Natural hexavalent chromium in groundwaters interacting with ophiolitic rocks

Thirty of the 58 groundwaters sampled in September-October 2000 in the study area (La Spezia Province, Italy) have Mg-HCO₃ to Ca-HCO₃ composition, undetectable Cr(III) contents, and virtually equal concentrations of total dissolved Cr and Cr(VI). Therefore, dissolved Cr is present in toto as Cr(VI), with concentrations of 5-73 ppb. These values are above the maximum permissible level for drinking waters (5 ppb). Local ophiolites, especially serpentinites and ultramafites, are Cr-rich and represent a Cr source for groundwaters. However, since Cr is present as Cr(III) in rock-forming minerals, its release to the aqueous solution requires oxidation of Cr(III) to Cr(VI). This can be performed by different electron acceptors, including Mn oxides, H₂O₂, gaseous O₂, and perhaps Fe(III) oxyhydroxides. Based on this evidence and due to the absence of anthropogenic Cr sources, the comparatively high Cr(VI) concentrations measured in the waters of the study area are attributed to natural pollution.     

Empirical prediction of the Pitzer’s interaction parameters for cationic Al species with both SiO2(aq) and CO2(aq): Implications for the geochemical modelling of very saline solutions

The Pitzer’s interaction parameters, λ_N–M, involving the Mth cationic Al species Al³⁺ or AlOH²⁺ or AlO⁺ and the Nth neutral species SiO_2(aq) (at temperatures of 25–300 °C) or CO_2(aq) (at temperatures of 25–150 °C), have been evaluated through empirical linear relationships between λ_N–M and the surface electrostatic field of the ionic species of interest. These relationships have been obtained starting from the known λ_N–M for both SiO_2(aq) and CO_2(aq) with the main dissolved cations. The Pitzer’s interaction parameter thus estimated for the pair CO_2(aq)–Al³⁺ at 25 °C, 0.327, is 20–40% higher than the corresponding values obtained from CO₂ solubilities in concentrated solutions of AlCl₃, 0.272 ± 0.010 (2σ), and Al₂(SO₄)₃, 0.232 ± 0.002 (2σ), partly corroborating the empirical approach adopted in this study. To test the Pitzer’s interaction coefficients for cationic Al species with aqueous SiO₂, the log K values of the kaolinite dissolution reaction have been computed starting from available experimental data at 23–25 °C and ionic strengths of 0.0001–0.12 mol/kg adopting, alternatively, the Pitzer’s equations and the Debye–Hückel equation. A satisfactory agreement has been found between the log K values obtained through these two approaches, with maximum deviations of 0.11–0.12 log units. This good convergence of results is encouraging as it represents a necessary condition to prove the reliability of the Pitzer’s interaction coefficients estimated in this work. These results are a first step to take into account specific interactions among solutes in concentrated electrolyte solutions, such as those hosted in sedimentary basins or geothermal waters, for instance through the Pitzer’s equations. However, experimental or field data at higher ionic strengths are absolutely necessary to validate the reliability of the Pitzer’s interaction coefficients determined in this study.     

The Buffon's needle problem and the design of a geophysical survey

A logical procedure for designing a geophysical survey when sampling an area with a regular grid can be summarized as follows: model the expected anomaly, estimate the expected noise level, estimate the area of the anomaly above the noise level, choose the spacing, in both the x - and y -directions, of the measurement grid. This last step can be approached according to two main strategies: either when applying the sampling theorem to the shortest dimension of the anomaly or when using a coarser grid, leaving a more complete definition of the anomaly to a later fitting. When following this second option, it can be constructive to estimate the probability of intercepting a given anomaly with a specific segment of profile and a given profile spacing. This latter procedure is analysed by considering a rectangle approximating the plane projection of the anomaly shape and taking into account various ratios between the grid spacing and the rectangle sides. The formulae for estimating the probability of intersecting a given anomaly with a given segment of a given profile spacing are calculated. To demonstrate the accuracy of the results, a Monte-Carlo simulation on a synthetic magnetic map was performed, obtaining, for different ratios between the sides, segment length and profile interval, an agreement better than 0.1% with the analytical formulae.     

The determination of deep temperatures by means of the CO-CO2-H2-H2O geothermometer: an example using fumaroles in the Campi Flegrei,Italy. A comment

Three points raised in the paper by Tedesco and Sabroux (1987) are dealt with. (1) The inconsistency between the water partial pressure calculated by Tedesco and Sabroux (1987) and saturation pressure is due to the improper use of the water-gas-shift reaction as a geothermometer. In fact Tedesco and Sabroux (1987) do not take into account the distribution of gas species between the coexisting vapour and liquid phases. (2) The depth of the “steam reservoir” is evaluated by Tedesco and Sabroux (1987) in too simplistic a way. This matter should be treated with greater care owing to the high social impact of any consideration on the Phlegraean Fields system. (3) The reliability of carbon monoxide determination at the concentration level encountered at Solfatara depends on the collection method rather than on the gas-chromatographic technique.     

