Lithium Intercalation into the Excitonic Insulator Candidate Ta2NiSe5.

A new reduced phase derived from the excitonic insulator candidate Ta2NiSe5 has been synthesized via the intercalation of lithium. LiTa2NiSe5 crystallizes in the orthorhombic space group Pmnb (no. 62) with lattice parameters a = 3.50247(3) Å, b = 13.4053(4) Å, c = 15.7396(2) Å, and Z = 4, with an increase of the unit cell volume by 5.44(1)% compared with Ta2NiSe5. Significant rearrangement of the Ta-Ni-Se layers is observed, in particular a very significant relative displacement of the layers compared to the parent phase, similar to that which occurs under hydrostatic pressure. Neutron powder diffraction experiments and computational analysis confirm that Li occupies a distorted triangular prismatic site formed by Se atoms of adjacent Ta2NiSe5 layers with an average Li-Se bond length of 2.724(2) Å. Li-NMR experiments show a single Li environment at ambient temperature. Intercalation suppresses the distortion to monoclinic symmetry that occurs in Ta2NiSe5 at 328 K and that is believed to be driven by the formation of an excitonic insulating state. Magnetometry data show that the reduced phase has a smaller net diamagnetic susceptibility than Ta2NiSe5 due to the enhancement of the temperature-independent Pauli paramagnetism caused by the increased density of states at the Fermi level evident also from the calculations, consistent with the injection of electrons during intercalation and formation of a metallic phase.

The upgraded Polaris powder diffractometer at the ISIS neutron source.

This paper describes the design and operation of the Polaris time-of-flight powder neutron diffractometer at the ISIS pulsed spallation neutron source, Rutherford Appleton Laboratory, UK. Following a major upgrade to the diffractometer in 2010-2011, its detector provision now comprises five large ZnS scintillator-based banks, covering an angular range of 6° ≤ 2θ ≤ 168°, with only minimal gaps between each bank. These detectors have a substantially increased solid angle coverage (Ω âˆ¼ 5.67 sr) compared to the previous instrument (Ω âˆ¼ 0.82 sr), resulting in increases in count rate of between 2× and 10×, depending on 2θ angle. The benefits arising from the high count rates achieved are illustrated using selected examples of experiments studying small sample volumes and performing rapid, time-resolved investigations. In addition, the enhanced capabilities of the diffractometer in the areas of in situ studies (which are facilitated by the installation of a novel design of radial collimator around the sample position and by a complementary programme of advanced sample environment developments) and in total scattering studies (to probe the nature of short-range atomic correlations within disordered crystalline solids) are demonstrated.

Investigation of the changes in hydrogen bonding accompanying the structural reorganization at 103†K in ammonium iodate.

Neutron powder diffraction has been used to observe the changes in hydrogen bonding that occur as a function of temperature in ND4IO3 and, thus, determine the structural features that occur during the low-temperature (103 K) phase transition. It is shown that in the deuterated material the change is not a phase change per se but rather a structural reorganization in which the hydrogen bonding becomes firmly locked in at the phase transition temperature, and stays in this configuration upon further cooling to 4.2 K. In addition, both the differences and changes in the axial thermal expansion coefficients in the region 100-290 K can be explained by the changes involving both the hydrogen bonding and the secondary I...O halogen bonds.

The role of copper in the thermal conductivity of thermoelectric oxychalcogenides: do lone pairs matter?

Understanding the underlying mechanisms that suppress thermal conduction in solids is of paramount importance for the targeted design of materials for thermal management and thermoelectric energy conversion applications. Bismuth copper oxychalcogenides, BiOCuQ (Q = Se, Te), are highly crystalline thermoelectric materials with an unusually low lattice thermal conductivity of ∼0.5 Wm(-1) K(-1), a value normally found in amorphous materials. Here we unveil the origin of the unusual thermal transport properties of these phases. First principles calculations of the vibrational properties combined with analysis of in-situ neutron diffraction data, demonstrate that weak bonding of copper atoms within the structure leads to an unexpected vibrational mode at low frequencies, which is likely to be a major contributor to the low thermal conductivity of these materials. In addition, we show that anharmonicity and the large Grüneisen parameter in these oxychalcogenides are mainly related to the low frequency copper vibrations, rather than to the Bi(3+) lone pairs.

