Strong aerosol-cloud interaction in altocumulus during updraft periods: Lidar observations over central Europe

For the first time, a liquid-water cloud study of the aerosol–cloud-dynamics relationship, solely based on lidar, was conducted. Twenty-nine cases of pure liquid-water altocumulus layers were observed with a novel dual-field-of-view Raman lidar over the polluted central European site of Leipzig, Germany, between September 2010 and September 2012. By means of the novel Raman lidar technique, cloud properties such as the droplet effective radius and cloud droplet number concentration (CDNC) in the lower part of altocumulus layers are obtained. The conventional aerosol Raman lidar technique provides the aerosol extinction coefficient (used as aerosol proxy) below cloud base. A collocated Doppler lidar measures the vertical velocity at cloud base and thus updraft and downdraft occurrence. Here, we present the key results of our statistical analysis of the 2010–2012 observations. Besides a clear aerosol effect on cloud droplet number concentration in the lower part of the altocumulus layers during updraft periods, turbulent mixing and entrainment of dry air is assumed to be the main reason for the found weak correlation between aerosol proxy and CDNC higher up in the cloud. The corresponding aerosol–cloud interaction parameter based on changes in cloud droplet number concentration with aerosol loading was found to be close to 0.8 at 30–70 m above cloud base during updraft periods and below 0.4 when ignoring vertical-wind information in the analysis. Our findings are extensively compared with literature values and agree well with airborne observations

Strong aerosol-cloud interaction in altocumulus during updraft periods: Lidar observations over central Europe

For the first time, a liquid-water cloud study of the aerosol–cloud-dynamics relationship, solely based on lidar, was conducted. Twenty-nine cases of pure liquid-water altocumulus layers were observed with a novel dual-field-of-view Raman lidar over the polluted central European site of Leipzig, Germany, between September 2010 and September 2012. By means of the novel Raman lidar technique, cloud properties such as the droplet effective radius and cloud droplet number concentration (CDNC) in the lower part of altocumulus layers are obtained. The conventional aerosol Raman lidar technique provides the aerosol extinction coefficient (used as aerosol proxy) below cloud base. A collocated Doppler lidar measures the vertical velocity at cloud base and thus updraft and downdraft occurrence. Here, we present the key results of our statistical analysis of the 2010–2012 observations. Besides a clear aerosol effect on cloud droplet number concentration in the lower part of the altocumulus layers during updraft periods, turbulent mixing and entrainment of dry air is assumed to be the main reason for the found weak correlation between aerosol proxy and CDNC higher up in the cloud. The corresponding aerosol–cloud interaction parameter based on changes in cloud droplet number concentration with aerosol loading was found to be close to 0.8 at 30–70 m above cloud base during updraft periods and below 0.4 when ignoring vertical-wind information in the analysis. Our findings are extensively compared with literature values and agree well with airborne observations

Thermodynamics of the formation of sulfuric acid dimers in the binary (H2SO4-H2O) and ternary (H2SO4-H2O-NH3) system

Sulfuric acid is an important gas influencing atmospheric new particle formation (NPF). Both the binary (H2SO4–H2O) system and the ternary system involving ammonia (H2SO4–H2O–NH3) may be important in the free troposphere. An essential step in the nucleation of aerosol particles from gas-phase precursors is the formation of a dimer, so an understanding of the thermodynamics of dimer formation over a wide range of atmospheric conditions is essential to describe NPF. We have used the CLOUD chamber to conduct nucleation experiments for these systems at temperatures from 208 to 248 K. Neutral monomer and dimer concentrations of sulfuric acid were measured using a chemical ionization mass spectrometer (CIMS). From these measurements, dimer evaporation rates in the binary system were derived for temperatures of 208 and 223 K. We compare these results to literature data from a previous study that was conducted at higher temperatures but is in good agreement with the present study. For the ternary system the formation of H2SO4·NH3 is very likely an essential step in the formation of sulfuric acid dimers, which were measured at 210, 223, and 248 K. We estimate the thermodynamic properties (dH and dS) of the H2SO4·NH3 cluster using a simple heuristic model and the measured data. Furthermore, we report the first measurements of large neutral sulfuric acid clusters containing as many as 10 sulfuric acid molecules for the binary system using chemical ionization–atmospheric pressure interface time-of-flight (CI-APi-TOF) mass spectrometry

