Nuclear and incommensurate magnetic structure of NaFeGe2O6 between 5?K and 298?K and new data on multiferroic NaFeSi2O6

The compound NaFeGe₂O₆ was grown synthetically as polycrystalline powder and as large single crystals suitable for X-ray and neutron-diffraction experiments to clarify the low temperature evolution of secondary structural parameters and to determine the low temperature magnetic spins structure. NaFeGe₂O₆ is isotypic to the clinopyroxene-type compound aegirine and adopts the typical HT-C2/c clinopyroxene structure down to 2.5?K. The Na-bearing M2 polyhedra were identified to show the largest volume expansion between 2.5?K and room temperature, while the GeO₄ tetrahedra behave as stiff units. Magnetic susceptibility measurements show a broad maximum around 33?K, which marks the onset of low-dimensional magnetic ordering. Below 12?K NaFeGe₂O₆ transforms to an incommensurately modulated magnetic spin state, with k?=?[0.323, 1.0, 0.080] and a helical order of spins within the M1-chains of FeO₆ octahedra. This is determined by neutron-diffraction experiments on a single crystal. Comparison of NaFeGe₂O₆ with NaFeSi₂O₆ is given and it is shown that the magnetic ordering in the latter compound, aegirine, also is complex and is best described by two different spin states, a commensurate one with C2??/c?? symmetry and an incommensurate one, best being described by a spin density wave, oriented within the (1 0 1) plane.     

Magnetic properties and cation ordering of nanopowders of the synthetic analogue of kuramite, Cu3SnS4

An extensive characterisation of the magnetic properties of synthetic powders of kuramite, with formal composition Cu₃SnS₄, was performed. Powders were investigated through superconducting quantum interference device (SQUID) magnetometry, electron paramagnetic resonance (EPR) spectroscopy, X-ray powder diffraction (XRPD), scanning and transmission electron microscopies (SEM and TEM) and microanalysis. SEM and TEM reveal the presence of nanodimensioned particles. XRPD clearly shows that Cu₃SnS₄ crystallised in a cubic sphalerite-type structural model, in spite of the stannite-type tetragonal structure described for the natural phase. This difference arises from a full random distribution of cations. Synthetic kuramite nanopowders exhibit a marked paramagnetism, originated by the presence of Cu(II), definitely assessed by EPR measurements. Moreover, the overall magnetic behaviour of the sample cannot be simply ascribed to diluted paramagnetism, and this suggests the presence of strong superexchange interactions among Cu(II) ions even at room temperature. The main consequences of these results are the definitive assessment of the chemical formula Cu(I)₂Cu(II)SnS₄ and of a random distribution of Cu(II), Cu(I) and Sn(IV) ions within the available tetrahedral sites.     

On the use of IPCC-class models to assess the impact of climate on Living Marine Resources

The study of climate impacts on Living Marine Resources (LMRs) has increased rapidly in recent years with the availability of climate model simulations contributed to the assessment reports of the Intergovernmental Panel on Climate Change (IPCC). Collaboration between climate and LMR scientists and shared understanding of critical challenges for such applications are essential for developing robust projections of climate impacts on LMRs. This paper assesses present approaches for generating projections of climate impacts on LMRs using IPCC-class climate models, recommends practices that should be followed for these applications, and identifies priority developments that could improve current projections. Understanding of the climate system and its representation within climate models has progressed to a point where many climate model outputs can now be used effectively to make LMR projections. However, uncertainty in climate model projections (particularly biases and inter-model spread at regional to local scales), coarse climate model resolution, and the uncertainty and potential complexity of the mechanisms underlying the response of LMRs to climate limit the robustness and precision of LMR projections. A variety of techniques including the analysis of multi-model ensembles, bias corrections, and statistical and dynamical downscaling can ameliorate some limitations, though the assumptions underlying these approaches and the sensitivity of results to their application must be assessed for each application. Developments in LMR science that could improve current projections of climate impacts on LMRs include improved understanding of the multi-scale mechanisms that link climate and LMRs and better representations of these mechanisms within more holistic LMR models. These developments require a strong baseline of field and laboratory observations including long time series and measurements over the broad range of spatial and temporal scales over which LMRs and climate interact. Priority developments for IPCC-class climate models include improved model accuracy (particularly at regional and local scales), inter-annual to decadal-scale predictions, and the continued development of earth system models capable of simulating the evolution of both the physical climate system and biosphere. Efforts to address these issues should occur in parallel and be informed by the continued application of existing climate and LMR models.     

