Magnetic-induced phonon anisotropy in ZnCr2_2O4_4 from first principles

We have studied the influence of magnetic order on the optical phonons of the geometrically frustrated spinel ZnCr$_2$O$_4$ from first-principles. By mapping the first-principles phonon calculations onto a Heisenberg-like model, we developed a method to calculate exchange derivatives and subsequently the spin-phonon couping parameter from first-principles. All calculations were performed within LSDA+U

13-month climatology of the aerosol hygroscopicity at the free tropospheric site Jungfraujoch (3580 m a.s.l.)

A hygroscopicity tandem differential mobility analyzer (HTDMA) was operated at the high-alpine site Jungfraujoch in order to characterize the hygroscopic diameter growth factors of the free tropospheric Aitken and accumulation mode aerosol. More than ~5000 h of valid data were collected for the dry diameters <i>D</i><sub>0</sub> = 35, 50, 75, 110, 165, and 265 nm during the 13-month measurement period from 1 May 2008 through 31 May 2009. No distinct seasonal variability of the hygroscopic properties was observed. Annual mean hygroscopic diameter growth factors (<i>D</i>/<i>D</i><sub>0</sub>) at 90% relative humidity were found to be 1.34, 1.43, and 1.46 for <i>D</i><sub>0</sub> = 50, 110, and 265 nm, respectively. This size dependence can largely be attributed to the Kelvin effect because corresponding values of the hygroscopicity parameter κ are nearly independent of size. The mean hygroscopicity of the Aitken and accumulation mode aerosol at the free tropospheric site Jungfraujoch was found to be κ≈0.24 with little variability throughout the year. <br><br> The impact of Saharan dust events, a frequent phenomenon at the Jungfraujoch, on aerosol hygroscopicity was shown to be negligible for <i>D</i><sub>0</sub><265 nm. Thermally driven injections of planetary boundary layer (PBL) air, particularly observed in the early afternoon of summer days with convective anticyclonic weather conditions, lead to a decrease of aerosol hygroscopicity. However, the effect of PBL influence is not seen in the annual mean hygroscopicity data because the effect is small and those conditions (weather class, season and time of day) with PBL influence are relatively rare. <br><br> Aerosol hygroscopicity was found to be virtually independent of synoptic wind direction during advective weather situations, i.e. when horizontal motion of the atmosphere dominates over thermally driven convection. This indicates that the hygroscopic behavior of the aerosol observed at the Jungfraujoch can be considered representative of the lower free troposphere on at least a regional if not continental scale

Spin-Electron-Phonon Excitation in Re-based Half-Metallic Double Perovskites

A remarkable hardening (~ 30 cm-1) of the normal mode of vibration associated with the symmetric stretching of the oxygen octahedra for the Ba2FeReO6 and Sr2CrReO6 double perovskites is observed below the corresponding magnetic ordering temperatures. The very large magnitude of this effect and its absence for the anti-symmetric stretching mode provide evidence against a conventional spin-phonon coupling mechanism. Our observations are consistent with a collective excitation formed by the combination of the vibrational mode with oscillations of local Fe or Cr 3d and Re 5d occupations and spin magnitudes.Comment: 12 pages, 4 figure

The influence of traffic and wood combustion on the stable isotopic composition of carbon monoxide

Carbon monoxide in the atmosphere is originating from various combustion and oxidation processes. Recently, the proportion of CO resulting from the combustion of wood for domestic heating may have increased due to political measures promoting this renewable energy source. Here, we used the stable isotope composition of CO (δ<sup>13</sup>C and δ<sup>18</sup>O) for the characterization of different CO sources in Switzerland, along with other indicators for traffic and wood combustion (NO<sub>x</sub>-concentration, aerosol light absorption at different wavelengths). We assessed diurnal variations of the isotopic composition of CO at 3 sites during winter: a village site dominated by domestic heating, a site close to a motorway and a rural site. The isotope ratios of wood combustion emissions were studied at a test facility, indicating significantly lower δ<sup>18</sup>O of CO from wood combustion compared to traffic emissions. At the village and the motorway site, we observed very pronounced diurnal δ<sup>18</sup>O-variations of CO with an amplitude of up to 8‰. Solving the isotope mass balance equation for three distinct sources (wood combustion, traffic, clean background air) resulted in diurnal patterns consistent with other indicators for wood burning and traffic. The average night-time contribution of wood-burning to total CO was 70% at the village site, 49% at the motorway site and 29% at the rural site based on the isotope mass balance. The results, however, depend strongly on the pure source isotope values, which are not very well known. We therefore additionally applied a combined CO/NO<sub>x</sub>-isotope model for verification. Here, we separated the CO emissions into different sources based on distinct CO/NO<sub>x</sub> emissions ratios for wood combustion and traffic, and inserted this information in the isotope mass balance equation. Accordingly, a highly significant agreement between measured and calculated δ<sup>18</sup>O-values of CO was found (<i>r</i>=0.67, <i>p</i><0.001). While different proxies for wood combustion all have their uncertainties, our results indicate that the oxygen isotope ratio of CO (but not the carbon isotope ratio) is an independent sensitive tool for source attribution studies

