Dual speciation of nitrogen in silicate melts at high pressure and temperature: An experimental study

Solubility and speciation of nitrogen in silicate melts have been investigated between 1400 and 1700 °C and at pressures ranging from 10 to 30 kbar for six different binary alkali and alkaline-earth silicate liquids and a Ca-Mg-alumino silicate. Experiments were performed in a piston-cylinder apparatus. The nitrogen source is silver azide, which breaks down to Ag and molecular N₂ below 300 °C. At high pressure and temperature, the nitrogen content may be as high as 0.7 wt% depending on the melt composition, pressure, and temperature. It increases with T, P and the polymerization state of the liquid. Characterization by Raman spectroscopy and ¹⁵N solid state MAS NMR indicates that nitrogen is not only physically dissolved as N₂ within the melt structure like noble gases, but a fraction of nitrogen interacts strongly with the silicate network. The most likely nitrogen-bearing species that can account for Raman and NMR results is nitrosyl group. Solubility data follow an apparent Henry’s law behavior and are in good agreement with previous studies when the nitrosyl content is low. On the other hand, a significant departure from a Henry’s law behavior is observed for highly depolymerized melts, which contain more nitrosyl than polymerized melts. Possible solubility mechanisms are also discussed. Finally, a multi-variant empirical relation is given to predict the relative content of nitrosyl and molecular nitrogen as a function of P, T, and melt composition and structure. This complex speciation of nitrogen in melts under high pressure may have significant implication concerning crystal-melt partitioning of nitrogen as well as for potential elemental and isotopic fractionation of nitrogen in the deep Earth.     

Behaviour of Fe-oxides relevant to contaminant uptake in the environment

The behaviour of Fe-oxides was investigated during precipitation and co-precipitation, phase transformation and dissolution, while their ability to adsorb and incorporate trace components was examined. Some samples were synthesised and studied under controlled laboratory conditions and other samples were taken from experiments designed to test the effectiveness of waste treatment strategies using iron. Surface-sensitive and high-resolution techniques were used to complement information gathered from classical, macroscopic methods.

Adsorption isotherms for Ni²⁺ uptake on synthetic ferrihydrite (Fe₅HO₈·4H₂O, often written simply Fe(OH)₃), goethite (-FeOOH), hematite (-Fe₂O₃) and magnetite (Fe₃O₄) were all similar, increasing as expected at higher pH. Desorption behaviour was also similar, but one third or more of the Ni²⁺ failed to return to solution. In the past, “irreversible sorption” has been blamed on uptake into micro-fractures or pores, but during examination (using Atomic force microscopy, AFM) of hundreds of Fe-oxide particles, no evidence for such features could be found, leading to the conclusion that Ni²⁺ must become incorporated onto or into the solids. When solutions of Fe(II) are oxidised in controlled laboratory conditions or during treatment of ash from municipal waste incinerators, two-line ferrihydrite forms rapidly and on never-dried samples, AFM shows abundant individual particles with diameter ranging from 0.5 to several tens of nanometers. Aging in solution at 70°C promotes growth of the particles into hematite and goethite and their identification (by X-ray powder diffraction, XRPD, with Rietveld refinement) becomes possible at the same aging stage as mineral morphology becomes recognisable by AFM. In other experiments that were designed to mimic natural attack by organic acids, colloidal lepidocrocite (γ-FeOOH) was observed in situ by AFM, while reductive dissolution removed material on specific crystal faces. Lath ends are eroded fastest while basal planes are more stable.

In order to help elucidate mechanisms of contaminant immobilisation by Fe-oxides, we examined samples from a reactive barrier made with 90% quartz sand, 5% bentonite and 5% zero-valent iron filings that had reacted with a solution typical of leachate from coal-burning fly ash using time-of-flight secondary ion mass spectroscopy (TOF-SIMS). Fe(0) oxidised to Fe(III), while soluble and toxic Cr(VI) was reduced to insoluble Cr(III). Chemical maps show Fe-oxide coatings on bentonite; Cr is associated with Fe-oxides to some extent but its association with Ca in a previously undescribed phase is much stronger. Other samples taken from municipal waste incinerator ash that had been treated by aeration in Fe(II) solutions were examined with transmission electron microscopy (TEM), selected area electron diffraction (SAED) and energy dispersive X-ray spectroscopy (EDS). Pb and some Zn are seen to be dispersed throughout two-line ferrihydrite aggregates, whereas Sn and some Zn are incorporated simply as a result of entrainment of individual ZnSn-oxide crystallites.

Geochemical speciation models that fail to account for contaminant uptake in solid solutions within major phases or as thin coatings or entrained crystals of uncommon phases such as those described here risk to underestimate contaminant retardation or immobilisation.     