Combined vertical-velocity observations with Doppler lidar, cloud radar and wind profiler

Case studies of combined vertical-velocity measurements of Doppler lidar, cloud radar and wind profiler are presented. The measurements were taken at the Meteorological Observatory, Lindenberg, Germany. Synergistic products are presented that are derived from the vertical-velocity measurements of the three instruments: a comprehensive classification mask of vertically moving atmospheric targets and the terminal fall velocity of water droplets and ice crystals corrected for vertical air motion. It is shown that this combination of instruments can up-value the measurement values of each single instrument and may allow the simultaneous sensing of atmospheric targets and the motion of clear air

Organofluorine chemistry : difluoromethylene motifs spaced 1,3 to each other imparts facial polarity to a cyclohexane ring

This work was supported by the Engineering and Physical Sciences Research Council (EPSRC) and the European Research Council (ERC). The authors acknowledge the EPSRC National Mass Spectrometry Facility (Swansea). D.O’H. thanks the Royal Society for a Wolfson Research Merit Award.2,2-Dimethyl-5-phenyl-1,1,3,3-tetrafluororocyclohexane has been prepared and characterised as an example of a facially polarised cyclohexane containing 1,3 related CF2 groups. The dipolar nature of the ring arises from the axial orientation of two of the C-F bonds pointing in the same direction, and set by the chair conformation of the cyclohexane. This electrostatic profile is revealed experimentally both in the solid-state (X-ray) packing of the rings and by solution (NMR) in different solvents. A computationally derived electrostatic profile of this compound is consistent with a more electronegative and a more electropositive face of the cyclohexane ring. This placing of CF2 groups 1,3 to each other in a cyclohexane ring is introduced as a new design strategy which could be applicable to the preparation of polar hydrophobic cyclohexane motifs.Publisher PDFPeer reviewe

Structure and dynamics of iron pentacarbonyl

The dynamics of CO ligand scrambling in Fe(CO)5 has been investigated by linear infrared spectroscopy in supercritical xenon solution. The activation barrier for the Berry pseudorotation in Fe(CO)5 was determined experimentally to be Ea = 2.5 ± 0.4 kcal mol–1 by quantitative analysis of the temperature-dependent spectral line shape. This compares well with the range of Ea/(kcal mol–1) = 2.0 to 2.3 calculated by various DFT methods and the value of 1.6 ± 0.3 previously obtained from 2D IR measurements by Harris et al. ( Science 2008, 319, 1820). The involvement of Fe(CO)5···Xe interactions in the ligand scrambling process was tested computationally at the BP86-D3/AE2 level and found to be negligible

Effect of ligand backbone on the selectivity and stability of rhodium hydroformylation catalysts derived from phospholane-phosphites

We thank the Eastman Chemical Company for funding and permission to publish. M.B. thanks the School of Chemistry and EaStCHEM for support.A study on how ligand backbone structure has an impact on selectivity, rate, and catalyst stability of hydroformylation catalysts was prompted by some longer-term stability issues being discovered for a phospholane-phosphite with a [−CH2O−] backbone. A series of phospholane-phosphite ligands were synthesized. Catalysts made in situ from these ligands and [Rh(acac)(CO)2] were found to give iso-butanal selectivities up to 75% at temperatures between 75 and 105 °C: the latter being a benchmark for iso-selectivity in reactions conducted at industrially meaningful temperatures. A racemic rhodium complex of a bidentate phospholane-phosphite from a tropos-biphenol with an extended backbone showed unusually high stability at high temperatures, combined with even better iso-selectivity in propene hydroformylation relative to the original complex. A related ligand with an electron-withdrawing group maintained the unusually high stability and improved activity. Characterization of the precatalysts of type [RhH(CO)2(L)] was accomplished using in situ HPIR spectroscopy and backed up by density functional theory calculations (B3PW91-D3 level) and by NMR studies; the latter showed that the variation of the backbone also had a pronounced impact on the precatalyst structure. A key finding is that it is now possible to prepare phospholane-phosphite ligands that deliver high iso-butanal selectivity and that show no signs of degradation after several days even above typical reaction temperatures. In one stability test, several kilograms of aldehydes were produced with TOF and selectivity being consistent over several days.PostprintPeer reviewe