Measured and predicted aerosol light scattering enhancement factors at the high alpine site Jungfraujoch

Ambient relative humidity (RH) determines the water content of atmospheric aerosol particles and thus has an important influence on the amount of visible light scattered by particles. The RH dependence of the particle light scattering coefficient (σ<sub>sp</sub>) is therefore an important variable for climate forcing calculations. We used a humidification system for a nephelometer which allows for the measurement of σ<sub>sp</sub> at a defined RH in the range of 20–95%. In this paper we present measurements of light scattering enhancement factors <i>f</i>(RH)=σ<sub>sp</sub>(RH)/σ<sub>sp</sub>(dry) from a 1-month campaign (May 2008) at the high alpine site Jungfraujoch (3580 m a.s.l.), Switzerland. Measurements at the Jungfraujoch are representative for the lower free troposphere above Central Europe. For this aerosol type hardly any information about the <i>f</i>(RH) is available so far. At this site, <i>f</i>(RH=85%) varied between 1.2 and 3.3. Measured <i>f</i>(RH) agreed well with <i>f</i>(RH) calculated with Mie theory using measurements of the size distribution, chemical composition and hygroscopic diameter growth factors as input. Good <i>f</i>(RH) predictions at RH<85% were also obtained with a simplified model, which uses the Ångström exponent of σ<sub>sp</sub>(dry) as input. RH influences further intensive optical aerosol properties. The backscatter fraction decreased by about 30% from 0.128 to 0.089, and the single scattering albedo increased on average by 0.05 at 85% RH compared to dry conditions. These changes in σ<sub>sp</sub>, backscatter fraction and single scattering albedo have a distinct impact on the radiative forcing of the Jungfraujoch aerosol

The Ice Selective Inlet: a novel technique for exclusive extraction of pristine ice crystals in mixed-phase clouds

Climate predictions are affected by high uncertainties partially due to an insufficient knowledge of aerosol-cloud interactions. One of the poorly understood processes is formation of mixed-phase clouds (MPCs) via heterogeneous ice nucleation. Field measurements of the atmospheric ice phase in MPCs are challenging due to the presence of supercooled liquid droplets. The Ice Selective Inlet (ISI), presented in this paper, is a novel inlet designed to selectively sample pristine ice crystals in mixed-phase clouds and extract the ice residual particles contained within the crystals for physical and chemical characterisation. Using a modular setup composed of a cyclone impactor, droplet evaporation unit and pumped counterflow virtual impactor (PCVI), the ISI segregates particles based on their inertia and phase, exclusively extracting small ice particles between 5 and 20 μm in diameter. The setup also includes optical particle spectrometers for analysis of the number size distribution and shape of the sampled hydrometeors. The novelty of the ISI is a droplet evaporation unit, which separates liquid droplets and ice crystals in the airborne state, thus avoiding physical impaction of the hydrometeors and limiting potential artifacts. The design and validation of the droplet evaporation unit is based on modelling studies of droplet evaporation rates and computational fluid dynamics simulations of gas and particle flows through the unit. Prior to deployment in the field, an inter-comparison of the WELAS optical particle size spectrometers and a characterisation of the transmission efficiency of the PCVI was conducted in the laboratory. The ISI was subsequently deployed during the Cloud and Aerosol Characterisation Experiment (CLACE) 2013 – an extensive international field campaign encompassing comprehensive measurements of cloud microphysics, as well as bulk aerosol, ice residual and ice nuclei properties. The campaign provided an important opportunity for a proof of concept of the inlet design. In this work we present the setup of the ISI, including the modelling and laboratory characterisation of its components, as well as a case study demonstrating the ISI performance in the field during CLACE 2013