A microslip model for the seismic response analysis of drained cohesionless soil deposits

Constitutive equations for drained cohesionless soils under triaxial stress states, based on a microslip model with internal friction, are proposed and applied to the analysis of the seismic response of soil deposits. The microslips, assumed localized in the discontinuity surfaces passing through the particle-to-particle contacts, describe the effects of the sliding and rolling between grains of sand. Once the response of the model under cyclic shearing stresses and strains superimposed on the geostatic stress state has been analysed, the constitutive equations are applied to a one-dimensional shear model for the dynamic analysis of the layered deposits. An application to an instrumented soil deposit is then developed, the experimental results of which refer to both strong and weak motion earthquakes; the comparisons between the experimental and theoretical results point out the peculiarities and validity limits of the model. The model here developed may be applied also to the analysis of two- and three-dimensional sites.     

Biodegradative potential and characterization of psychrotolerant polychlorinated biphenyl-degrading marine bacteria isolated from a coastal station in the Terra Nova Bay (Ross Sea, Antarctica)

Antarctic marine bacteria were screened for their ability to degrade polychlorinated biphenyls (PCB) as the sole carbon and energy source at both 4 degrees C and 15 degrees C. PCB-degrading isolates (7.1%) were identified by sequencing their 16S rDNA as Pseudoalteromonas, Psychrobacter and Arthrobacter members. One representative isolate per genera was selected for evaluating the biodegradative potential under laboratory scale and phenotypically characterized. Removal of individual PCB congeners was between 35.6% and 79.8% at 4 degrees C and between 0.4% and 82.8% at 15 degrees C. Differences in the removal patterns of PCB congeners were observed in relation to the phylogenetic affiliation: Arthrobacter isolate showed similar biodegradation efficiencies when growing at 4 degrees C and 15 degrees C, while Pseudoalteromonas better degraded PCBs at 15 degrees C. No biodegradation was detected for Psychrobacter isolate at 4 degrees C. Results obtained highlight the occurrence of PCB-degrading bacteria in Antarctic seawater and suggest the potential exploitation of autochthonous bacteria for PCB bioremediation in cold marine environments.     

Biochemical and microbial features of shallow marine sediments along the Terra Nova Bay (Ross Sea,Antarctica)

Shallow marine sediments were collected from seven stations (three of which located at Gerlache Inlet, two at Tethys Bay, one at Adelie Cove and one just beneath the Italian Research Base) along the Terra Nova Bay coast (Ross Sea, Antarctica). Their chemical, biochemical and microbiological properties were studied in order to provide further insights in the knowledge of this Antarctic benthic ecosystem. Overall, the organic carbon (OC) represented the major fraction of total carbon (TC) and displayed concentrations similar to or slightly lower than those previously measured in Antarctic bottom sediments. The biopolymeric carbon within OC ranged from 4.1% to 19.9% and showed a wide trophic range (65–834 μg g⁻¹ d.w.). Proteins (PRT) represented on average the main biochemical class contributing to labile organic carbon, followed by lipids (LIP) and carbohydrates (CHO). The activity of aminopeptidase, β-d-glucosidase, alkaline phosphatase and esterase was checked, giving the highest values at Tethys Bay and at the deepest water sediments. The principal component analysis, which was computed considering physical, chemical (elemental and biochemical sedimentary composition) and microbiological parameters (including bacterial abundance, ectoenzymatic activities, T-RFs richness and diversity indices), allowed to obtain two main clusters (“Tethys Bay” and “other stations”). Based on data obtained, two representative 16S rRNA clone libraries using samples from Tethys Bay and Gerlache Inlet were constructed. The sequences of 171 clones were compared to those available in public databases to determine their approximate phylogenetic affiliations. Both aerobic and anaerobic bacteria were disclosed, with the majority of them affiliated with the Gamma- and Deltaproteobacteria, Bacteroidetes and Acidobacteria. The occurrence of strictly anaerobic bacteria suggests that sediments might also undergo anoxic conditions that, in turn, could favor the accumulation of PRT in respect to CHO, assuming that fermentation of amino acids is slower than that of sugars from decomposing polysaccharides.     

A proof of Nekhoroshev's theorem for the stability times in nearly integrable Hamiltonian systems

In the present paper we give a proof of Nekhoroshev's theorem, which is concerned with an exponential estimate for the stability times in nearly integrable Hamiltonian systems. At variance with the already published proof, which refers to the case of an unperturbed Hamiltonian having the generic property of steepness, we consider here the particular case of a convex unperturbed Hamiltonian. The corresponding simplification in the proof might be convenient for an introduction to the subject.