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).

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 midlatitudinal 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 wave 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 northwestern 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.

Trajectory mapping of middle atmospheric water vapor by a mini network of NDACC instruments

The important task to observe the global coverage of middle atmospheric trace gases like water vapor or ozone usually is accomplished by satellites. Climate and atmospheric studies rely upon the knowledge of trace gas distributions throughout the stratosphere and mesosphere. Many of these gases are currently measured from satellites, but it is not clear whether this capability will be maintained in the future. This could lead to a significant knowledge gap of the state of the atmosphere. We explore the possibilities of mapping middle atmospheric water vapor in the Northern Hemisphere by using Lagrangian trajectory calculations and water vapor profile data from a small network of five ground-based microwave radiometers. Four of them are operated within the frame of NDACC (Network for the Detection of Atmospheric Composition Change). Keeping in mind that the instruments are based on different hardware and calibration setups, a height-dependent bias of the retrieved water vapor profiles has to be expected among the microwave radiometers. In order to correct and harmonize the different data sets, the Microwave Limb Sounder (MLS) on the Aura satellite is used to serve as a kind of traveling standard. A domain-averaging TM (trajectory mapping) method is applied which simplifies the subsequent validation of the quality of the trajectory-mapped water vapor distribution towards direct satellite observations. Trajectories are calculated forwards and backwards in time for up to 10 days using 6 hourly meteorological wind analysis fields. Overall, a total of four case studies of trajectory mapping in different meteorological regimes are discussed. One of the case studies takes place during a major sudden stratospheric warming (SSW) accompanied by the polar vortex breakdown; a second takes place after the reformation of stable circulation system. TM cases close to the fall equinox and June solstice event from the year 2012 complete the study, showing the high potential of a network of ground-based remote sensing instruments to synthesize hemispheric maps of water vapor.

Effect of the Tiger Stripes on the water vapor distribution in Enceladus' exosphere

The jet activity emanating from Enceladus' exosphere south pole region observed by Cassini is a subject of intensive study. The in situ and remote sensing observations performed since 2005 triggered an active modeling campaign. Such modeling is essential for better understanding of the measurements performed by individual instruments as well as to link them for a more complete picture of the volatile and ice grain distribution in Enceladus' exosphere. This paper is focused on the investigation of the effect that diffuse gas sources along the Tiger Stripes have on distribution of the water vapor in Enceladus' exosphere using the updated version of our multiplume model. We have found that accounting for the gas production by Tiger Stripes is critical for interpretation of the Cassini data. According to our calculations, sources along the Tiger Stripes (apart from those originally identified by Spitale and Porco (2007)) must contribute about 23–32% to the total plume source rate, which varies in the range of (6.4–29) ×1027 s−1. The effect of the previously unidentified source suggested in the paper is found to be critical for explaining the Ultraviolet Imaging Spectrograph 2007 and 2010 observations in the whole range of the elapsed times.

Vapor phase composition as an indicator of thermal stability of the Sm, Eu, and Yb chlorides

The Sm, Eu, and Yb tri- and dichlorides were investigated by Knudsen effusion mass spectrometry. It was found out by the analysis of mass spectra and ionization efficiency curves that the vapor composition is complex due to the partial high temperature decomposition/disproportionation of the samples. Up to five vapor species were identified for both LnCl3 (LnCl3, LnCl2, Ln2Cl4, Ln2Cl5, and Ln2Cl6) and LnCl2 (LnCl3, LnCl2, LnCl, Ln, and Ln2Cl4). The quantitative evaluation of vapor composition was made. It indicates that the disproportionation of SmCl2 and EuCl2 is negligible in the temperature range studied whereas that of YbCl2 and the decomposition of SmCl3 and YbCl3 cannot be neglected.

Vapor deposition coating of fused silica tubes with amorphous selenium

A set of optimized deposition conditions for the inner wall coating of fused silica tubes with amorphous selenium was elaborated. The method is based on the vapor transport deposition of pure elemental selenium on a cooled substrate held at liquid nitrogen temperatures. Morphological and structural examination of the deposited layer was performed by optical microscopy and X-ray diffraction studies. Neutron activated selenium was used to monitor the deposition pattern and its stability under high gas flows. Monte Carlo simulations allowed the estimation of the different Se species composing the amorphous phase, at the given experimental deposition conditions. The versatility of the coating method presented in this work allows for the coating of tubes of different lengths and diameters, opening the way for several applications of amorphous selenium films in various fields.

