The contribution of global aviation to anthropogenic climate forcing for 2000 to 2018.

Global aviation operations contribute to anthropogenic climate change via a complex set of processes that lead to a net surface warming. Of importance are aviation emissions of carbon dioxide (CO2), nitrogen oxides (NOx), water vapor, soot and sulfate aerosols, and increased cloudiness due to contrail formation. Aviation grew strongly over the past decades (1960-2018) in terms of activity, with revenue passenger kilometers increasing from 109 to 8269 billion km yr-1, and in terms of climate change impacts, with CO2 emissions increasing by a factor of 6.8 to 1034 Tg CO2 yr-1. Over the period 2013-2018, the growth rates in both terms show a marked increase. Here, we present a new comprehensive and quantitative approach for evaluating aviation climate forcing terms. Both radiative forcing (RF) and effective radiative forcing (ERF) terms and their sums are calculated for the years 2000-2018. Contrail cirrus, consisting of linear contrails and the cirrus cloudiness arising from them, yields the largest positive net (warming) ERF term followed by CO2 and NOx emissions. The formation and emission of sulfate aerosol yields a negative (cooling) term. The mean contrail cirrus ERF/RF ratio of 0.42 indicates that contrail cirrus is less effective in surface warming than other terms. For 2018 the net aviation ERF is +100.9 milliwatts (mW) m-2 (5-95% likelihood range of (55, 145)) with major contributions from contrail cirrus (57.4 mW m-2), CO2 (34.3 mW m-2), and NOx (17.5 mW m-2). Non-CO2 terms sum to yield a net positive (warming) ERF that accounts for more than half (66%) of the aviation net ERF in 2018. Using normalization to aviation fuel use, the contribution of global aviation in 2011 was calculated to be 3.5 (4.0, 3.4) % of the net anthropogenic ERF of 2290 (1130, 3330) mW m-2. Uncertainty distributions (5%, 95%) show that non-CO2 forcing terms contribute about 8 times more than CO2 to the uncertainty in the aviation net ERF in 2018. The best estimates of the ERFs from aviation aerosol-cloud interactions for soot and sulfate remain undetermined. CO2-warming-equivalent emissions based on global warming potentials (GWP* method) indicate that aviation emissions are currently warming the climate at approximately three times the rate of that associated with aviation CO2 emissions alone. CO2 and NOx aviation emissions and cloud effects remain a continued focus of anthropogenic climate change research and policy discussions.

Micro-Scale Device-An Alternative Route for Studying the Intrinsic Properties of Solid-State Materials: The Case of Semiconducting TaGeIr.

An efficient application of a material is only possible if we know its physical and chemical properties, which is frequently obstructed by the presence of micro- or macroscopic inclusions of secondary phases. While sometimes a sophisticated synthesis route can address this issue, often obtaining pure material is not possible. One example is TaGeIr, which has highly sample-dependent properties resulting from the presence of several impurity phases, which influence electronic transport in the material. The effect of these minority phases was avoided by manufacturing, with the help of focused-ion-beam, a µm-scale device containing only one phase-TaGeIr. This work provides evidence for intrinsic semiconducting behavior of TaGeIr and serves as an example of selective single-domain device manufacturing. This approach gives a unique access to the properties of compounds that cannot be synthesized in single-phase form, sparing costly and time-consuming synthesis efforts.

µm- and nm-Sized Catalytic Structures in Heat Sources for Thermoelectric Generators.

Micro- and nano-structural organization and its influence on the efficiency of catalysts used in the heat sources for permeable thermoelectric generators were investigated. Two types of catalyst were studied­elemental platinum on aluminum oxide granulate Pt/Al2O3 and mixed transition-metal catalyst on fibrous silicon dioxide Co­Cr­Pd­Sr/SiO2. The distribution of active components in catalytic structures which contribute to the maximum combustion completeness of organic fuel in heat sources was investigated. Practically full conversion of hydrocarbons was achieved already with 1 mass.% of platinum in the Pt/Al2O3 catalyst with sub-µm- and nm-sized particles placed at the input of the gas-air mixture into the channel of the permeable thermoelement. The propane-butane conversion rate of 97% for the catalyst Co­Cr­Pd/SiO2 with was further enhanced by addition of 0.5 mass.% of Sr. The catalytic centers are formed by CoCr2O4 nanocrystals (10 to 40 nm in size) with Pd promotor in form of single crystals on the fibrous SiO2 matrix.