The sinkhole enigma in the Alpine Foreland, Southeast Germany: Evidence of impact-induced rock liquefaction processes

Sudden collapse of the Quaternary soil to form sinkholes on the order of meters and tens of meters has been a geologic phenomenon within living memory in a localized area north of Lake Chiemsee in Southeast Germany. Failing a satisfying explanation, a relation with an undefined glaciation process has always been proposed. Excavations and geophysical measurements at three newly affected sites show underground features such as prominent sandy-gravelly intrusions and extrusions typical of rock liquefaction processes well known to occur during strong earthquakes. Since strong earthquakes can reasonably be excluded to have affected the area under discussion, it has been suggested that the observed widespread liquefaction is related with the recently proposed Holocene Chiemgau meteorite impact event. Except for one earlier proposed but unassertive relation between impact and liquefaction, the obviously direct association of both processes in the Chiemgau area emphasizes that observed paleoliquefaction features need not necessarily have originated solely from paleoseismicity but can provide a recognizable regional impact signature.     

A review of the NEMURO and NEMURO.FISH models and their application to marine ecosystem investigations

The evolution of the North Pacific Ecosystem Model for Understanding Regional Oceanography (NEMURO) family of models to study marine ecosystems is reviewed. Applications throughout the North Pacific have shown the models to be robust and to be able to reproduce 1D, 2D and 3D components of nutrient, carbon cycle and biogeochemical cycles as well as aspects of the lower trophic levels ecosystem (phyto- and zooplankton). NEMURO For Including Saury and Herring, an extension that includes higher trophic levels, can be run uncoupled or coupled to NEMURO. In the uncoupled mode, the growth and weight of an individual fish is computed using plankton densities simulated by NEMURO but with no feedback between fish consumption and plankton mortality. In the coupled mode, the feeding, growth and weight of a representative fish are computed, and prey removals due to feeding by fish appear as mortality terms on the prey. The NEMURO family of models continues to evolve, including effects of the microbial loop and iron limitation at lower trophic levels, and full life cycle, multi-species and multi-generational simulations at higher trophic levels. We outline perspectives for future end-to-end modeling efforts that can be used to study marine ecosystems in response to global environmental change.     

Chemical fluid transport (CFT): A window into Earth and its development

Gas phase transport according to chemical fluid transport (CFT) in Earth's crust as well as in the solar nebula is characterized by very high transport efficiency. Systematic investigations of mobilization, transport and deposition of gaseous MeX (Me = metal, X = F or Cl) compounds by solid gas equilibrium reactions are suitable to explain numerous extensive accumulations of minerals and ores. More than 40 of the considered chemical elements form volatile MeX compounds. Some elements tend to form MeF compounds, whereas others are more likely to form MeCl compounds. Silicon reacts with HF to form SiF₄ and replaces other elements to form MeF compounds at low temperature ranges. Accumulations caused by SiF₄ transport explain the formation of numerous quartz varieties and silicate minerals in Earth's crust. Iron most likely reacts with HCl to form FeCl₂ as well as FeCl₃ and explain the formation of iron or iron compounds. Thermodynamically directed transport from cool to hot areas in connection with cyclic processes increases the transport efficiency of MeX-species. Such species are SiF₄, Al₂F₆, POF₃, Cu₃Cl₃, SnCl₄, BF₃, GeF₄, GeCl₄, Ga₂Cl₆, ZrF₄, NbF₅ and TiF₄. The transport gases SiF₄ and POF₃ often react with environmental compounds forming pneumatolytic and metasomatical mineral accumulations. CFT is the “motor” of pneumatolytic and metasomatical processes.     