Seismic‐stratigraphic record of a deglaciation sequence: from the marine Laflamme Gulf to Lake Saint‐Jean (late Quaternary,Québec,Canada)

The stratigraphy of the last deglaciation sequence is investigated in Lake Saint‐Jean (Québec Province, Canada) based on 300 km of echo‐sounder two dimensional seismic profiles. The sedimentary archive of this basin is documented from the Late Pleistocene Laurentidian ice‐front recession to the present‐day situation. Ten seismic units have been identified that reflect spatio‐temporal variations in depositional processes characterizing different periods of the Saint‐Jean basin evolution. During the postglacial marine flooding, a high deposition rate of mud settling, from proglacial glacimarine and then prodeltaic plumes in the Laflamme Gulf, produced an extensive, up to 50 m thick mud sheet draping the isostatically depressed marine basin floor. Subsequently, a closing of the water body due to glacio‐isostatic rebound occurred at 8.5 cal. ka BP, drastically modifying the hydrodynamics. Hyperpycnal flows appeared because fresh lake water replaced dense marine water. River sediments were transferred towards the deeper part of the lake into river‐related sediment drifts and confined lobes. The closing of the water body is also marked by the onset of a wind‐driven internal circulation associating coastal hydrodynamics and bottom currents with sedimentary features including shoreface deposits, sediment drifts and a prograding shelf‐type body. The fingerprints of a forced regression are well expressed by mouth‐bar systems and by the shoreface–shelf system, the latter unexpected in such a lacustrine setting. In both cases, a regressive surface of lacustrine erosion (RSLE) has been identified, separating sandy mouth‐bar from glaciomarine to prodeltaic muds, and sandy shoreface wedges from the heterolithic shelf‐type body, respectively. The Lake Saint‐Jean record is an example of a regressive succession driven by a glacio‐isostatic rebound and showing the transition from late‐glacial to post‐glacial depositional systems.     

Experimental and numerical investigations of the behaviour of a heat exchanger pile

The geothermal use of concrete geostructures (piles, walls and slabs) is an environmentally friendly way of cooling and heating buildings. With such geothermal structures, it is possible to transfer energy from the ground to fluid‐filled pipes cast in concrete and then to building environments. To improve the knowledge in the field of geothermal structures, the behaviour of a pile subjected to thermo‐mechanical loads is studied in situ. The aim is to study the increased loads on pile due to thermal effects. The maximum thermal increment applied to the pile is on the order of 21°C and the mechanical load reached 1300 kN. Coupled multi‐physical finite element modelling is carried out to simulate the observed experimental results. It is shown that the numerical model is able to reproduce the most significant thermo‐mechanical effects. Copyright © 2006 John Wiley & Sons, Ltd.     

The Planeterrella,a pedagogic experiment in planetology and plasma physics

We present here a plasma physics experiment which makes it possible to simulate, in a naive yet useful way, the formation of polar lights. It involves shooting electrons at a magnetized sphere placed in a vacuum chamber. This experiment, inspired by K. Birkeland’s Terrella, built at the turn of 19th century, allows the visualization of very many geophysical and astrophysical situations. Although delicate, it is feasible at undergraduate level.     

Nonuniform cratering of the Moon and a revised crater chronology of the inner Solar System

We model the cratering of the Moon and terrestrial planets from the present knowledge of the orbital and size distribution of asteroids and comets in the inner Solar System, in order to refine the crater chronology method. Impact occurrences, locations, velocities and incidence angles are calculated semi-analytically, and scaling laws are used to convert impactor sizes into crater sizes. Our approach is generalizable to other moons or planets. The lunar cratering rate varies with both latitude and longitude: with respect to the global average, it is about 25% lower at (±65°N, 90°E) and larger by the same amount at the apex of motion (0°N, 90°W) for the present Earth-Moon separation. The measured size-frequency distributions of lunar craters are reconciled with the observed population of near-Earth objects under the assumption that craters smaller than a few kilometers in diameter form in a porous megaregolith. Varying depths of this megaregolith between the mare and highlands is a plausible partial explanation for differences in previously reported measured size-frequency distributions. We give a revised analytical relationship between the number of craters and the age of a lunar surface. For the inner planets, expected size-frequency crater distributions are calculated that account for differences in impact conditions, and the age of a few key geologic units is given. We estimate the Orientale and Caloris basins to be 3.73 Ga old, and the surface of Venus to be 240 Ma old. The terrestrial cratering record is consistent with the revised chronology and a constant impact rate over the last 400 Ma. Better knowledge of the orbital dynamics, crater scaling laws and megaregolith properties are needed to confidently assess the net uncertainty of the model ages that result from the combination of numerous steps, from the observation of asteroids to the formation of craters. Our model may be inaccurate for periods prior to 3.5 Ga because of a different impactor population, or for craters smaller than a few kilometers on Mars and Mercury, due to the presence of subsurface ice and to the abundance of large secondaries, respectively. Standard parameter values allow for the first time to naturally reproduce both the size distribution and absolute number of lunar craters up to 3.5 Ga ago, and give self-consistent estimates of the planetary cratering rates relative to the Moon.