica (in summer) have low light requirements and are well adapted to a high mixing frequency, which defines the S1 functional group in Reynolds' typology for phytoplankton. Although widely studied in north-temperate lakes, blooms of these typically freshwater species are almost unreported in the Mediterranean area, especially in brackish ecosystems that are not their normal habitat. In the Bolmon lagoon, all their requirements for nutrients, light and mixing are satisfied and they seem to cope with a moderate presence of salt but P. agardhii was less competitive than P. limnetica at highest salinities, the latter being probably more halophytic. Contrary to the observations in lakes located at higher latitudes, the Mediterranean climate seems to induce a typical seasonal pattern of succession characterised by the dominance of P. agardhii (winter) – Chroococcales (spring) – Pseudanabaenaceae (summer) – P. agardhii (autumn, winter). The warm temperatures seemed to have a major influence on the phytoplankton succession, being responsible for the survival of Planktothrix during winter and its rapid and intense development in early spring. Intense mixing and high irradiance in summer promoted the development of Pseudanabaenaceae, as reported in another south-temperate lagoon, the Albufera of Valencia (Spain). The ecological success of Oscillatoriales observed in the Bolmon lagoon is a perfect example of a shift to the “turbid stable state” as proposed for freshwater shallow lakes only. Our work demonstrated that hypereutrophic Mediterranean lagoons can function very similarly to shallow lakes at higher latitudes; but the warmer climate and higher irradiances are probably responsible for differences in the seasonal pattern of species dominance.     

Metasomatism and melting history of a Variscan lithospheric mantle domain: evidence from the Puy Beaunit xenoliths (French Massif Central)

Mantle xenoliths from Puy Beaunit (French Massif Central) are compositionally varied, ranging from relatively fertile spinel lherzolites to refractory spinel dunites. Fertile peridotites have registered a modal (amphibole-bearing lherzolites) and cryptic metasomatic event that took place before the last Permian (257 Ma) melting episode. Depletion processes have been constrained by chemical modelling: the depletion is related to different degrees of partial melting, but two major melt extraction episodes are needed to explain the range of major element composition. The second event was responsible for the local large-scale dunitification of former residues. The first melting event (F25%) and metasomatic enrichment are attributed to an ancient fluid and/or liquid infiltration that could be related to a pre-Variscan regional subduction (located to the north of the Beaunit area). Texture acquisition and major deformation of the mantle xenoliths were sub-contemporaneous of the subduction and would result from lithospheric delamination. The second melting event (F17%) produced high-Mg basalts with calc-alkaline trace element signature that gave rise to the Permian underplating episode recognised in western Europe.     

Improving the assessment of ICESat water altimetry accuracy accounting for autocorrelation

Given that water resources are scarce and are strained by competing demands, it has become crucial to develop and improve techniques to observe the temporal and spatial variations in the inland water volume. Due to the lack of data and the heterogeneity of water level stations, remote sensing, and especially altimetry from space, appear as complementary techniques for water level monitoring. In addition to spatial resolution and sampling rates in space or time, one of the most relevant criteria for satellite altimetry on inland water is the accuracy of the elevation data. Here, the accuracy of ICESat LIDAR altimetry product is assessed over the Great Lakes in North America. The accuracy assessment method used in this paper emphasizes on autocorrelation in high temporal frequency ICESat measurements. It also considers uncertainties resulting from both in situ lake level reference data. A probabilistic upscaling process was developed. This process is based on several successive ICESat shots averaged in a spatial transect accounting for autocorrelation between successive shots. The method also applies pre-processing of the ICESat data with saturation correction of ICESat waveforms, spatial filtering to avoid measurement disturbance from the land–water transition effects on waveform saturation and data selection to avoid trends in water elevations across space. Initially this paper analyzes 237 collected ICESat transects, consistent with the available hydrometric ground stations for four of the Great Lakes. By adapting a geostatistical framework, a high frequency autocorrelation between successive shot elevation values was observed and then modeled for 45% of the 237 transects. The modeled autocorrelation was therefore used to estimate water elevations at the transect scale and the resulting uncertainty for the 117 transects without trend. This uncertainty was 8 times greater than the usual computed uncertainty, when no temporal correlation is taken into account. This temporal correlation, corresponding to approximately 11 consecutive ICESat shots, could be linked to low transmitted ICESat GLAS energy and to poor weather conditions. Assuming Gaussian uncertainties for both reference data and ICESat data upscaled at the transect scale, we derived GLAS deviations statistics by averaging the results at station and lake scales. An overall bias of −4.6 cm (underestimation) and an overall standard deviation of 11.6 cm were computed for all lakes. Results demonstrated the relevance of taking autocorrelation into account in satellite data uncertainty assesment.     