Tracing uptake and assimilation of NO2 in spruce needles with 13N

For the first time, spruce shoots (Picea abies [L.] Karst.) were fumigated in vivo with 13N-labelled NO2 with the aim of elucidating the mechanism of NO2− trapping in the apoplast of the substomatal cavity. Uptake by the needles could be monitored on-line, and a quantitative analysis of the activity records delivered a deposition velocity in agreement with the common dry deposition estimates and ruled out rapid export processes. A fast extraction procedure was applied which revealed that NO2 did not produce any detectable traces of nitrite. In needles in which the enzymes of nitrate reduction were not induced by prior fumigation with NO2, incorporation of NO2 was partially inhibited as compared to the fully induced shoots which took up and assimilated NO2 as expected from a constant influx. The only labelled inorganic species found in the extracts was nitrate (60%), whereas the rest of the label (40%) was assimilated organic nitrogen.A quantitative analysis of the data shows that the reaction of NO2 in the apoplast yields at least three times more nitrate than nitrite, so that the existing models about the apoplastic trapping reaction, disproportionation or antioxidant scavenging, which both postulate substantial production of nitrite, have to be reconsidere

Effects of relative humidity on aerosol light scattering in the Arctic

Aerosol particles experience hygroscopic growth in the ambient atmosphere. Their optical properties – especially the aerosol light scattering – are therefore strongly dependent on the ambient relative humidity (RH). In-situ light scattering measurements of long-term observations are usually performed under dry conditions (RH>30–40%). The knowledge of this RH effect is of eminent importance for climate forcing calculations or for the comparison of remote sensing with in-situ measurements. This study combines measurements and model calculations to describe the RH effect on aerosol light scattering for the first time for aerosol particles present in summer and fall in the high Arctic. For this purpose, a field campaign was carried out from July to October 2008 at the Zeppelin station in Ny-Ålesund, Svalbard. The aerosol light scattering coefficient σ<sub>sp</sub>(λ) was measured at three distinct wavelengths (λ=450, 550, and 700 nm) at dry and at various, predefined RH conditions between 20% and 95% with a recently developed humidified nephelometer (WetNeph) and with a second nephelometer measuring at dry conditions with an average RH<10% (DryNeph). In addition, the aerosol size distribution and the aerosol absorption coefficient were measured. The scattering enhancement factor <i>f</i>(RH, λ) is the key parameter to describe the RH effect on σ<sub>sp</sub>(λ) and is defined as the RH dependent σ<sub>sp</sub>(RH, λ) divided by the corresponding dry σ<sub>sp</sub>(RH<sub>dry</sub>, λ). During our campaign the average <i>f</i>(RH=85%, λ=550 nm) was 3.24±0.63 (mean ± standard deviation), and no clear wavelength dependence of <i>f</i>(RH, λ) was observed. This means that the ambient scattering coefficients at RH=85% were on average about three times higher than the dry measured in-situ scattering coefficients. The RH dependency of the recorded <i>f</i>(RH, λ) can be well described by an empirical one-parameter equation. We used a simplified method to retrieve an apparent hygroscopic growth factor <i>g</i>(RH), defined as the aerosol particle diameter at a certain RH divided by the dry diameter, using the WetNeph, the DryNeph, the aerosol size distribution measurements and Mie theory. With this approach we found, on average, <i>g</i>(RH=85%) values to be 1.61±0.12 (mean±standard deviation). No clear seasonal shift of <i>f</i>(RH, λ) was observed during the 3-month period, while aerosol properties (size and chemical composition) clearly changed with time. While the beginning of the campaign was mainly characterized by smaller and less hygroscopic particles, the end was dominated by larger and more hygroscopic particles. This suggests that compensating effects of hygroscopicity and size determined the temporal stability of <i>f</i>(RH, λ). During sea salt influenced periods, distinct deliquescence transitions were observed. At the end we present a method on how to transfer the dry in-situ measured aerosol scattering coefficients to ambient values for the aerosol measured during summer and fall at this location