Trajectory mapping of middle atmospheric water vapor by a mini network of NDACC instruments

The important task to observe the global coverage of middle atmospheric trace gases like water vapor or ozone usually is accomplished by satellites. Climate and atmospheric studies rely upon the knowledge of trace gas distributions throughout the stratosphere and mesosphere. Many of these gases are currently measured from satellites, but it is not clear whether this capability will be maintained in the future. This could lead to a significant knowledge gap of the state of the atmosphere. We explore the possibilities of mapping middle atmospheric water vapor in the Northern Hemisphere by using Lagrangian trajectory calculations and water vapor profile data from a small network of five ground-based microwave radiometers. Four of them are operated within the frame of NDACC (Network for the Detection of Atmospheric Composition Change). Keeping in mind that the instruments are based on different hardware and calibration setups, a height-dependent bias of the retrieved water vapor profiles has to be expected among the microwave radiometers. In order to correct and harmonize the different data sets, the Microwave Limb Sounder (MLS) on the Aura satellite is used to serve as a kind of traveling standard. A domain-averaging TM (trajectory mapping) method is applied which simplifies the subsequent validation of the quality of the trajectory-mapped water vapor distribution towards direct satellite observations. Trajectories are calculated forwards and backwards in time for up to 10 days using 6 hourly meteorological wind analysis fields. Overall, a total of four case studies of trajectory mapping in different meteorological regimes are discussed. One of the case studies takes place during a major sudden stratospheric warming (SSW) accompanied by the polar vortex breakdown; a second takes place after the reformation of stable circulation system. TM cases close to the fall equinox and June solstice event from the year 2012 complete the study, showing the high potential of a network of ground-based remote sensing instruments to synthesize hemispheric maps of water vapor.

Variability of mesospheric water vapor above Bern in relation to the 27-day solar rotation cycle

Many studies investigated solar–terrestrial responses (thermal state, O₃ , OH, H₂O) with emphasis on the tropical upper atmosphere. In this paper the Focus is switched to water vapor in the mesosphere at a mid-latitudinal location. Eight years of water vapor profile measurements above Bern (46.88°N/7.46°E) are investigated to study oscillations with the Focus on periods between 10 and 50 days. Different spectral analyses revealed prominent features in the 27-day oscillation band, which are enhanced in the upper mesosphere (above 0.1 hPa, ∼64 km) during the rising sun spot activity of solar cycle 24. Local as well as zonal mean Aura MLS observations Support these results by showing a similar behavior. The relationship between mesospheric water and the solar Lyman-α flux is studied by comparing thesi-milarity of their temporal oscillations. The H₂O oscillation is negatively correlated to solar Lyman-α oscillation with a correlation coefficient of up to −0.3 to −0.4, and the Phase lag is 6–10 days at 0.04 hPa. The confidence level of the correlation is ≥99%. This finding supports the assumption that the 27-day oscillation in Lyman-α causes a periodical photo dissociation loss in mesospheric water. Wavelet power spectra, cross-wavelet transform and wavelet coherence analysis (WTC)complete our study. More periods of high common wavelet power of H₂O and solar Lyman-α are present when amplitudes of the Lyman-α flux increase. Since this is not a measure of physical correlation a more detailed view on WTC is necessary, where significant (two sigma level)correlations occur intermittently in the 27 and 13-day band with variable Phase lock behavior. Large Lyman-α oscillations appeared after the solar super storm in July 2012 and the H₂O oscillations show a well pronounced anticorrelation. The competition between advective transport and photo dissociation loss of mesospheric water vapor may explain the sometimes variable Phase relationship of mesospheric H₂O and solar Lyman-α oscillations. Generally, the WTC analysis indicates that solar variability causes observable photochemical and dynamical processes in the mid-latitude mesosphere.

