How stacking disorder can conceal the actual structure of micas: the case of phengites

The present study deals with how stochastic stackings of tetrahedral/octahedral phengitic sheets bearing diverse cation distributions affect diffraction signals and the structural inferences therefrom derived. The interest for such minerals is dictated by that the stability of phengite polytypes, their cation distributions and P/T conditions of crystallization are related to each other. We focus our attention on layers’ probabilistic sequences that preserve the topology of the polytypes 2M ₁(SG: C2/c) and 3T(SG: P3₁12). Neutron diffraction intensities are modelled by a Monte Carlo approach and then used as artificial experimental data for conventional structure refinements that yield the occupancy factors in the fourfold (Si, Al) and sixfold (Al, Mg) coordination sites of 2M ₁ and 3T. The cation ordering from structure refinement tallies with the one of the “average structure” of a stochastic stacking, but it can significantly differ from those of the individual tetrahedral/octahedral sheets. For instance, sheets having ordered cation arrangements can lead to a stochastic structure which is supposed to bear a fully disordered cation partitioning according to structure refinement. This affects the configuration entropy contributions: the values obtained by conventional refinements can deviate from the correct ones up to 30 %. The analysis of the equivalent reflection intensities brings to light the anomalies hinting at the occurrence of such stacking disorder (using modelled reflections, the mean ratio between standard deviation and average intensity of symmetry equivalent reflections is ideally 0 for perfect crystal structures, but it can amount up to 6 in stochastically disordered phengites). However, taking into account the instrumental uncertainties and the deviations from ideality of actual crystals, such phenomena are very difficult to be detected experimentally.     

Oxygen Consumption in Permeable and Cohesive Sediments of the Gulf of Aqaba

Oxygen profiles were measured in the sediments of the Gulf of Aqaba (Red Sea), an oligotrophic marine system affected by episodic seasonal flash floods and intense aeolian dry deposition. Sediment cores were retrieved from shallow (15–45 m), intermediate (250–561 m) and deep (700 m) water sites of south–north and east–west transects. Dissolved oxygen concentrations were measured simultaneously by using microelectrodes and microoptodes immediately after sampling and after transportation. Oxygen penetration depths were found to increase from 2 to 5 mm at the shallow water sites with sandy permeable sediments to 10–21 mm at the deeper sites with cohesive muddy sediments. This increase corresponds to decrease in oxygen diffusive fluxes at the sediment–water interface and oxygen consumption rates with depth. Oxygen consumption rates exhibit local maxima at the oxic–anoxic sediment boundary, which may be attributed to oxygen reduction coupled to oxidation of dissolved Fe(II) and Mn(II) at deep and intermediate water sites and of hydrogen sulfide at shallow water sites. Microelectrodes and microoptodes measurements of cohesive sediments from deep and intermediate water sites yielded similar results. By comparison, the microoptodes displayed more robust measurements than microelectrodes in sandy near-shore sediments. This was attributed to their flexible fiber structure that is less likely to break or to abruptly displace sand particles. After transportation of sediment cores from Eilat to Beer Sheva followed by ≤?24-h storage, no changes in oxygen fluxes and consumption rates were detected.     

The Averno 2 fissure eruption: a recent small-size explosive event at the Campi Flegrei Caldera (Italy)

The Averno 2 eruption (3,700 ± 50 a B.P.) was an explosive low-magnitude event characterized by magmatic and phreatomagmatic explosions, generating mainly fall and surge beds, respectively. It occurred in the Western sector of the Campi Flegrei caldera (Campanian Region, South Italy) at the intersection of two active fault systems, oriented NE and NW. The morphologically complex crater area, largely filled by the Averno lake, resulted from vent activation and migration along the NE-trending fault system. The eruption generated a complex sequence of pyroclastic deposits, including pumice fall deposits in the lower portion, and prevailing surge beds in the intermediate-upper portion. The pyroclastic sequence has been studied through stratigraphical, morphostructural and petrological investigations, and subdivided into three members named A through C. Member A was emplaced during the first phase of the eruption mainly by magmatic explosions which generated columns reaching a maximum height of 10 km. During this phase the eruption reached its climax with a mass discharge rate of 3.2 10⁶ kg/s. Intense fracturing and fault activation favored entry of a significant amount of water into the system, which produced explosions driven by variably efficient water-magma interaction. These explosions generated wet to dry surge deposits that emplaced Member B and C, respectively. Isopachs and isopleths maps, as well as areal distribution of ballistic fragments and facies variation of surge deposits allow definition of four vents that opened along a NE oriented, 2 km long fissure. The total volume of magma extruded during the eruption has been estimated at about 0.07 km³ (DRE). The erupted products range in composition from initial, weakly peralkaline alkali-trachyte, to last-emplaced alkali-trachyte. Isotopic data and modeling suggest that mixing occurred during the Averno 2 eruption between a more evolved, less radiogenic stored magma, and a less evolved, more radiogenic magma that entered the shallow reservoir to trigger the eruption. The early phases of the eruption, during which the vent migrated from SW to the center of the present lake, were fed by the more evolved, uppermost magma, while the following phases extruded the less evolved, lowermost magma. Integration of the geological and petrological results suggests that the Averno 2 complex eruption was fed from a dyke-shaped shallow reservoir intruded into the NE-SW fault system bordering to the west the La Starza resurgent block, within the caldera floor.     