How to tackle the molecular species inventory for an industrialized nation-lessons from the first phase of the German Barcode of Life initiative GBOL (2012-2015).

Biodiversity loss is mainly driven by human activity. While concern grows over the fate of hot spots of biodiversity, contemporary species losses still prevail in industrialized nations. Therefore, strategies were formulated to halt or reverse the loss, driven by evidence for its value for ecosystem services. Maintenance of the latter through conservation depends on correctly identified species. To this aim, the German Federal Ministry of Education and Research is funding the GBOL project, a consortium of natural history collections, botanic gardens, and universities working on a barcode reference database for the country's fauna and flora. Several noticeable findings could be useful for future campaigns: (i) validating taxon lists to serve as a taxonomic backbone is time-consuming, but without alternative; (ii) offering financial incentives to taxonomic experts, often citizen scientists, is indispensable; (iii) completion of the libraries for widespread species enables analyses of environmental samples, but the process may not hold pace with technological advancements; (iv) discoveries of new species are among the best stories for the media; (v) a commitment to common data standards and repositories is needed, as well as transboundary cooperation between nations; (vi) after validation, all data should be published online via the BOLD to make them searchable for external users and to allow cross-checking with data from other countries.

Evidence for localized moment picture in Mn-based Heusler compounds.

X-ray absorption spectroscopy (XAS) and X-ray magnetic circular dichroism (XMCD) were used to probe the electronic structure and magnetic moment of Mn in Heusler compounds with different crystallographic structure. The results were compared with theoretical calculations of the magnetic and electronic properties, and it was found that in full and half Heusler alloys, Mn is metallic on both sublattices. The magnetic moment is large and localized when octahedrally coordinated by the main group element, consistent with previous theoretical work, and reduced when the main group coordination is tetrahedral. The magnetic and electronic properties of Mn in full and half Heusler compounds are strongly dependent on the structure and sublattice, a fact that can be exploited to design new materials.

Diffusion-controlled formation of Ti2O3 during spark-plasma synthesis.

The spark-plasma-sintering (SPS) technique has successfully been applied for the single-step direct synthesis of Ti2O3 from a mixture of powders of rutile/anatase with titanium. The components react by diffusion through the grain boundaries, forming several intermediate phases locally. A single-phase material of titanium(III) oxide is obtained in compact bulk form after 180 min of SPS treatment at 1473 K. The electrical and thermal transport properties of such a SPS-prepared material measured in the temperature range between 300 and 800 K reflect the known semiconductor-to-metal transition above 400 K. The observed metallic-like electrical and thermal conductivity above this temperature is in good agreement with previously reported results. A maximum of the thermoelectric figure-of-merit ZT = 0.04 is achieved at 350 K.

Synthesis and properties of type-I clathrate phases Rb(8-x-t)K(x□t)Au(y)Ge(46-y).

Type-I clathrates Rb(8-x-t)K(x□t)Au(y)Ge(46-y) are synthesized from Rb4Ge9, K4Ge9, Au, and Ge. Crystal structures and compositions are determined by single-crystal and powder X-ray diffraction methods. The lattice parameters are 10.8103(2), 10.7956(2), 10.7850(2), and 10.7723(2) Šin space group Pm3n for Rb7.88(2)Au2.47(2)Ge43.53(2), Rb3.69(4)K4.31(4)Au2.17(2)Ge43.83(2), Rb1.66(5)K6.34(5)Au2.17(1)Ge43.83(1), and K6.71(4)Au2.28(2)Ge43.72(2), respectively. Bonding analysis for Rb8Au6Ge40 suggests ionic interaction of Rb with the framework besides covalent interactions between Ge and Au/Ge. Rb7.88Au2.47Ge43.53 and K6.71(4)Au2.28Ge43.72 are both diamagnetic. The heat capacity of K6.71Au2.28Ge43.72 is analyzed. Transport properties of Rb7.88Au2.47Ge43.53 reveal n-type conducting, and low thermal conductivity.

Structural transformation with "negative volume expansion": chemical bonding and physical behavior of TiGePt.

