ALBERT

Description: Surfaced-enhanced Raman spectroscopy has been used to study rotational isomers of succinonitrile and N-methyl-thioacetamide on Cu and Ag surfaces. Both the gauche and trans conformers of succinonitrile are found to chemisorb on the metal surface. The doubly degenerate nu(C-triple bond-N) in the free molecules is removed when succinonitrile adsorbs on copper, which indicates that the two (C-triple bond-N) groups are no longer chemically equivalent. Both conformers are found to coordinate to the copper surface through the pi system of one of the two (C-triple bond-N) groups. In the case of N-methyl-thioacetamide, the population of the cis isomer is greatly increased on Cu and Ag surfaces. This is probably due to surface-induced cis-trans isomerization, in which the predominant trans isomer is converted to the cis isomer.

Description: Surface-enhanced Raman spectroscopy has been used to study the molecular interactions of malononitrile with copper electrode surfaces. The doubly degenerate CN stretching frequency at 2263/cm is removed when malononitrile adsorbs on copper. Two nu(CN) bands are observed at 2096 and 2204/cm at -0.6 V(SCE). The result shows that only one CN group is pi-coordinated with Cu, which contributes to the observed large shift (-167/cm) in nu(CN). The other CN group is not coordinated to the metal surface.

Description: Fourier transform infrared (FTIR) and Raman spectroscopic techniques were used to study the solution concentration gradient in succino nitrile-rich and water-rich homogeneous solutions. The spectroscopic data shows significant concentration dependency. Although FTIR-attenuated total reflectance could not yield surface spectra since the evanescent infrared wave penetrated deep into the bulk solution, it showed that water-rich clusters were decreased at higher temperatures. This result is consistent with the calorimetric results reported earlier.

Description: Recently, temporal changes in Aerosol Optical Thickness (AOT) have been investigated based on model simulations, satellite and ground-based observations. Most AOT trend studies used monthly or annual arithmetic means that discard details of the generally right-skewed AOT distributions. Potentially, such results can be biased by extreme values (including outliers). This study additionally uses percentiles (i.e., the lowest 5%, 25%, 50%, 75% and 95% of the monthly cumulative distributions fitted to Aerosol Robotic Network (AERONET)-observed and ECHAM/MESSy Atmospheric Chemistry (EMAC)-model simulated AOTs) that are less affected by outliers caused by measurement error, cloud contamination and occasional extreme aerosol events. Since the limited statistical representativeness of monthly percentiles and means can lead to bias, this study adopts the number of observations as a weighting factor, which improves the statistical robustness of trend estimates. By analyzing the aerosol composition of AERONET-observed and EMAC-simulated AOTs in selected regions of interest, we distinguish the dominant aerosol types and investigate the causes of regional AOT trends. The simulated and observed trends are generally consistent with a high correlation coefficient (R = 0.89) and small bias (slope+/-2(sigma) = 0.75 +/- 0.19). A significant decrease in EMAC-decomposed AOTs by water-soluble compounds and black carbon is found over the USA and the EU due to environmental regulation. In particular, a clear reversal in the AERONET AOT trend percentiles is found over the USA, probably related to the AOT diurnal cycle and the frequency of wildfires. In most of the selected regions of interest, EMAC-simulated trends are mainly attributed to the significant changes of the dominant aerosols; e.g., significant decrease in sea salt and water soluble compounds over Central America, increase in dust over Northern Africa and Middle East, and decrease in black carbon and organic carbon over Australia.