Growing spherulitic calcite grains in saline, hyperalkaline lakes: experimental evaluation of the effects of Mg-clays and organic acids

The origin of spherical-radial calcite bodies – spherulites – in sublacustrine, hyperalkaline and saline systems is unclear, and therefore their palaeoenvironmental significance as allochems is disputed. Here, we experimentally investigate two hypotheses concerning the origin of spherulites. The first is that spherulites precipitate from solutions super-saturated with respect to magnesium-silicate clays, such as stevensite. The second is that spherulite precipitation happens in the presence of dissolved, organic acid molecules. In both cases, experiments were performed under sterile conditions using large batches of a synthetic and cell-free solution replicating waters found in hyperalkaline, saline lakes (such as Mono Lake, California). Our experimental results show that a highly alkaline and highly saline solution supersaturated with respect to calcite (control solution) will precipitate euhedral to subhedral rhombic and trigonal bladed calcite crystals. The same solution supersaturated with respect to stevensite precipitates sheet-like stevensite crystals rather than a gel, and calcite precipitation is reduced by ~ 50% compared to the control solution, producing a mixture of patchy prismatic subhedral to euhedral, and minor needle-like, calcite crystals. Enhanced magnesium concentration in solution is the likely the cause of decreased volumes of calcite precipitation, as this raised equilibrium ion activity ratio in the solution. On the other hand, when alginic acid was present then the result was widespread development of micron-size calcium carbonate spherulite bodies. With further growth time, but falling supersaturation, these spherules fused into botryoidal-topped crusts made of micron-size fibro-radial calcite crystals. We conclude that the simplest tested mechanism to deposit significant spherical-radial calcite bodies is to begin with a strongly supersaturated solution that contains specific but environmentally-common organic acids. Furthermore, we found that this morphology is not a universal consequence of having organic acids dissolved in the solution, but rather spherulite development requires specific binding behaviour. Finally, we found that the location of calcite precipitation was altered from the air:water interface to the surface of the glassware when organic acids were present, implying that attached calcite precipitates reflect precipitation via metal–organic intermediaries, rather than direct forcing via gas exchange

Crystal structure of dichlorido(4,11-dimethyl-1,4,8,11-tetraazabicyclo[6.6.2]hexadecane)iron(III) hexafluoridophosphate

The title compound, [FeCl₂(C₁₄H₃₀N₄)]PF₆, contains Fe³⁺ coordinated by the four nitro­gen atoms of an ethyl­ene cross-bridged cyclam macrocycle and two cis chloride ligands in a distorted octa­hedral environment. In contrast to other similar compounds this is a monomer. Inter­molecular C-H...Cl inter­actions exist in the structure between the complex ions. Comparison with the mononuclear Fe²⁺ complex of the same ligand shows that the smaller Fe³⁺ ion is more fully engulfed by the cavity of the bicyclic ligand. Comparison with the μ-oxido dinuclear complex of an unsubstituted ligand of the same size demonstrates that the methyl groups of 4,11-dimethyl-1,4,8,11-tetra­aza­bicyclo­[6.6.2]hexa­decane prevent dimerization upon oxidation

Above- and below-ground biomass accumulation, production, and distribution of sweetgum and loblolly pine grown with irrigation and fertilization.

Abstract: Increased forest productivity has been obtained by improving resource availability through water and nutrient amendments. However, more stress-tolerant species that have robust site requirements do not respond consistently to irrigation. An important factor contributing to robust site requirements may be the distribution of biomass belowground, yet available information is limited. We examined the accumulation and distribution of above- and below-ground biomass in sweetgum (Liqrridambar sfyrac$lua L.) and loblolly pine (Pinus taeda L.) stands receiving irrigation and fertilization. Mean annual aboveground production after 4 years ranged from 2.4 to 5.1 ~g.ha-'.year' for sweetgum and from 5.0 to 6.9 ~g.ha-l.year-l for pine. Sweetgum responded positively to irrigation and fertilization with an additive response to irrigation + fertilization. Pine only responded to fertilization. Sweetgum root mass fraction (RME)in creased with fertilization at 2 years and decreased with fertilization at 4 years. There were no detectable treatment differences in loblolly pine RMF. Development explained from 67% to 98% of variation in shoot versus root allometry for ephemeral and perennial tissues, fertilization explained no more than 5% of the variation in for either species, and irrigation did not explain any. We conclude that shifts in allocation from roots to shoots do not explain nutrient-induced growth stimulations

On the mechanisms governing gas penetration into a tokamak plasma during a massive gas injection

A new 1D radial fluid code, IMAGINE, is used to simulate the penetration of gas into a tokamak plasma during a massive gas injection (MGI). The main result is that the gas is in general strongly braked as it reaches the plasma, due to mechanisms related to charge exchange and (to a smaller extent) recombination. As a result, only a fraction of the gas penetrates into the plasma. Also, a shock wave is created in the gas which propagates away from the plasma, braking and compressing the incoming gas. Simulation results are quantitatively consistent, at least in terms of orders of magnitude, with experimental data for a D 2 MGI into a JET Ohmic plasma. Simulations of MGI into the background plasma surrounding a runaway electron beam show that if the background electron density is too high, the gas may not penetrate, suggesting a possible explanation for the recent results of Reux et al in JET (2015 Nucl. Fusion 55 093013)

Measurement of the νe and total 8B solar neutrino fluxes with the Sudbury Neutrino Observatory phase-III data set

This paper details the solar neutrino analysis of the 385.17-day phase-III data set acquired by the Sudbury Neutrino Observatory (SNO). An array of 3He proportional counters was installed in the heavy-water target to measure precisely the rate of neutrino-deuteron neutral-current interactions. This technique to determine the total active 8B solar neutrino flux was largely independent of the methods employed in previous phases. The total flux of active neutrinos was measured to be 5.54-0.31+0.33(stat.)-0.34+0.36(syst.)×106 cm-2 s-1, consistent with previous measurements and standard solar models. A global analysis of solar and reactor neutrino mixing parameters yielded the best-fit values of Δm2=7.59-0.21+0.19×10 -5eV2 and θ=34.4-1.2+1.3degrees

Modification of the anion sublattice in metal nitrides

The main goal of solid-state chemistry is the synthesis and characterisation of new compounds with technologically exploitable properties. To this aim, one established chemical route is the modification of known inorganic materials, in most cases oxides, via substitution or insertion of cations different from the original makeup. An alternative, and less frequently adopted, approach is the manipulation of the anion sublattice to yield mixed-anion materials. Recent examples of materials with structural and physical properties tunable via both anionic and cationic substitutions are bringing more attention to the potential of this approach as an alternative and/or complementary chemical approach to cationic modifications. Within this review, structural relationships and differences between nitrides and mixed-anion nitrides, such as nitride-halides, nitride-sulfides, nitride-carbides and nitride-borides will be highlighted to set the scenery and the future challenges to a fuller exploitation of the ‘anionic route’ as a strategy towards the design of new materials