New insights into the phase diagram of a magnetic perovskite, LaCo1/3Mn2/3O3.

We report the crystal structure of the orthorhombic perovskite LaCo1/3Mn2/3O3 as determined by neutron diffraction from 5-300 K. A high-temperature x-ray diffraction study is also reported from 290-900 K. At temperatures above 570 K, LaCo1/3Mn2/3O3 transforms to a rhombohedral structure with space group R3̄c. This rhombohedral phase is also observed in the material at high pressure and the crystal structure has been determined by in situ neutron diffraction at 4.7 GPa. Finally, the ferromagnetic behaviour has been determined by magnetometry and the magnetic structure has been determined using low temperature neutron diffraction at ambient pressure.

Integrating health and environmental impact analysis.

Scientific investigations have progressively refined our understanding of the influence of the environment on human health, and the many adverse impacts that human activities exert on the environment, from the local to the planetary level. Nonetheless, throughout the modern public health era, health has been pursued as though our lives and lifestyles are disconnected from ecosystems and their component organisms. The inadequacy of the societal and public health response to obesity, health inequities, and especially global environmental and climate change now calls for an ecological approach which addresses human activity in all its social, economic and cultural complexity. The new approach must be integral to, and interactive, with the natural environment. We see the continuing failure to truly integrate human health and environmental impact analysis as deeply damaging, and we propose a new conceptual model, the ecosystems-enriched Drivers, Pressures, State, Exposure, Effects, Actions or 'eDPSEEA' model, to address this shortcoming. The model recognizes convergence between the concept of ecosystems services which provides a human health and well-being slant to the value of ecosystems while equally emphasizing the health of the environment, and the growing calls for 'ecological public health' as a response to global environmental concerns now suffusing the discourse in public health. More revolution than evolution, ecological public health will demand new perspectives regarding the interconnections among society, the economy, the environment and our health and well-being. Success must be built on collaborations between the disparate scientific communities of the environmental sciences and public health as well as interactions with social scientists, economists and the legal profession. It will require outreach to political and other stakeholders including a currently largely disengaged general public. The need for an effective and robust science-policy interface has never been more pressing. Conceptual models can facilitate this by providing theoretical frameworks and supporting stakeholder engagement process simplifications for inherently complex situations involving environment and human health and well-being. They can be tools to think with, to engage, to communicate and to help navigate in a sea of complexity. We believe models such as eDPSEEA can help frame many of the issues which have become the challenges of the new public health era and can provide the essential platforms necessary for progress.

Enhanced thermoelectric performance in TiNiSn-based half-Heuslers.

Thermoelectric figures of merit, ZT > 0.5, have been obtained in arc-melted TiNiSn-based ingots. This promising conversion efficiency is due to a low lattice thermal conductivity, which is attributed to excess nickel in the half-Heusler structure.

Ammonia absorption in calcium graphite intercalation compound: in situ neutron diffraction, Raman spectroscopy and magnetization.

The structure and superconducting properties of ammoniated calcium-graphite intercalation compound (Ca-GIC) have been investigated using in situ time-of-flight neutron diffraction, Raman spectroscopy and magnetization studies. Ammonia absorption has been carried out by exposing preformed Ca-GIC to ammonia vapour at various pressures. Our in situ neutron diffraction data reveal a complex ammonia pressure dependent structural transformation, in which the growth of secondary ammoniated Ca-GIC phases are observed at the expense of the pristine CaC(6) and graphite. The ammonia absorption is irreversible in nature, and degassing the sample at elevated temperature leads to the formation of calcium amide and hydrogen. The Raman spectroscopy and magnetization studies show that the ammonia absorption not only leads to a large stacking disorder, but it also reduces the superconducting CaC(6) phase fraction. Finally, we propose a molecular stacking model which accounts for the observed ammonia absorption and concomitant structural phase transitions.

