Prediction of the thermodynamic properties of metal–arsenate and metal–arsenite aqueous complexes to high temperatures and pressures and some geological consequences

The standard thermodynamic properties at 25°C, 1 bar (ΔG _f^o, ΔH _f^o, S ^o, C _P^o, V ^o, ω) and the coefficients of the revised Helgeson–Kirkham–Flowers equations of state were evaluated for several aqueous complexes formed by dissolved metals and either arsenate or arsenite ions. The guidelines of Shock and Helgeson (Geochim Cosmochim Acta 52:2009–2036, 1988) and Sverjensky et al. (Geochim Cosmochim Acta 61:1359–1412, 1997) were followed and corroborated with alternative approaches, whenever possible. The SUPCRT92 computer code was used to generate the log K of the destruction reactions of these metal–arsenate and metal–arsenite aqueous complexes at pressures and temperatures required by the EQ3/6 software package, version 7.2b. Apart from the AlAsO₄^o and FeAsO₄^o complexes, our log K at 25°C, 1 bar are in fair agreement with those of Whiting (MS Thesis, Colorado School of Mines, Golden, CO, 1992). Moreover, the equilibrium constants evaluated in this study are in good to fair agreement with those determined experimentally for the Ca–dihydroarsenate and Ca–hydroarsenate complexes at 40°C (Mironov et al., Russ J Inorg Chem 40:1690, 1995) and for Fe(III)–hydroarsenate complex at 25°C (Raposo et al., J Sol Chem 35:79–94, 2006), whereas the disagreement with the log K measured for the Ca–arsenate complex at 40°C (Mironov et al., Russ J Inorg Chem 40:1690, 1995) might be due to uncertainties in this measured value. The implications of aqueous complexing between dissolved metals and arsenate/arsenite ions were investigated for seawater, high-temperature geothermal liquids and acid mine drainage and aqueous solutions deriving from mixing of acid mine waters and surface waters. Electronic Supplementary Material The online version of this article () contains supplementary material, which is available to authorized users.     

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.     

Sequence stratigraphy based on high-resolution seismic profiles in the late Pleistocene and Holocene deposits of the Venice area

The sequence-stratigraphic investigation by Very High-Resolution (VHR) seismic profiles allowed recognition of the detailed architecture of the late Pleistocene and Holocene succession of the Venice area. In this way deposits previously known by the analyses of scattered cores, mainly taken along the lagoon margin and the littoral strips, have been correlated at regional scale including the near offshore sector and the result has pointed out the lateral variability of the stratal architecture. Late Pleistocene deposits consist of an aggrading floodplain and fluvial channel fills accumulated during decreasing eustatic sea level, and they are coeval with offlapping forced regressive marine wedges in the Central Adriatic basin. The Holocene sequence is composed of three main seismic units separated by major stratal surfaces. Unit 1 (up to 9 m thick) is formed by channelized deposits separated by areas showing sub-horizontal and hummocky reflectors, and is bounded at the base by a surface that records prolonged conditions of subaerial exposure and at the top by a flatter surface resulting from erosion by marine processes. Deposits of Unit 1 are interpreted as estuarine and distributary channel fills, and back-barrier strata. Unit 2 is well distinguishable from Unit 1 only in the offshore area and at the barrier island bounding the Venice Lagoon, and is composed of a prograding marine wedge (up to 10 m thick) that interacts laterally with ebb tidal deltas. Unit 3 consists of a tidal channel complex and inlet deposits, which testify the evolution of the lagoon area. Tidal channels are entrenched in the lagoon mud flat (coeval with Units 1–2) and cut the Pleistocene–Holocene boundary in several places.Following current sequence-stratigraphic concepts, the Holocene sequence is composed of a paralic transgressive systems tract (TST) (Unit 1) overlying a sequence boundary (the Pleistocene–Holocene boundary) and overlain by a marine highstand systems tract (HST) (Unit 2) in seaward locations and by highstand lagoonal deposits landwards. TST and HST are separated by a downlap surface that is amalgamated with a wave ravinement surface in several places. Unit 3 is coeval with the upper part of Unit 2, and its development has been favoured by human interventions, which led to a transgression limited to the lagoon area.Local factors during the deposition, i.e. subsidence, sediment supply, physiography, and current/wave regimes, led to a significant lateral variability in the architecture of the Holocene sequence, as evidenced by the extreme thickness variation of the TST along both depositional strike and dip. The HST, instead, shows less pronounced strike variations in the stratal architecture. Also, present data clearly evidence that the human impact has a great relevance in influencing the late Holocene sedimentation.     