Assessment of the performance of 3m 3500 organic vapor monitors over extended sampling durations

The purpose of this study was to assess the accuracy and precision of airborne volatile organic compound (VOC) concentrations measured using passive air samplers (3M 3500 organic vapor monitors) over extended sampling durations (9 and 15 days). A total of forty-five organic vapor monitor samples were collected at a State of Texas air monitoring site during two different sampling periods (July/August and November 2008). The results of this study indicate that for most of the tested compounds, there was no significant difference between long-term (9 or 15 days) sample concentrations and the means of parallel consecutive short-term (3 days) sample concentrations. Biases of 9 or 15-day measurements vs. consecutive 3-day measurements showed considerable variability. Those compounds that had percent bias values of <10% are suggested as acceptable for long-term sampling (9 and 15 days). Of the twenty-one compounds examined, 10 compounds are classified as acceptable for long-term sampling; these include m,p-xylene, 1,2,4-trimethylbenzene, n-hexane, ethylbenzene, benzene, toluene, o-xylene, d-limonene, dimethylpentane and methyl tertbutyl ether. The ratio of sampling procedure variability relative to variability within days was approximately 1.89 for both sampling periods for the 3-day vs. 9-day comparisons and approximately 2.19 for both sampling periods for the 3-day vs. 15-day comparisons. Considerably higher concentrations of most VOCs were measured during the November sampling period compared to the July/August period. These differences may be a result of varying meteorological conditions during these two time periods, e.g., the differences in wind direction, and wind speed. Further studies are suggested to further evaluate the accuracy and precision of 3M 3500 organic vapor monitors over extended sampling durations. ^

An assessment of the relative influence of a vapor recovery system in reducing occupational exposure to volatile organic compounds in high performance liquid chromatography

Occupational exposures to organic solvents, specifically acetonitrile and methanol, have the potential to cause serious long-term health effects. In the laboratory, these solvents are used extensively in protocols involving the use of high performance liquid chromatography (HPLC). Operators of HPLC equipment may be potentially exposed to these organic solvents when local exhaust ventilation is not employed properly or is not available, which can be the case in many settings. The objective of this research was to characterize the various sites of vapor release in the HPLC process and then to determine the relative influence of a novel vapor recovery system on the overall exposure to laboratory personnel. The effectiveness of steps to reduce environmental solvent vapor concentrations was assessed by measuring exposure levels of acetonitrile and methanol before and after installation of the vapor recovery system. With respect to acetonitrile, the concentration was not statistically significant with p=0.938; moreover, exposure after the intervention was actually higher than prior to intervention. With respect to methanol, the concentration was not statistically significant with p=0.278. This indicates that the exposure to methanol after the intervention was not statistically significantly higher or lower than prior to intervention. Thus, installation of the vapor recovery device did not result in statistically significant reduction in exposures in the settings encountered, and acetonitrile actually increased significantly.^

Chamber evaluation of a personal organic vapor dosimeter at ppb concentrations of VOCs, varying temperatures and humidities with 24 -hour exposures

An exposure system was constructed to evaluate the performance of a personal organic vapor dosimeter (3520 OVM) at ppb concentrations of nine selected target volatile organic compounds (VOCs). These concentration levels are generally encountered in community air environments, both indoor and outdoor. It was demonstrated that the chamber system could provide closely-controlled conditions of VOC concentrations, temperature and relative humidity (RH) required for the experiments. The target experimental conditions included combinations of three VOC concentrations (10, 20 and 200 $\rm\mu g/m\sp3),$ three temperatures (10, 25 and 40$\sp\circ$C) and three RHs (12, 50 and 90% RH), leading to a total of 27 exposure conditions. No backgrounds of target VOCs were found in the exposure chamber system. In the exposure chamber, the variation of the temperature was controlled within $\pm$1$\sp\circ$C, and the variation of RH was controlled within $\pm$1.5% at 12% RH, $\pm$2% at 50% RH and $\pm$3% at 90% RH. High-emission permeation tubes were utilized to generate the target VOCs. Various patterns of the permeation rates were observed over time. The lifetimes and permeation rates of the tubes differed by compound, length of the tube and manufacturer. By carefully selecting the source and length of the tubes, and closely monitoring tube weight loss over time, the permeation tubes can be used for delivering low and stable concentrations of VOCs during multiple days.^ The results of this study indicate that the performance of the 3520 OVM is compound-specific and depends on concentration, temperature and humidity. With the exception of 1,3-butadiene under most conditions, and styrene and methylene chloride at very high relative humidities, recoveries were generally within $\pm$25% of theory, indicating that the 3520 OVM can be effectively used over the range of concentrations and environmental conditions tested with a 24-hour sampling period. Increasing humidities resulted in increasing negative bias from full recovery. Reverse diffusion conducted at 200 $\rm\mu g/m\sp3$ and five temperature/humidity combinations indicated severe diffusion losses only for 1,3-butadiene, methylene chloride and styrene under increased humidity. Overall, the results of this study do not support the need to employ diffusion samplers with backup sections for the exposure conditions tested. ^