Effects of nitrogen enrichment on phosphatase activity and nitrogen : phosphorus relationships in Cladonia portentosa.

*Relationships between nitrogen deposition in the UK and phosphomonoesterase (PME) activity and nitrogen (N) and phosphorus (P) concentrations in Cladonia portentosa were quantified to understand factors limiting lichen growth and to further develop biomarkers for N pollution. *Lichen was collected from sites differing either in rates of wet N (NH(4)(+) + NO(3)(-)) deposition or in annual mean N concentration in rainfall based on both measured and modelled data sets. The PME activity, and total N and P concentrations were measured in specific horizontal strata in lichen mats and PME activity in the thallus was located using an enzyme-labelled fluorescent phosphatase substrate. *With an increase in modelled N deposition from 4.1 to 32.8 kg N ha(-1) yr(-1), PME activity, thallus N and N : P ratio increased by factors of 2.3, 1.4 and 1.8, respectively. Correlations with modelled data were generally stronger than with measured data and those with N deposition were stronger than those with N concentration in rainfall. The PME activity was located solely in the lichen fungus in outer regions of the thallus. *Nitrogen enrichment changes lichen N : P ratios from values typical of N limitation (for example, 10) to those indicative of P limitation (for example, 26) driving upregulation of PME activity.

Strategies of survival and resource exploitation in the Antarctic fellfield ecosystem.

Antarctic fellfields present organisms with a heterogeneous habitat characterised by a wide variety of environmental stresses. These include low temperatures, limited moisture availability, frequent and often rapid freeze-thaw and hydration-dehydration cycles, exposure to high photosynthetic photon flux density and ultraviolet (uv) irradiance, seasonal snow cover, high winds, cryoturbation and, depending on location south of the Antarctic Circle, considerable daylight in summer. Most of these factors vary both predictably and unpredictably in spatial and temporal planes. In response to this adverse environment, fellfield organisms have developed a variety of strategies to overcome physiological stress and to exploit the limited resources available during the short austral growing season. A high degree of synchronisation exists, so that investment in non-essential activity and adaptations is minimised. Here, we review the combined suites of co-adapted traits used by different fellfield taxa to achieve energy acquisition, growth and reproduction under adverse levels of two principal limiting factors: low temperatures and the scarcity of water. To this end, a detailed characterisation of the Antarctic fellfield microenvironment is followed by a synthesis of available data on the morphology, physiology, life history and behaviour of successful Antarctic flora and fauna. Tolerance of low temperatures by fellfield organisms is achieved by elevation of standard metabolism, production and accumulation of cryoprotectants, supercooling, melanic pigmentation, behavioural avoidance, compact growth forms and synchronised reproduction and extended life cycles. Low moisture conditions are overcome by dehydration resistance, anhydrobiosis, development of resting stages and by behavioural avoidance of desiccating conditions. Occupancy of the Antarctic fellfield habitat is considered to require the ability to respond rapidly to ephemeral resources and to tolerate severe environmental stresses. During summer, organisms rely on opportunism to maintain a positive energy balance. During winter, resistance adaptations are used to withstand the potentially lethal climate, especially in habitats not protected by snow cover. This deterministic framework has led to the selection of species that are genetically and physiologically pre-adapted for resource acquisition yet sufficiently robust to withstand cold and desiccation stresses. Non-adapted taxa fail to become established. Despite the environmental selection pressures, available evidence suggests that colonisation of the fellfield habitat has not required the evolution of any adaptations, only the refinement of those already possessed to an extent by some temperate forms. This has led to the convergence of survival strategies. It is hypothesised that, in the short term, the majority of Antarctic fellfield biota are able to absorb the predicted effects of a changing climate by their high levels of physiological tolerance and life-cycle flexibility.

Cation ordering in Li containing garnets: synthesis and structural characterisation of the tetragonal system, Li7La3Sn2O12.