Phytoremediation of Pyrene Contaminated Soils by Different Plant Species

Polycyclic aromatic hydrocarbons (PAHs) present serious problems in the environment because they may affect negatively human health and alter native ecological communities. Phytoremediation has long been recognized as an efficient method of eliminating PAH pollutants from soil. A pot experiment was conducted in greenhouse conditions to investigate the capability of three plant species, Medicago sativa, Brassica napus, and Lolium perenne, to promote the degradation of pyrene by measuring their growth on pyrene‐contaminated soils. After 90 days, pyrene concentration in soils declined by 32, 30, and 28%, respectively, with M. sativa, B. napus, and L. perenne, whereas it decreased only by 18% in the control soil without plants. These results indicated that pyrene was successfully removed by plants used. In particular, M. sativa showed the highest capacity for pyrene dissipation in soil, whereas L. perenne was more efficient in limiting adverse effects of pyrene contamination. In addition, the contaminant pyrene was undetectable in shoots and roots of the three species, likely because plant roots can stimulate soil microbial biomass and oxygen transport to the rhizosphere, thus facilitating indirectly the degradation process of pyrene. Further studies are in progress to evaluate the possible adsorption of pyrene to soil organic matter.     

Petrology of lavas from the 2004–2005 flank eruption of Mt. Etna,Italy: inferences on the dynamics of magma in the shallow plumbing system

Following the 2001 and 2002–2003 flank eruptions, activity resumed at Mt. Etna on 7 September 2004 and lasted for about 6 months. This paper presents new petrographic, major and trace element, and Sr–Nd isotope data from sequential samples collected during the entire 2004–2005 eruption. The progressive change of lava composition allowed defining three phases that correspond to different processes controlling magma dynamics inside the central volcano conduits. The compositional variability of products erupted up to 24 September is well reproduced by a fractional crystallization model that involves magma already stored at shallow depth since the 2002–2003 eruption. The progressive mixing of this magma with a distinct new one rising within the central conduits is clearly revealed by the composition of the products erupted from 24 September to 15 October. After 15 October, the contribution from the new magma gradually becomes predominant, and the efficiency of the mixing process ensures the emission of homogeneous products up to the end of the eruption. Our results give insights into the complex conditions of magma storage and evolution in the shallow plumbing system of Mt. Etna during a flank eruption. Furthermore, they confirm that the 2004–2005 activity at Etna was triggered by regional movements of the eastern flank of the volcano. They caused the opening of a complex fracture zone extending ESE which drained a magma stored at shallow depth since the 2002–2003 eruption. This process favored the ascent of a different magma in the central conduits, which began to be erupted on 24 September without any significant change in eruptive style, deformation, and seismicity until the end of eruption.     

Exosphere generation of the Moon investigated through a high-energy neutral detector

Observation of the lunar exosphere is a tool for remote sensing of the surface properties. The sources of this exosphere are related to the interactions of the lunar surface with the solar radiation, with the solar wind or Earth??s magnetospheric plasma, and with the interplanetary dust and meteorites. In fact, the exospheric particles are continuously created and subsequently lost in the interplanetary space, photo-ionized or re-adsorbed by the surface. Eventually, the estimation of the surface composition is not possible without the knowledge of the active release mechanisms. The relative weight of the different release processes of the various atoms, ions and molecules from the surface is still an open debate. Investigation of the Moon??s release processes and interaction with the near-Earth environment is of crucial importance for both determining the relative process release contribution and understanding the surface evolution of other airless bodies, like Mercury and the giant planets?? moons. In this work, an attempt to analyze the processes that take place on the surface of these small airless bodies, as a result of their exposure to the space environment, has been realized by means of the MonteCarlo Environment Simulation Tool (EST), applied to the Moon. The model results show that the different release processes can be identified by analysing the exospheric energy distribution. Finally, the instrument concept of the ??Analizzatore Lunare di ENA?? (ALENA), part of the MAGIA payload and specifically designed for detecting the high-energy particles released from the lunar surface is presented.     