The synthesis and a joint experimental and theoretical study of the crystal structure and physical properties of the new ternary intermetallic compound TiGePt are presented. Upon heating, TiGePt exhibits an unusual structural phase transition with a huge volume contraction of about 10 %. The transformation is characterized by a strong change in the physical properties, in particular, by an insulator-metal transition. At temperatures below 885 °C TiGePt crystallizes in the cubic MgAgAs (half-Heusler) type (LT phase, space group F43m, a = 5.9349(2) Å). At elevated temperatures, the crystal structure of TiGePt transforms into the TiNiSi structure type (HT phase, space group Pnma, a = 6.38134(9) Å, b = 3.89081(5) Å, c = 7.5034(1) Å). The reversible, temperature-dependent structural transition was investigated by in-situ neutron powder diffraction and dilatometry measurements. The insulator-metal transition, indicated by resistivity measurements, is in accord with band structure calculations yielding a gap of about 0.9 eV for the LT phase and a metallic HT phase. Detailed analysis of the chemical bonding in both modifications revealed an essential change of the Ti-Pt and Ti-Ge interactions as the origin of the dramatic changes in the physical properties.

Synthesis, crystal structure, and physical properties of the type-I clathrate Ba(8-δ)Ni(x)□(y)Si(46-x-y).

Type-I clathrate phase Ba(8)Ni(x)□(y)Si(46-x-y) (□ = vacancy) was obtained from the elements at 1000 °C with the homogeneity range 2.4 ≤ x ≤ 3.8 and 0 ≤ y ≤ 0.9. In addition, samples with low Ni content (x = 1.4 and 1.6; y = 0) and small Ba deficiency were prepared from the melt by steel-quenching. Compositions were established by microprobe analysis and crystal structure determination. Ba(8-δ)Ni(x)□(y)Si(46-x-y) crystallizes in the space group Pm ̅3n (No. 223) with lattice parameter ranging from a = 10.3088(1) Å for Ba(7.9(1))Ni(1.4(1))Si(44.6(1)) to a = 10.2896(1) Å for Ba(8.00(3))Ni(3.82(4))Si(41.33(6)). Single-crystal X-ray diffraction data together with microprobe analysis indicate an increasing number of framework vacancies toward compositions with higher Ni content. For all compositions investigated, Ni K-edge X-ray absorption spectroscopy measurements showed an electronic state close to that of elemental Ni. All samples exhibit metallic-like behavior with moderate thermopower and low thermal conductivity in the temperature range 300-773 K. Samples with compositions Ba(7.9(1))Ni(1.4(1))Si(44.6(1)) and Ba(7.9(1))Ni(1.6(1))Si(44.4(1)) are superconducting with T(c) values of 6.0 and 5.5 K, respectively.

Non-centrosymmetric superconductor Th[Formula: see text]Be[Formula: see text]Pt[Formula: see text] and heavy-fermion U[Formula: see text]Be[Formula: see text]Pt[Formula: see text] cage compounds.

Unconventional superconductivity in non-centrosymmetric superconductors has attracted a considerable amount of attention. While several lanthanide-based materials have been reported previously, the number of actinide-based systems remains small. In this work, we present the discovery of a novel cubic complex non-centrosymmetric superconductor [Formula: see text] ([Formula: see text] space group). This intermetallic cage compound displays superconductivity below [Formula: see text] K, as evidenced by specific heat and resistivity data. [Formula: see text] is a type-II superconductor, which has an upper critical field [Formula: see text] T and a moderate Sommerfeld coefficient [Formula: see text] mJ [Formula: see text] [Formula: see text]. A non-zero density of states at the Fermi level is evident from metallic behavior in the normal state, as well as from electronic band structure calculations. The isostructural [Formula: see text] compound is a paramagnet with a moderately enhanced electronic mass, as indicated by the electronic specific heat coefficient [Formula: see text] mJ [Formula: see text] [Formula: see text] and Kadowaki-Woods ratio [Formula: see text] [Formula: see text] [Formula: see text] cm [Formula: see text] [Formula: see text] (mJ)[Formula: see text]. Both [Formula: see text] and [Formula: see text] are crystallographically complex, each hosting 212 atoms per unit cell.