In this paper we report synthesis, conductivity and structural data for the novel tetragonal garnet-related system, Li7La3Sn2O12. Neutron diffraction data shows that the tetragonal distortion is related to ordering of Li in three sites within the structure to ensure no short Li-Li interactions. Consistent with the ordered nature of the Li ions, the conductivity is low, with a high activation energy. The results are relevant to related highly conducting cubic garnets, Li5+xLn3-xAxM2O12 (Ln=rare earth, A=alkaline earth; M=Nb, Ta, Sb), showing how a high Li content can be accommodated by Li ordering within the garnet structure, supporting previous suggestions by Cussen for the cubic garnets, who proposed the presence of local ordering/clustering of Li in tetrahedral and "octahedral" sites to limit unfavourable short Li-Li interactions.

The influence of nitrogen in stemflow and precipitation on epiphytic bryophytes, Isothecium myosuroides Brid., Dicranum scoparium Hewd. and Thuidium tamariscinum (Hewd.) Schimp of Atlantic oakwoods.

The spatial relationship between the concentration and deposition of the major ions in precipitation and stemflow and their influence on the tissue nitrogen concentration of three epiphytic bryophytes on Quercus petraea (Matt) Liebl. and Q. robur L. was investigated at seven UK Atlantic oak woodland sites with a range of total N deposition of 55-250 mmol m(-2). The main driver of change in tissue N concentrations of three epiphytic bryophytes (Isothecium myosuroides Brid. (Eurhynchium myosuroides (Brid.) Schp.), Dicranum scoparium Hewd. and Thuidium tamariscinum (Hewd.) Schimp.) was total N deposition in stemflow, dominated by ammonium deposition. The three epiphytic species also showed strong relationships between tissue N concentration and total N deposition in rainfall but a poor correlation with total N ion concentration in rainfall. This study shows that epiphytic bryophytes utilise stemflow N and thus increase their risk from inputs of total N deposition compared to terricolous species at the same site.

Neutron powder diffraction studies of sulfuric acid hydrates. II. The structure, thermal expansion, incompressibility, and polymorphism of sulfuric acid tetrahydrate (D2SO4.4D2O).

We report results of the first neutron powder diffraction study of sulfuric acid tetrahydrate (SAT); D(2)SO(4)4D(2)O is tetragonal, space group P42(1)c, with two formula units per unit cell. At 1.7 K the unit-cell dimensions are a=b=7.475 12(6) A, c=6.324 66(5) A and V=353.405(5) A(3). At 225 K the unit-cell dimensions are a=b=7.4833(1) A, c=6.4103(1) A, and V=358.98(1) A(3). The deuteron positions refined from the neutron data are in excellent agreement with the single crystal x-ray analysis of Kjallman and Olovsson [Acta Crystallogr., Sect. B: Struct. Crystallogr. Cryst. Chem. B28, 1692 (1972)]; the structure consists of SO(4) (2-) and D(5)O(2) (+) ions hydrogen bonded to form a three dimensional network. Although no structural change is observed between 2 K and the melting point at approximately 232 K, the thermal expansion and incompressibility of the crystal are highly anisotropic. The bulk modulus of SAT at 200 K is 9.2(2) GPa, ( partial differentialK partial differentialP)(T)=7.9(8), and -( partial differentialK partial differentialT)(P)=10.6(5) MPa K(-1), values which are very similar to D(2)O ice Ih. A new polymorph of SAT has been discovered above 235 K at 5.5 kbars. The structure of this phase could not be determined, but we have indexed the diffraction pattern with a monoclinic unit cell of likely space-group P2(1)a (Z=2). SAT-II has a lower density than SAT-I under the same PT conditions; the refined unit-cell parameters at 235 K, 5.435 kbars are a=6.1902(3) A, b=11.1234(5) A, c=5.6446(3) A, beta=110.287(4) degrees , and V=364.56(2) A(3). This phase has been quenched to low pressures and temperatures, and we have obtained estimates of the thermal expansivity and incompressibility which reveal SAT-II to be significantly stiffer and more isotropic than SAT-I.

On the compression mechanism of FeF3.