Benthic invertebrate assemblages and functional feeding groups in the Paraná River floodplain (Argentina)

The benthic invertebrate assemblages and functional feeding groups in different mesohabitats of the Middle Paraná River–floodplain system were analyzed. Benthic invertebrates and bottom sediments were sampled in a secondary channel (center and bank mesohabitats), a temporal marginal fluvial wetland adjacent to the river, an isolated lake and a connected lake during low water level. Cluster analysis of average invertebrate densities based on the Bray Curtis dissimilarity index yielded a group composed by the mesohabitats with higher species richness, the floodplain lakes, banks mesohabitats and the wetland. The center mesohabitat of the main channel characterized by sandy sediments with low organic matter content and the lowest invertebrate densities and species richness was classified separately. Alpha diversity increased from the center mesohabitat (6 taxa) to the adjacent wetland (71 taxa), and were similar between the floodplain lakes (24 and 22 taxa) and the river bank mesohabitat (24 taxa). Gamma and beta diversities (Whittaker index) were 92 and 2.19, respectively. The highest turnover of taxa was between the river and the other mesohabitats and the lowest between floodplain lakes. Detrended correspondence analysis (DCA) showed a clear separation of wetland and banks from other mesohabitats (axis 1 and 2 explained 52.25% variance) explained by shredders and collector-filterers. The other mesohabitats were arranged in a gradient from the main channel mostly related to collector-gatherers to the connected lake and the isolated lake that were mostly characterized by predators and scrapers. The invertebrate assemblage complexity and functional feeding groups composition increased in the lateral dimension, from the center of the main channel to the temporal marginal fluvial wetland due to the influences of the spatial heterogeneity caused by different sources of organic matter inputs.     

Denitrification and the stoichiometry of nutrient regeneration in Waquoit Bay, Massachusetts

To determine the removal of regenerated nitrogen by estuarine sediments, we compared sediment N₂ fluxes to the stoichiometry of nutrient and O₂ fluxes in cores collected in the Childs River, Cape Cod, Massachusetts. The difference between the annual PO₄ ³⁻ (0.2 mol P m⁻² yr⁻¹) and NH₄ ⁺ (1.6 mol N m⁻² yr⁻¹) flux and the Redfield N∶P ratio of 16 suggested an annual deficit of 1.5 mol N m⁻² yr⁻¹. Denitrification predicted from O₂∶NH₄ ⁺ flux ratios and measured as N₂ flux suggested a nitrogen sink of roughly the same magnitude (1.4 mol N m⁻² yr⁻¹). Denitrification accounted for low N∶P ratios of benthic flux and removed 32–37% of nitrogen inputs entering the relatively highly nutrient loaded Childs River, despite a relatively brief residence time for freshwater in this system. Uptake of bottom water nitrate could only supply a fraction of the observed N₂ flux. Removal of regenerated nitrogen by denitrification in this system appears to vary seasonally. Denitrification efficiency was inversely correlated with oxygen and ammonium flux and was lowest in summer. We investigated the effect of organic matter on denitrification by simulating phytoplankton deposition to cores incubated in the lab and by deploying chambers on bare and macroaglae covered sediments in the field. Organic matter addition to sediments increased N₂ flux and did not alter denitrification efficiency. Increased N₂ flux co-varied with O₂ and NH₄ ⁺ fluxes. N₂ flux (261±60 μmol m⁻² h⁻¹) was lower in chambers deployed on macroalgal beds than deployed on bare sediments (458±70 μmol m⁻² h⁻¹), and O₂ uptake rate was higher in chambers deployed on macroalgal beds (14.6±2.2 mmol m⁻² h⁻¹) than on bare sediments (9.6±1.5 mmol m⁻² h⁻¹). Macroalgal cover, which can retain nitrogen in the system, is a link between nutrient loading and denitrification. Decreased denitrification due to increasing macroalgal cover could create a positive feedback because decreasing denitrification would increase nitrogen availability and could increase macroalgae cover.     

Surface and groundwater pollution by organochlorine compounds in a typical soybean system from the south Pampa,Argentina

Organochlorine pesticides (OCPs) use has been restricted or forbidden in Argentina since 1998 and technical endosulfan is the last currently used OCPs on the soybean-wheat production. As they persist in soil for several years after application, OCPs constitute a source of environmental pollution. This work aims to assess OCPs contamination of groundwater (Gw) and streamwater (Sw) in the Quequén Grande River watershed from south Argentinean Pampas in relation to the hydrogeological characteristics. OCPs were analyzed in Sw, Gw, surface bottom sediments, soils and borehole cutting sediments (Cs) by gas chromatograph-electron capture detector. Pesticide distribution in Cs was dependent on the characteristic of the non-saturated zone. Leached pesticides over 3 m in Cs showed the pattern: HCHs = endosulfan > chlordanes > DDTs, and from 3 to 6 m heptachlor was the main group as a consequence of the past use of this compound in the area, mainly on potato crops. Endosulfan reaches Gw during application season as well as during flooding events while a retard effect was observed for Sw. Levels of α- and β-isomers were in certain cases above national (7 ng L⁻¹) and international (3 ng L⁻¹) limits for aquatic biota protection. As the endosulfan sulfate metabolite was present in Gw and Sw and due to its high toxicity, it should be considered in the establishment of water quality criteria for human and environmental protection.