Estimating River Conductance from Prior Information to Improve Surface‐Subsurface Model Calibration

Most groundwater models simulate stream‐aquifer interactions with a head‐dependent flux boundary condition based on a river conductance (CRIV). CRIV is usually calibrated with other parameters by history matching. However, the inverse problem of groundwater models is often ill‐posed and individual model parameters are likely to be poorly constrained. Ill‐posedness can be addressed by Tikhonov regularization with prior knowledge on parameter values. The difficulty with a lumped parameter like CRIV, which cannot be measured in the field, is to find suitable initial and regularization values. Several formulations have been proposed for the estimation of CRIV from physical parameters. However, these methods are either too simple to provide a reliable estimate of CRIV, or too complex to be easily implemented by groundwater modelers. This paper addresses the issue with a flexible and operational tool based on a 2D numerical model in a local vertical cross section, where the river conductance is computed from selected geometric and hydrodynamic parameters. Contrary to other approaches, the grid size of the regional model and the anisotropy of the aquifer hydraulic conductivity are also taken into account. A global sensitivity analysis indicates the strong sensitivity of CRIV to these parameters. This enhancement for the prior estimation of CRIV is a step forward for the calibration and uncertainty analysis of surface‐subsurface models. It is especially useful for modeling objectives that require CRIV to be well known such as conjunctive surface water‐groundwater use.     

Nickel speciation in Sebertia acuminata,a plant growing on a lateritic soil of New Caledonia

Nickel speciation in a nickel hyperaccumulating plant (Sebertia acuminata) and its associated soil of southern New Caledonia was studied using various analytical methods. The soil is formed of iron oxides (goethite, hematite), which contain almost all the nickel. The available nickel is probably linked to the organic matter in the litter. Sebertia acuminata, acts as a nickel pump, and concentrates the metal in its leaves. It partitions nickel and silica; nickel is concentrated in the cells (probably in the vacuoles) as organometallic complexes, whereas silica forms the framework of the cells, and the phytolithes. A thorough study of these plants seems essential in order to define the soil–plant relations, and to propose appropriate ways for ecological restoration. To cite this article: N. Perrier et al., C. R. Geoscience 336 (2004).     

Spectral and geological study of the sulfate-rich region of West Candor Chasma, Mars

Sulfates have been discovered by the OMEGA spectrometer in different locations of the planet Mars. They are strongly correlated to light toned layered deposits in the equatorial regions. West Candor Chasma is the canyon with the thickest stack of layers and one with the largest area covered by sulfates. A detailed study coupling mineralogy derived from OMEGA spectral data and geology derived from HRSC imager and other datasets leads to some straightforward issues. The monohydrated sulfate kieserite is found mainly over heavily eroded scarps of light toned material. It likely corresponds to a mineral present in the initial rock formed either during formation and diagenesis of sediments, or during hydrothermal alteration at depth, because it is typically found on outcrops that are eroded and steep. Polyhydrated sulfates, that match any Ca-, Na-, Fe-, or Mg-sulfates with more than one water molecule, are preferentially present on less eroded and darker outcrops than outcrops of kieserite. These variations can be the result of a diversity in the composition and/or of the rehydration of kieserite on surfaces with longer exposure. The latter possibility of rehydration in the current, or recent, atmosphere suggests the low surface temperatures preserve sulfates from desiccation, and, also can rehydrate part of them. Strong signatures of iron oxides are present on sulfate-rich scarps and at the base of layered deposits scarps. They are correlated with TES gray hematite signature and might correspond to iron oxides present in the rock as sand-size grains, or possibly larger concretions, that are eroded and transported down by gravity at the base of the scarp. Pyroxenes are present mainly on sand dunes in the low lying terrains. Pyroxene is strongly depleted or absent in the layered deposits. When mixed with kieserite, local observations favor a spatial mixing with dunes over layered deposits. Sulfates such as those detected in the studied area require the presence of liquid water to form by precipitation, either in an intermittent lacustrine environment or by hydrothermal fluid circulation. Both possibilities require the presence of sulfur-rich groundwater to explain fluid circulation. The elevation of the uppermost sulfate signatures suggests the presence of aquifers up to 2.5 km above datum, only 1 km below the plateau surface.