Knudsen effusion mass spectrometric determination of the complex vapor composition of samarium, europium, and ytterbium bromides

RATIONALE The vaporization of Sm, Eu, and Yb tri- and dibromides is accompanied by decomposition and disproportionation reactions. These result in complex vapor compositions whose analysis is an intricate problem for experimentalists. Approaches have been developed to interpret mass spectra and accurately determine the vapor composition of thermally unstable compounds. METHODS A sector type magnet instrument was used. A combined ion source allowed the study of both the molecular and ionic vapor compositions in the electron ionization (EI) and the thermionic emission (TE) modes. The methodological approaches were based on a joint analysis of the ionization efficiency functions, the temperature and time dependences of the ion currents, and special mathematical data evaluation. RESULTS The vaporization of SmBr3, YbBr3, SmBr2, EuBr2, and YbBr2 was studied in the temperature range of 850–1300 K. An initial stage of incongruent vaporization was observed in the case of the tribromides, SmBr2, and YbBr2. This eventually changed to a congruent vaporization stage. Various neutral (Ln, Br, Br2, LnBr, LnBr2, LnBr3, Ln2Br4, Ln2Br5, and Ln2Br6) and charged (Br–, LnBr3–, LnBr4–) species were detected at different vaporization stages. CONCLUSIONS The quantitative vapor composition of Sm, Eu, and Yb tri- and dibromides was determined. It was found that only EuBr2 was stable in the studied temperature range. The developed approaches can be useful in the case of other thermally unstable compounds.

The quasi 16-day wave in mesospheric water vapor during boreal winter 2011/2012

This study investigates the characteristics of the quasi 16-day wave in the mesosphere during boreal winter 2011/2012 using observations of water vapor from ground-based microwave radiometers and satellite data. The ground-based microwave radiometers are located in Seoul (South Korea, 37° N), Bern (Switzerland, 47° N) and Sodankylä (Finland, 67° N). The quasi 16-day wave is observed in the mesosphere at all three locations, while the dominant period increases with latitude from 15 days at Seoul to 20 days at Sodankylä. The observed evolution of the quasi 16-day wave confirms that the wave activity is strongly decreased during a sudden stratospheric warming that occurred in mid-January 2012. Using satellite data from the Microwave Limb Sounder on the Aura satellite, we examine the zonal characteristics of the quasi 16-day wave and conclude that the observed waves above the mid-latitudinal stations Seoul and Bern are eastward-propagating s=−1 planetary waves with periods of 15 to 16 days, while the observed oscillation above the polar station Sodankylä is a standing oscillation with a period of approximately 20 days. The strongest relative wave amplitudes in water vapor during the investigated time period are approximately 15%. The wave activity varies strongly along a latitude circle. The activity of the quasi 16-day wave in mesospheric water vapor during boreal winter 2011/2012 is strongest over Northern Europe, the North Atlantic ocean and North-West Canada. The region of highest wave activity seems to be related to the position of the polar vortex. We conclude that the classic approach to characterize planetary waves zonally averaged along a latitude circle is not sufficient to explain the local observations because of the strong longitudinal dependence of the wave activity.

Diurnal variations in middle-atmospheric water vapor by ground-based microwave radiometry

Abstract. In this paper, we compare the diurnal variations in middle-atmospheric water vapor as measured by two ground-based microwave radiometers in the Alpine region near Bern, Switzerland. The observational data set is also compared to data from the chemistry–climate model WACCM. Due to the small diurnal variations of usually less than 1%, averages over extended time periods are required. Therefore, two time periods of five months each, December to April and June to October, were taken for the comparison. The diurnal variations from the observational data agree well with each other in amplitude and phase. The linear correlation coefficients range from 0.8 in the upper stratosphere to 0.5 in the upper mesosphere. The observed diurnal variability is significant at all pressure levels within the sensitivity of the instruments. Comparing our observations with WACCM, we find that the agreement of the phase of the diurnal cycle between observations and model is better from December to April than from June to October. The amplitudes of the diurnal variations for both time periods increase with altitude in WACCM, but remain approximately constant at 0.05 ppm in the observations. The WACCM data are used to separate the processes that lead to diurnal variations in middle-atmospheric water vapor above Bern. The dominating processes were found to be meridional advection below 0.1 hPa, vertical advection between 0.1 and 0.02 hPa and (photo-)chemistry above 0.02 hPa. The contribution of zonal advection is small. The highest diurnal variations in water vapor as seen in the WACCM data are found in the mesopause region during the time period from June to October with diurnal amplitudes of 0.2 ppm (approximately 5% in relative units).