Impact of inversion symmetry on a quasi-1D S = 1 system.

Here, we report the synthesis and magnetic properties of a novel, centrosymmetric, quasi-1D spin chain system La3VWS3O6, with hexagonal crystal structure (P63/m, a = 9.460 76(3), c = 5.518 09(2) Å). Pure powders were obtained by solid-state reactions from La2O3, WO3 and metal powders of V and W. X-ray powder diffraction, specific heat, magnetization, 139La-nuclear magnetic resonance (NMR), and electric resistivity measurements indicate that the compound is a low dimensional magnet with an S = 1 spin chain that exhibits no sign of magnetic ordering above 2 K. A single ion anisotropy (D/k B ~ 10 K), caused by magneto-crystalline effects, is probably responsible for a thermodynamic entropy release at lower temperatures, which concurs with 139La-NMR data. By detailed comparison with non-centrosymmetric Ba3V2S4O3, having a very similar magnetic lattice, it is obvious that the presence of crystallographic inversion symmetry has an effect on the behaviour of the magnetic chains.

Cationic clathrate I Si(46-x)P(x)Te(y) (6.6(1) < or = y < or = 7.5(1), x < or = 2y): crystal structure, homogeneity range, and physical properties.

A new cationic clathrate I Si(46-x)P(x)Te(y) (6.6(1) < or = y < or = 7.5(1), x < or = 2y at 1375 K) was synthesized from the elements and characterized by X-ray powder diffraction, thermal analysis, scanning electron microscopy, wavelength dispersive X-ray spectroscopy (WDXS), neutron powder diffraction, and (31)P NMR spectroscopy. The thermal behaviors of the magnetic susceptibility and resistivity were investigated as well. Si(46-x)P(x)Te(y) reveals a wide homogeneity range due to the presence of vacancies in the tellurium guest positions inside the smaller cage of the clathrate I structure. The vacancy ordering in the structure of Si(46-x)P(x)Te(y) causes the change of space group from Pm3n (ideal clathrate I) to Pm3 accompanied by the redistribution of P and Si atoms over different framework positions. Neutron powder diffraction confirmed that P atoms preferably form a cage around the vacancy-containing tellurium guest position. Additionally, (31)P NMR spin-spin relaxation experiments revealed the presence of sites with different coordination of phosphorus atoms. Precise determination of the composition of Si(46-x)P(x)Te(y) by WDXS showed slight but noticeable deviation (x < or = 2y) of phosphorus content from the Zintl counting scheme (x = 2y). The compound is diamagnetic while resistivity measurements show activated behavior or that of heavily doped semiconductors. Thermal analysis revealed high stability of the investigated clathrate: Si(46-x)P(x)Te(y) melts incongruently at approximately 1460 K in vacuum and is stable in air against oxidation up to 1295 K.

EuTM(2)Ga(8) (TM = Co, Rh, Ir) - a contribution to the chemistry of the CeFe(2)Al(8)-type compounds.

The isostructural compounds EuTM(2)Ga(8) (TM = Co, Rh, Ir) were prepared by direct reaction of the elements by high-frequency thermal treatment. All three phases are isotypic with CeFe(2)Al(8) (space group Pbam, Pearson symbol oP44, Z = 4). The crystal structure was established from single-crystal X-ray diffraction data: a = 12.4322(7) A, b = 14.3814(9) A, and c = 4.0378(2) A for EuCo(2)Ga(8); a = 12.6001(6) A, b = 14.6757(7) A, and c = 4.1172(2) A for EuRh(2)Ga(8); and a = 12.6237(7) A, b = 14.6978(8) A, and c = 4.1486(2) A for EuIr(2)Ga(8), respectively. Analysis of the chemical bonding in EuRh(2)Ga(8) with the electron localizability tools reveals formation of the 3D [Rh(2)Ga(8)] polyanion build by polar covalent bonds. Europium interacts in two ways with the polyanion: mainly as a cation by charge transfer and additionally covalently by means of the electrons of the inner shells. Magnetic susceptibility measurements show Curie-Weiss paramagnetic behavior above 40 K with effective magnetic moments of 7.81, 8.05, and 8.27 micro(B)/f.u. for EuTM(2)Ga(8) (TM = Co, Rh, Ir). Antiferromagnetic ordering of Eu moments is observed in all three compounds below 20 K. Independently on the chemical composition of the coordination sphere, magnetic behavior and, especially, X-ray absorption spectra indicate predominantly the 4f(7) electronic configuration of europium with small admixture of the 4f(6) state.

