Atomistic simulation of the mechanisms of noble gas incorporation in minerals

Atomistic simulations have been carried out to investigate the mechanisms of noble gas incorporation in minerals using both the traditional two-region approach and the “supercell” method. The traditional two-region approach has been used to calculate defect energies for Ne, Ar, Kr and Xe incorporation in MgO, CaO, diopside and forsterite in the static limit and at one atmosphere pressure. The possibilities of noble gas incorporation via both substitution and interstitial mechanisms are studied. The favored mechanism varies from mineral to mineral and from noble gas to noble gas. In all minerals studied, the variation of the solution energies of noble gas substitution with atomic radius appears approximately parabolic, analogous to those for 1⁺, 2⁺, 3⁺ and 4⁺ trace element incorporation on crystal lattice sites. Noble gas solution energies thus also fall on a curve, similar to those previously observed for cations with different charges, but with much lower curvature.The “supercell” method has been used to investigate the pressure dependence of noble gas incorporation in the same systems. Results indicate a large variation of the solubility of the larger noble gases, Kr and Xe with pressure. In addition, explicit simulation of incorporation at the (0 0 1) surface of MgO shows that the solubility of the heavier noble gases may be considerably enhanced by the presence of interfaces.     

A dipole field model for axisymmetric alfvén waves with finite ionosphere conductivities

An axisymmetric model for approximate solution of the magnetospheric Alfvén wave problem at latitudes above the plasmapause is proposed, in which a realistic dipole geometry is combined with finite anisotropic ionosphere conductivities, thus bringing together various ideas of previous authors. It is confirmed that the axisymmetric toroidal and poloidal modes interact via the ionospheric Hall effect, and an approximate method of solution is suggested using previously derived closed solutions of the uncoupled wave equations.A solution for zero Hall conductivity is obtained, which consists of sets of independent shell oscillations, regardless of the magnitude of the Pedersen conductivity. One set reduces to the classical solutions for infinite Pedersen conductivity, while another predicts a new set of harmonics of a quarter-wave fundamental, with longer eigenperiods than the classical solutions for a given L-shell.     

Temperature and its control of isotope fractionation by a sulfate-reducing bacterium

A synthesis of previous results, which we dub the “standard model,” provides a prediction as to how isotope fractionation during sulfate reduction should respond to physiological variables such as specific rate of sulfate reduction and environmental variables such as substrate availability and temperature. The standard model suggests that isotope fractionation should decrease with increasing specific rates of sulfate reduction (rate per cell). Furthermore, the standard model predicts that low fractionations should be found at both high and low temperatures whereas the highest fractionations should be found in the intermediate temperature range. These fractionation trends are controlled, as a function of temperature, by the balance between the transfer rates of sulfate into and out of the cell and the exchange between the sulfur pools internal to the organism. We test this standard model by conducting experiments on the growth physiology and isotope fractionation, as a function of temperature, by the sulfate-reducing bacterium Desulfovibrio desulfuricans (DSMZ 642). Our results contrast with the “standard model” by showing a positive correlation between specific rates of sulfate reduction and fractionation. Also by contrast with the standard model, we found the highest fractionations at low and high temperatures and the lowest fractionations in the intermediate temperature range. We develop a fractionation model which can be used to explain both our results as well as the results of the “standard model.” Differences in fractionation with temperature relate to differences in the specific temperature response of internal enzyme kinetics as well as the exchange rates of sulfate in and out of the cell. It is expected that the kinetics of these processes will show strain-specific differences.     

Pollution history and recovery of a boreal lake exposed to a heavy bleached pulping effluent load

We examined the effects of heavy pulp mill discharges on the Lake Lievestuoreenjärvi ecosystem and the later recovery of diatom and chironomid communities from age-dated short core samples. Beginning in 1927 the lake received a heavy effluent load from a sulphite pulp mill. Except for the recession during the Second World War and the temporary closure of the mill from 1967 to 1971, the industrial load, containing large quantities of nutrients, organic matter and toxic compounds, increased continuously. In the early 1980s, laboratory documents were falsified by the directors of the mill and the systematic illegal effluent overload led to a collapse of the whole lake ecosystem. In 1985, the outdated plant was finally closed down. Based on the assessment of chemical properties and biological remains of the sediment, we distinguished five developmental phases in the ecological state of the lake. In the pre-industrial phase, the pelagic and profundal benthic communities were dominated by species preferring ultraoligotrophic or oligotrophic lakes. Concomitant with the increasing discharge and deposition of chlorine compounds, resin acids, and mercury, as well as strong acidity and hypolimnetic and epilimnetic anoxia, the ecological status changed in a short period from excellent to bad. Finally, in the early 1960s, the majority of the lake was virtually dead and the aquatic life survived only in the uppermost littoral zone. Since 1985, a fast recovery in the water quality has led to a strong, but temporary eutrophy in pelagic communities. The main peak of eutrophication was caused by the invasion of a species new to the lake,Aulacoseira granulata var.angustissima. Later, the pelagic communities shifted towards oligotrophy, but the original, pre-industrial status has not been re-established. The profundal benthic communities have not achieved the pre-industrial structure, but at present indicate mesotrophy.     