The structure of FeF3, iron trifluoride, has been studied in the pressure range from ambient to 8.28 GPa by time-of-flight neutron powder diffraction. No structural phase transitions were found within the investigated pressure range, and least-squares refinements of the crystal structures were performed in the space group R3c for all recorded data sets. It was found that volume reduction is achieved through rotation of the FeF6 octahedra, and the Fe-F-Fe bond angle decreases from 152.5 (2) to 134.8 (3) degrees within the investigated pressure range. A small octahedral strain was found to develop during compression, which reflects an elongation of the FeF6 octahedra along the c axis. The zero-pressure bulk modulus Bo and its pressure derivative B'o were determined to be 14 (1) GPa and 12 (1), respectively.

Genetic heterogeneity of day blindness in Alaskan Malamutes.

Day blindness is a progressive and specific degeneration of cone photoreceptors in the retina of young dogs. This disorder has been associated with a breed-specific non-synonymous substitution in exon 6 of the cyclic nucleotide gated channel beta3 (CNGB3) gene in German Shorthaired Pointer dogs and a genomic deletion removing the entire gene in Alaskan Malamute dogs from the USA. To further investigate this disorder, we characterized CNGB3 in a three-generation pedigree of Alaskan Malamute dogs from Australia segregating for day blindness. Fifteen of the dogs showed clinical signs of day blindness. Four of these were definitively diagnosed by standardized electroretinography. Polymerase chain reaction amplification of exon 6 of CNGB3 was attempted, and as expected, amplification was successful in the 18 unaffected or carrier dogs. However, a non-mutated exon 6 was also amplified and sequenced in six of the 15 affected dogs. On sequencing each exon and exon/intron boundary in two such affected individuals and two unaffected individuals, three exonic substitutions and 12 intronic changes were noted. These sequence variations in affected individuals were also present in one or both unaffected dogs and so appear to have no obvious effect on the protein's function. Hence, day blindness shows genetic heterogeneity within the Alaskan Malamute population of Australia, a result that is somewhat unexpected given the relatively small effective population size of this breed.

Changes in the atmospheric deposition of acidifying compounds in the UK between 1986 and 2001.

Emissions of a precursor of acidity in precipitation, sulphur dioxide (SO2), declined in the UK and the EU (15) by 71% and 72%, respectively, between 1986 and 2001, while nitrous oxide emissions declined by about 40%. Acidity in UK precipitation and the deposition of sulphate in precipitation halved during this period, but reductions were larger in the English Midlands than at the west coast and in high rainfall areas (>2000 mm). There is evidence that the smaller reductions in sulphur deposition in the west and south are due in part to shipping sources of SO2. Reductions in sulphur dry deposition (74%) are larger than in wet deposition (45%), due to changes in the canopy resistance to dry deposition. For reduced nitrogen, there has been a small (10%) reduction in emissions and deposition, while for oxidized nitrogen, a substantial reduction in emissions (40%) occurred but wet deposition of nitrate changed by less than 10%.

Analytical and clinical sensitivity of West Nile virus RNA screening and supplemental assays available in 2003.

BACKGROUND: Transfusion-transmitted West Nile virus (WNV) infections were first reported in 2002, which led to rapid development of investigational nucleic acid amplification tests (NAT). A study was conducted to evaluate sensitivities of WNV screening and supplemental NAT assays first employed in 2003. STUDY DESIGN AND METHODS: Twenty-five member-coded panels were distributed to NAT assay manufacturers. Panels included five pedigreed WNV standards (1, 3, 10, 30, and 100 copies/mL), 15 or 16 donor units with very-low-level viremia identified through 2003 screening, and four or five negative control samples. Samples were tested neat in 10 replicates by all assays; for NAT screening assays, 10 replicates were also performed on dilutions consistent with minipool (MP)-NAT. The viral load distribution for 142 MP-NAT yield donations was characterized, relative to the analytical sensitivity of MP-NAT systems. RESULTS: Analytical sensitivities (50% limits of detection [LoD] based on Poisson model of detection of WNV standards) for screening NAT assays ranged from 3.4 to 29 copies per mL; when diluted consistent with MP pool sizes, the 50 percent LoD of screening NAT assays was reduced to 43 to 309 copies per mL. Analytical sensitivity of supplemental assays ranged from 1.5 to 7.7 copies per mL (50% LoD). Detection of RNA in donor units varied consistent with analytical LoD of assays. Detection of low-level viremia after MP dilutions was particularly compromised for seropositive units, probably reflecting lower viral loads in the postseroconversion phase. Based on the viral load distribution of MP-NAT yield donations (median, 3519 copies/mL; range, < 50-690,000), 13 to 24 percent of units had viral loads below the 50 percent LoD of screening NAT assays run in MP-NAT format. CONCLUSION: WNV screening and supplemental assays had generally excellent analytical sensitivity, comparable to human immunodeficiency virus-1 and hepatitis C virus NAT assays. The presence of low-level viremic units during epidemic periods and the impact of MP dilutions on sensitivity, however, suggest the need for further improvements in sensitivity as well as a role for targeted individual-donation NAT in epidemic regions.