Electronic band structure and low-temperature transport properties of the type-I clathrate Ba8Ni(x)Ge(46-x-y□y).

We present the evolution of the low-temperature thermodynamic, galvanomagnetic and thermoelectric properties of the type-I clathrate Ba8Ni(x)Ge(46-x-y□y) with the Ni concentration studied on polycrystalline samples with 0.0 ≤ x ≤ 6.0 by means of specific heat, Hall effect, electrical resistivity, thermopower and thermal conductivity measurements in the 2-350 K temperature range and supported by first-principles calculations. The experimental results evidence a 2a × 2a × 2a supercell described in the space group Ia3d for x ≤ 1.0 and a primitive unit cell a × a × a (space group Pm3n) above this Ni content. This concentration also marks the limit between a regime where both electrons and holes contribute to the electrical conduction (x ≤ 1.0) and a conventional, single-carrier regime (x > 1.0). This evolution is traced by the variations in the thermopower and Hall effect with x. In agreement with band structure calculations, increasing the Ni content drives the system from a nearly-compensated semimetallic state (x = 0.0) towards a narrow-band-gap semiconducting state (x = 4.0). A crossover from an n-type to a p-type conduction occurs when crossing the x = 4.0 concentration i.e. for x = 4.1. The solid solution Ba8Ni(x)Ge(46-x-y□y) therefore provides an excellent experimental platform to probe the evolution of the peculiar properties of the parent type-I clathrate Ba8Ge43□3 upon Ge/Ni substitution and filling up of the vacancies, which might be universal among the ternary systems at low substitution levels.

Intermetallic germanides with non-centrosymmetric structures derived from the Yb3Rh4Sn13 type.

New germanides with composition RE3Pt4Ge13 (RE = Y, Pr, Sm, Gd, Tb, Tm) have been prepared by high-pressure, high-temperature synthesis. Their crystal structures have been refined, and the relationship of this new rhombohedral and monoclinic structure types with the primitive cubic Yb3Rh4Sn13 prototype is discussed. Band structure calculations within density functional theory confirm the distorted rhombohedral and monoclinic structural arrangements to be energetically more favorable than the simple cubic one. X-ray absorption spectroscopy and magnetic susceptibility measurements indicate that the RE-atoms are in the +3 oxidation state in all studied compounds.

Risk of iodine-induced thyrotoxicosis after coronary angiography: an investigation in 788 unselected subjects.

In this study, the risk of iodine-induced thyrotoxicosis in unselected patients from an iodine-deficient area was investigated. The patients were consecutively enrolled. Thyroid hormone values and urinary iodine excretion were determined before, as well as 1, 4 and 12 weeks after iodine contamination by coronary angiography. Two of 788 unselected patients developed hyperthyroidism within 12 weeks. The two patients did not belong to a risk group for iodine-induced thyrotoxicosis (i.e. old people, patients with goiter or possible thyroid autonomy, low TSH). Both patients had normal TSH levels at baseline and ultrasound of the thyroid was without evidence of nodules. The study shows that in euthyroid unselected patients from an iodine-deficient area short-term iodine contamination by contrast media rarely leads to hyperthyroidism. On account of these facts, prophylactic therapy, e.g. by perchlorate or thiamazole, is not generally recommended, because the risk of side-effects is perhaps even greater than the risk of iodine-induced thyrotoxicosis.

Heavy fermion and Kondo lattice behavior in the itinerant ferromagnet CeCrGe3.