Gaps in cubic closest packing: from MgO via spinel to the pharmacosiderite crystal structure type

Numerous ordered defect structures are known that are related to the sodium chloride (or MgO) structure type, thus they are basically cubic closest packed (ccp) arrangements with vacancies. For example the NbO type is an MgO type in which one quarter each of the anions and the cations are missing compared to the ccp in such a way that both anions and cations are in square-planar coordination. In spinel, Al₂MgO₄, one half of the octahedrally coordinated cations are missing compared with the MgO type and only one eighth of the tetrahedrally coordinated sites within the ccp are occupied. What these cases have in common is that all these derivatives are rather dense. This is different in pharmacosiderite, K[Fe₄(OH)₄As₃O₁₂]. 6 to 7H₂O, where one half of the anion positions, three quarters of the octahedral sites and five eighth of the tetrahedral sites remain vacant, compared to the spinel type. Pharmacosiderite is a wide open porous structure with zeolitic properties. We are illustrating these relationships using a Bärnighausen symmetry tree and by tables relating the various structure types to each other.     

Volatile emissions and gas geochemistry of Hot Spring Basin,Yellowstone National Park,USA

We characterize and quantify volatile emissions at Hot Spring Basin (HSB), a large acid-sulfate region that lies just outside the northeastern edge of the 640 ka Yellowstone Caldera. Relative to other thermal areas in Yellowstone, HSB gases are rich in He and H₂, and mildly enriched in CH₄ and H₂S. Gas compositions are consistent with boiling directly off a deep geothermal liquid at depth as it migrates toward the surface. This fluid, and the gases evolved from it, carries geochemical signatures of magmatic volatiles and water–rock reactions with multiple crustal sources, including limestones or quartz-rich sediments with low K/U (or ^40?Ar/^4?He). Variations in gas chemistry across the region reflect reservoir heterogeneity and variable degrees of boiling. Gas-geothermometer temperatures approach 300 °C and suggest that the reservoir feeding HSB is one of the hottest at Yellowstone. Diffuse CO₂ flux in the western basin of HSB, as measured by accumulation-chamber methods, is similar in magnitude to other acid-sulfate areas of Yellowstone and is well correlated to shallow soil temperatures. The extrapolation of diffuse CO₂ fluxes across all the thermal/altered area suggests that 410 ± 140 t d^− 1 CO₂ are emitted at HSB (vent emissions not included). Diffuse fluxes of H₂S were measured in Yellowstone for the first time and likely exceed 2.4 t d^− 1 at HSB. Comparing estimates of the total estimated diffuse H₂S emission to the amount of sulfur as SO₄²⁻ in streams indicates ~ 50% of the original H₂S in the gas emission is lost into shallow groundwater, precipitated as native sulfur, or vented through fumaroles. We estimate the heat output of HSB as ~ 140–370 MW using CO₂ as a tracer for steam condensate, but not including the contribution from fumaroles and hydrothermal vents. Overall, the diffuse heat and volatile fluxes of HSB are as great as some active volcanoes, but they are a small fraction (1–3% for CO₂, 2–8% for heat) of that estimated for the entire Yellowstone system.     

Functioning of intertidal flats inferred from temporal and spatial dynamics of O<Subscript>2</Subscript>, H<Subscript>2</Subscript>S and pH in their surface sediment

In this article, we describe the dynamics of pH, O₂ and H₂S in the top 5–10 cm of an intertidal flat consisting of permeable sand. These dynamics were measured at the low water line and higher up the flat and during several seasons. Together with pore water nutrient data, the dynamics confirm that two types of transport act as driving forces for the cycling of elements (Billerbeck et al. 2006b): Fast surface dynamics of pore water chemistry occur only during inundation. Thus, they must be driven by hydraulics (tidal and wave action) and are highly dependent on weather conditions. This was demonstrated clearly by quick variation in oxygen penetration depth: Seeps are active at low tide only, indicating that the pore water flow in them is driven by a pressure head developing at low tide. The seeps are fed by slow transport of pore water over long distances in the deeper sediment. In the seeps, high concentrations of degradation products such as nutrients and sulphide were found, showing them to be the outlets of deep-seated degradation processes. The degradation products appear toxic for bioturbating/bioirrigating organisms, as a consequence of which, these were absent in the wider seep areas. These two mechanisms driving advection determine oxygen dynamics in these flats, whereas bioirrigation plays a minor role. The deep circulation causes a characteristic distribution of strongly reduced pore water near the low water line and rather more oxidised sediments in the centre of the flats. The two combined transport phenomena determine the fluxes of solutes and gases from the sediment to the surface water and in this way create specific niches for various types of microorganisms.