The compression mechanism of CrF3.

The structure of CrF3 has been studied in the pressure range from ambient to 9.12 GPa by time-of-flight neutron powder diffraction. Rietveld refinements of the crystal structure were performed in the space group R3 c for all the recorded data sets. It was found that volume reduction is achieved through rotation of the CrF6 octahedra and that the Cr-F-Cr bond angle decreases from 144.80 (7) to 133.9 (4) degrees within the investigated pressure range. Furthermore, a small octahedral strain was found to develop during compression. The octahedral strain reflects an elongation of the CrF6 octahedra along the c-axis direction. The zero-pressure bulk modulus Bo and its pressure derivative Bo' were determined to be Bo = 29.2 (4) GPa and Bo' = 10.1 (3).

Ammonia emission and deposition in Scotland and its potential environmental impacts.

The main source of atmospheric ammonia (NH3) in Scotland is livestock agriculture, which accounts for 85% of emissions. The local magnitude of emissions therefore depends on livestock density, type, and management, with major differences occurring in various parts of Scotland. Local differences in agricultural activities therefore result in a wide range of NH3 emissions, ranging from less than 0.2 kg N ha(-1) year(-1) in remote areas of the Scottish Highlands to over 100 kg N ha(-1) year-1 in areas with intensive poultry farming. Scotland can be divided loosely into upland and lowland areas, with NH3 emission being less than and more than 5 kg N ha(-1) year(-1), respectively. Many semi-natural ecosystems in Scotland are vulnerable to nitrogen deposition, including bogs, moorlands, and the woodland ground flora. Because NH3 emissions occur in the rural environment, the local deposition to sensitive ecosystems may be large, making it essential to assess the spatial distribution of NH3 emissions and deposition. A spatial model is applied here to map NH3 emissions and these estimates are applied in atmospheric dispersion and deposition models to estimate atmospheric concentrations of NH3 and NH4+, dry deposition of NH3, and wet deposition of NHx. Although there is a high level of local variability, modelled NH3 concentrations show good agreement with the National Ammonia Monitoring Network, while wet deposition is largest at high altitude sites in the south and west of Scotland. Comparison of the modelled NHx deposition fields with estimated thresholds for environmental effects ("critical loads") shows that thresholds are exceeded across most of lowland Scotland and the Southern Uplands. Only in the cleanest parts of the north and west is nitrogen deposition not a cause for concern. Given that the most intense effects occur within a few kilometres of sources, it is suggested that local spatial abatement policies would be a useful complement to traditional policies that mitigate environmental effects based on emission reduction technologies.

No evidence for large-scale proton ordering in Antarctic ice from powder neutron diffraction.

We have examined a sample of 3000 year old Antarctic ice, collected at the Kohnen Station, by time-of-flight powder neutron diffraction to test the hypothesis of Fukazawa et al. [e.g., Ann. Glaciol. 31, 247 (2000)] that such ice may be partially proton ordered. Great care was taken to keep our sample below the proposed ordering temperature (237 K) at all times, but we did not observe any evidence of proton ordering.