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 impact of dolomite and plagioclase weathering on the chemistry of shallow groundwaters circulating in a granodiorite-dominated catchment of the Sila Massif (Calabria,Southern Italy)

This work is aimed at investigating the weathering processes of the granodiorites cropping out in a small catchment of the Sila Massif. The mineral constituents in this granodiorite are plagioclase, often zoned with a Ca-rich core and a Na-rich rim, quartz, chlorite, K-feldspar, white mica and epidote. During this study, dolomite was discovered in local stream sediments, as separate monomineralic grains, probably resulting from erosion of veins cutting the crystalline rocks. Prevailing dissolution of foreign dolomite and a Ca-rich plagioclase is suggested by the Ca–Mg–HCO₃ chemical composition of local groundwaters and stream waters, which is rather unexpected for waters interacting with granitoid rocks. These qualitative observations are quantitatively confirmed by reaction path modelling of the weathering processes occurring in the study area, which was carried out using the EQ3/6 software package, version 8.0, and the Double Solid Reactant Method. Indeed, it was possible to ascertain that the release of both major dissolved constituents and several trace elements (Ba, Co, Cr, Fe, Mn, Ni, Pb, Sr, V and Zn), from rocks to waters, is chiefly controlled by the dissolution of foreign dolomite and the Ca-rich core of zoned plagioclases.     

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.     

Propagation of P and S-waves in magmas with different crystal contents: Insights into the crystallinity of magmatic reservoirs

Increasing amount of crystals tends to reduce the mobility of magmas and modifies its elastic characteristics (e.g. [Caricchi, L. et al., 2007. Non-Newtonian rheology of crystal-bearing magmas and implications for magma ascent dynamics. Earth and Planetary Science Letters, 264: 402–419.; Bagdassarov, N., Dingwell, D.B. and Webb, S.L., 1994. Viscoelasticity of crystal- and bubble-bearing rhyolite melts. Physics of the Earth and Planetary Interior, 83: 83–99.]). To quantify the effect of crystals on the elastic properties of magmas the propagation speed of shear and compressional waves have been measured at pressure and temperatures relevant for natural magmatic reservoirs. The measurements have been performed in aggregates at variable particle fractions (? = 0–0.7). The measurements were carried out at 200 MPa confining pressure and temperatures between 300 K and 1273 K (i.e. across the glass transition temperature (Tg) from glass to melt). The specimens were mixtures of a haplogranitic melt containing 5.25 wt.% H₂O and variable amounts of sub-spherical alumina particles. Additional experiments were carried out on a sample containing both, crystals and air bubbles. The temperature derivatives of the shear (dVs/dT) and compressional wave (dVp/dT) velocities for pure glass and samples with a crystal fraction of 0.5 are different below and above the glass transition temperature. For a crystal fraction 0.7, only dVp/dT changed above the Tg. In the presence of gas bubbles, Vp and Vs decrease constantly with increasing temperature. The bubble-bearing material yields a lower bulk modulus relative to its shear modulus. The propagation velocities of compressional and shear waves increase non-linearly with increasing crystal fraction with a prominent raise in the range 0.5 < ? < 0.7. The speed variations are only marginally related to the density increase due to the presence of crystals, but are dominantly related to the achievement of a continuous crystal framework. The experimental data set presented here can be utilized to estimate the relative proportions of crystals and melt present in a magmatic reservoir, which, in turn, is one of the fundamental parameters determining the mobility of magma and, consequently, exerting a prime control on the likelihood of an eruption from a sub-surficial magma reservoir.     

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.     

Mass function of dormant black holes and the evolution of active galactic nuclei

Under the assumption that accretion on to massive black holes (BHs) powers active galactic nuclei (AGNs), the mass function (MF) of the BHs responsible for their past activity is estimated. For this, we take into account not only the activity related to the optically selected AGNs, but also that required to produce the hard X-ray background (HXRB). The MF of the massive dark objects (MDOs) in nearby quiescent galaxies is computed by means of the most recent results on their demography. The two mass functions match well under the assumption that the activity is concentrated in a single significant burst with λ L L _Edd being a weakly increasing function of luminosity. This behaviour may be indicative of some level of recurrence and/or of accretion rates insufficient to maintain the Eddington rates in low-luminosity/low-redshift objects. Our results support the scenario in which the early phase of intense nuclear activity occurred mainly in early-type galaxies (E/S0) during the relatively short period in which they still had an abundant interstellar medium. Only recently, with the decline of the quasi-stellar object (QSO) luminosities, did the activity in late‐type galaxies (Sa/Sab) become statistically significant.     

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.