Combining cloud radar and radar wind profiler for a value added estimate of vertical air motion and particle terminal velocity within clouds

Vertical-stare observations from a 482 MHz radar wind profiler and a 35 GHz cloud radar are combined on the level of individual Doppler spectra to measure vertical air motions in clear air, clouds and precipitation. For this purpose, a separation algorithm is proposed to remove the influence of falling particles from the wind profiler Doppler spectra and to calculate the terminal fall velocity of hydrometeors. The remaining error of both vertical air motion and terminal fall velocity is estimated to be better than 0.1 m s−1 using numerical simulations. This combination of instruments allows direct measurements of in-cloud vertical air velocity and particle terminal fall velocity by means of ground-based remote sensing. The possibility of providing a profile every 10 s with a height resolution of  &lt; 100 m allows further insight into the process scale of in-cloud dynamics. The results of the separation algorithm are illustrated by two case studies, the first covering a deep frontal cloud and the second featuring a shallow mixed-phase cloud.</p

Application of the shipborne remote sensing supersite OCEANET for profiling of Arctic aerosols and clouds during Polarstern cruise PS106

From 25 May to 21 July 2017, the research vessel Polarstern performed the cruise PS106 to the high Arctic in the region north and northeast of Svalbard. The mobile remote-sensing platform OCEANET was deployed aboard Polarstern. Within a single container, OCEANET houses state-of-the-art remote-sensing equipment, including a multiwavelength Raman polarization lidar PollyXT and a 14-channel microwave radiometer HATPRO (Humidity And Temperature PROfiler). For the cruise PS106, the measurements were supplemented by a motion-stabilized 35 GHz cloud radar Mira-35. This paper describes the treatment of technical challenges which were immanent during the deployment of OCEANET in the high Arctic. This includes the description of the motion stabilization of the cloud radar Mira-35 to ensure vertical-pointing observations aboard the moving Polarstern as well as the applied correction of the vessels heave rate to provide valid Doppler velocities. The correction ensured a leveling accuracy of ±0.5◦ during transits through the ice and an ice floe camp. The applied heave correction reduced the signal induced by the vertical movement of the cloud radar in the PSD of the Doppler velocity by a factor of 15. Low-level clouds, in addition, frequently prevented a continuous analysis of cloud conditions from synergies of lidar and radar within Cloudnet, because the technically determined lowest detection height of Mira-35 was 165 m above sea level. To overcome this obstacle, an approach for identification of the cloud presence solely based on data from the near-field receiver of PollyXT at heights from 50 m and 165 m above sea level is presented. We found low-level stratus clouds, which were below the lowest detection range of most automatic ground-based remote-sensing instruments during 25 % of the observation time. We present case studies of aerosol and cloud studies to introduce the capabilities of the data set. In addition, new approaches for ice crystal effective radius and eddy dissipation rates from cloud radar measurements and the retrieval of aerosol optical and microphysical properties from the observations of PollyXT are introduced. © Author(s) 2020. This work is distributed under the Creative Commons Attribution 4.0 License

Artificial Metalloenzymes as Catalysts for Oxidative Lignin Degradation

We report novel artificial metalloenzymes (ArMs), containing tris­(pyridylmethyl)­amine (TPA), for the atom economic oxidation of lignin β-O-4 model compounds, using hydrogen peroxide. The protein scaffold alters the selectivity of the reaction from a low yielding cleavage reaction when using the parent Fe-tpa complex to a high yielding benzylic alcohol oxidation when using the complex incorporated into a protein scaffold, SCP-2L A100C. Engineering the protein scaffold to incorporate glutamic acid was found to improve the ArM activity, showing that rational design of the protein environment using metal binding amino acids can be a first step toward improving the overall activity of an artificial metalloenzyme