Millimetric properties of IRAS galaxies – III. Luminosity functions, sub-mm counts and contributions to the sky background

We exploit observations at 1.25 mm with the ESO–SEST telescope of a southern galaxy sample, selected from the IRAS PSC and complete to S ₆₀=2 Jy, to derive the FIR and mm luminosity functions and the conditional probability distributions of FIR and mm luminosity of galaxies. The reliability of these estimates is ensured by the good observed correlation of the far-infrared and mm emissions. This detailed knowledge of the millimetric properties of galaxies is used to simulate the extragalactic sub-mm sky (background intensity, small-scale anisotropy signals and discrete source statistics), which is the target of a variety of ground-based and space observatories. We find, in particular, that a recent tentative detection of a sub-mm background would require, if confirmed, strong evolution with cosmic time of the galaxy long-wavelength emissivity. We finally discuss ways to test such evolution with present and forthcoming facilities: while emphasizing the difficulty of achieving this with large mm telescopes on the ground (because of the poor atmospheric conditions of current sub-mm sites), we mention an interesting opportunity with the long-wavelength camera on ISO . Preliminary results of deep surveys, both from space and from the ground, seem indeed to require excess emission in the past by dusty galaxies with respect to no-evolution predictions.     

Microscopic impactor debris in the soil around Kamil crater (Egypt): Inventory,distribution, total mass,and implications for the impact scenario

We report on the microscopic impactor debris around Kamil crater (45 m in diameter, Egypt) collected during our 2010 geophysical expedition. The hypervelocity impact of Gebel Kamil (Ni‐rich ataxite) on a sandstone target produced a downrange ejecta curtain of microscopic impactor debris due SE–SW of the crater (extending ~300,000 m², up to ~400 m from the crater), in agreement with previous determination of the impactor trajectory. The microscopic impactor debris include vesicular masses, spherules, and coatings of dark impact melt glass which is a mixture of impactor and target materials (Si‐, Fe‐, and Al‐rich glass), plus Fe‐Ni oxide spherules and mini shrapnel, documenting that these products can be found in craters as small as few tens of meters in diameter. The estimated mass of the microscopic impactor debris (<290 kg) derived from Ni concentrations in the soil is a small fraction of the total impactor mass (~10 t) in the form of macroscopic shrapnel. That Kamil crater was generated by a relatively small impactor is consistent with literature estimates of its pre‐atmospheric mass (>20 t, likely 50–60 t).     

Characteristics of quadrant and octant advection schemes in wave models

We point out one problem of the grid advection schemes when used in wave models in coastal areas. The deficiency of the schemes is investigated by means of the ‘third' generation WAM wave model, in which the wave energy is advected by a first order upwind scheme. Two similar, alternative modifications of this scheme are analyzed, the second of which is shown to solve most of the problems encountered with advection along the co-ordinate axes.     

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.     

Spatial and temporal intercomparison of four global burned area products

We characterize the agreement and disagreement of four publically available burned products (Fire CCI, Copernicus Burnt Area, MODIS MCD45A1, and MODIS MCD64A1) at a finer spatial and temporal scale than previous assessments using a grid of three-dimensional cells defined both in space and in time. Our analysis, conducted using seven years of data (2005–2011), shows that estimates of burned area vary greatly between products in terms of total area burned, the location of burning, and the timing of the burning. We use regional and monthly units for analysis to provide insight into the variation between products that can be lost when considering products yearly and/or globally. Comparison with independent, contemporaneous MODIS active fire observations provides one indication of which products most reasonably capture the burning regime. Our results have implications for the use of global burned area products in fire ecology, management and emissions applications.     

Correction to: Rip current hazard assessment on a sandy beach in Liguria,NW Mediterranean

Natural Hazards - The article was published showing the first two author names in the wrong order.     

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.