A modeling of the structure and favorable H-docking sites and defects for the high-pressure silica polymorph stishovite

Employing first-principles methods, the docking sites for H were determined and H, Al, and vacancy defects were modeled with an infinite periodic array of super unit cells each consisting of 27 contiguous symmetry nonequivalent unit cells of the crystal structure of stishovite. A geometry optimization of the super-cell structure reproduces the observed bulk structure within the experimental error when P1 translational symmetry was assumed and an array of infinite extent was generated. A mapping of the valence electrons for the structure displays mushroom-shaped isosurfaces on the O atom, one on each side of the plane of the OSi₃ triangle in the nonbonded region. An H atom, placed in a cell near the center of the super cell, was found to dock upon geometry optimization at a distance of 1.69 Å from the O atom with the OH vector oriented nearly perpendicular to the plane of the triangle such that the OH vector makes a angle of 91° with respect to [001]. However, an optimization of a super cell with an Al atom replacing Si and an H atom placed nearby in a centrally located cell resulted in an OH distance of 1.02 Å with the OH vector oriented perpendicular to [001] as observed in infrared studies. The geometry-optimized position of the H atom was found to be in close agreement with that (0.44, 0.12, 0.0) determined in an earlier study of the theoretical electron density distribution. The docking of the H atom at this site was found to be 330 kJ mol^–1 more stable than a docking of the atom just off the shared OO edge of the octahedra as determined for rutile. A geometry optimization of a super cell with a missing Si generated a vacant octahedra that is 20% larger than that of the SiO₆ octahedra. The valence electron density distribution displayed by the two-coordinate O atoms that coordinate the vacant octahedral site is very similar to those displayed by the bent SiOSi angles in coesite. The internal distortions induced by the defect were found to diminish rather rapidly with distance, with the structure annealing to that observed in the bulk crystal to within about three coordination spheres.     

Bistability of the thermohaline circulation identified through comprehensive 2-parameter sweeps of an efficient climate model

The effect of changes in zonal and meridional atmospheric moisture transports on Atlantic overturning is investigated. Zonal transports are considered in terms of net moisture export from the Atlantic sector. Meridional transports are related to the vigour of the global hydrological cycle. The equilibrium thermohaline circulation (THC) simulated with an efficient climate model is strongly dependent on two key parameters that control these transports: an anomaly in the specified Atlantic–Pacific moisture flux (F_a) and atmospheric moisture diffusivity (K_q). In a large ensemble of spinup experiments, the values of F_a and K_q are varied by small increments across wide ranges, to identify sharp transitions of equilibrium THC strength in a 2-parameter space (between Conveyor On and Off states). Final states from this ensemble of simulations are then used as the initial states for further such ensembles. Large differences in THC strength between ensembles, for identical combinations of F_a and K_q, reveal the co-existence of two stable THC states (Conveyor On and Off)—i.e. a bistable regime. In further sensitivity experiments, the model is forced with small, temporary freshwater perturbations to the mid-latitude North Atlantic, to establish the minimum perturbation necessary for irreversible THC collapse in this bistable regime. A threshold is identified in terms of the forcing duration required. The model THC, in a Conveyor On state, irreversibly collapses to a Conveyor Off state under additional freshwater forcing of just 0.1 Sv applied for around 100 years. The irreversible collapse is primarily due to a positive feedback associated with suppressed convection and reduced surface heat loss in the sinking region. Increased atmosphere-to-ocean freshwater flux, under a collapsed Conveyor, plays a secondary role.     

Fall days of the SNC meteorites: Evidence for an SNC meteoroid stream,and a common site of origin

Abstract— Four of the SNC meteorites of putative Martian origin are falls. Two of these fell on October 3: Chassigny in 1815 and Zagami in 1962. The probability of this coincidence arising from random fall days is approximately 1 in 60. If this coincidence is not the result of chance, it suggests that some of the SNC meteorites are derived from a meteoroid stream. In that Chassigny and Zagami span nearly the full range of SNC lithologies and histories, the coincidence of fall days is consistent with suggestions that all of the SNCs came from a single site (impact crater) on their parent planet.