Physical properties of polycrystalline CeCrGe3 and LaCrGe3 have been investigated by x-ray absorption spectroscopy, magnetic susceptibility χ(T), isothermal magnetization M(H), electrical resistivity ρ(T), specific heat C(T) and thermoelectric power S(T) measurements. These compounds are found to crystallize in the hexagonal perovskite structure (space group P63/mmc), as previously reported. The ρ(T), χ(T) and C(T) data confirm the bulk ferromagnetic ordering of itinerant Cr moments in LaCrGe3 and CeCrGe3 with TC = 90 K and 70 K respectively. In addition, a weak anomaly is also observed near 3 K in the C(T) data of CeCrGe3. The T dependences of ρ and finite values of Sommerfeld coefficient γ obtained from the specific heat measurements confirm that both the compounds are of metallic character. Further, the T dependence of ρ of CeCrGe3 reflects a Kondo lattice behavior. An enhanced γ of 130 mJ mol(-1) K(-2) together with the Kondo lattice behavior inferred from the ρ(T) establish CeCrGe3 as a moderate heavy fermion compound with a quasi-particle mass renormalization factor of ∼45.

Structural investigations on YbRh2Si2: from the atomic to the macroscopic length scale.

YbRh2Si2 has advanced to a prototype material for investigating physics related to the Kondo effect. An optimization of the synthesis resulted in single crystals of extraordinary crystalline quality. At the atomic scale, we utilize scanning tunneling microscopy to study the topography of cleaved single crystals. A structural and chemical analysis was conducted by highly accurate x-ray diffraction and wavelength dispersive x-ray spectroscopy measurements. The latter indicate a homogeneity range of the YbRh2Si2 phase between approximately 40.0­40.2 at.% Rh. For our high-quality samples the number of defects found on the atomic scale (of the order of 0.3% of the visible lattice sites) is in quantitative agreement with a very small off-stoichiometry within this homogeneity range. Comparing our results for these samples allows an assignment of the structural defects observed at the cleaved surfaces to Rh occupying Si sites and, even less numerous Si in Rh sites. Such an analysis is hampered for samples of lesser quality, but there seem to be numerous empty Si-sites. Based on these observations the results of scanning tunneling spectroscopy can be analyzed in further detail and provide insight into the Kondo physics.

Magnetic properties and electronic structures of intermediate valence systems CeRhSi2 and Ce2Rh3Si5.

The crystal structures and the physical (magnetic, electrical transport and thermodynamic) properties of the ternary compounds CeRhSi(2) and Ce(2)Rh(3)Si(5) (orthorhombic CeNiSi(2)- and U(2)Co(3)Si(5)-type structures, respectively) were studied over wide ranges of temperature and magnetic field strength. The results revealed that both materials are valence fluctuating systems, in line with previous literature reports. Direct evidence for valence fluctuations was obtained by means of Ce L(III)-edge x-ray absorption spectroscopy and Ce 3d core-level x-ray photoelectron spectroscopy. The experimental data were confronted with the results of ab initio calculations of the electronic band structures in both compounds.

Atomic ordering and thermoelectric properties of the n-type clathrate Ba8Ni3.5Ge42.1square0.4.

Single crystals of the type-I clathrate Ba(8)Ni(3.5)Ge(42.1)square(0.4) (space group Pm3n, no. 223, a = 10.798(2) A, l = 30 mm, slashed circle = 8 mm) were grown from the melt using the Bridgman technique. Their composition, determined by microprobe analysis, reveals a distinctly lower Ni content than previously reported for the lower limit (x = 5.4) of the homogeneity range of the clathrate-I phase Ba(8)Ni(x)Ge(46-x). From single crystal X-ray diffraction data we introduce a crystal structure model that takes point defects (vacancies) square in the Ge network into account. It reveals that both Ni and square accumulate at a single site (6c) and that, as a consequence, the Ge network distorts considerably. Ba(8)Ni(3.5)Ge(42.1)square(0.4) shows metal-like behaviour (drho/dT > 0) albeit with high resistivity at room temperature (rho(300 K) approximately 1 mOmega cm). Together with the low charge carrier concentration of 2.3 e(-)/unit cell at 300 K this is typical of a degenerate semiconductor. The lattice thermal conductivity is distinctly smaller than that of Ba(8)Ge(43)square(3), where the vacancies partially order, and smaller than those of Ba-Ni-Ge type-I clathrates without vacancies, suggesting that disordered vacancies efficiently scatter heat-transporting phonons. We provide evidence that the maximum value of the thermoelectric figure of merit reached in Ba(8)Ni(3.5)Ge(42.1)square(0.4), ZT(680 K) congruent with 0.21, can be further improved by adjusting the charge carrier concentration.