Abstract. Water vapor is the most important greenhouse gas and its spatiotemporal variability strongly exceeds that of all other greenhouse gases. However, this variability has hardly been studied quantitatively so far. We present an analysis of a 5-year period of water vapor measurements in the free troposphere above the Zugspitze (2962 m a.s.l., Germany). Our results are obtained from a combination of measurements of vertically integrated water vapor (IWV), recorded with a solar Fourier transform infrared (FTIR) spectrometer on the summit of the Zugspitze and of water vapor profiles recorded with the nearby differential absorption lidar (DIAL) at the Schneefernerhaus research station. The special geometrical arrangement of one zenith-viewing and one sun-pointing instrument and the temporal resolution of both instruments allow for an investigation of the spatiotemporal variability of IWV on a spatial scale of less than 1 km and on a timescale of less than 1 h. The standard deviation of differences between both instruments σ IWV calculated for varied subsets of data serves as a measure of variability. The different subsets are based on various spatial and temporal matching criteria. Within a time interval of 20 min, the spatial variability becomes significant for horizontal distances above 2 km, but only in the warm season (σ IWV = 0.35 mm). However, it is not sensitive to the horizontal distance during the winter season. The variability of IWV within a time interval of 30 min peaks in July and August (σ IWV > 0.55 mm, mean horizontal distance = 2.5 km) and has its minimum around midwinter (σ IWV < 0.2 mm, mean distance > 5 km). The temporal variability of IWV is derived by selecting subsets of data from both instruments with optimal volume matching. For a short time interval of 5 min, the variability is 0.05 mm and increases to more than 0.5 mm for a time interval of 15 h. The profile variability of water vapor is determined by analyzing subsets of water vapor profiles recorded by the DIAL within time intervals from 1 to 5 h. For all altitudes, the variability increases with widened time intervals. The lowest relative variability is observed in the lower free troposphere around an altitude of 4.5 km. Above 5 km, the relative variability increases continuously up to the tropopause by about a factor of 3. Analysis of the covariance of the vertical variability reveals an enhanced variability of water vapor in the upper troposphere above 6 km. It is attributed to a more coherent flow of heterogeneous air masses, while the variability at lower altitudes is also driven by local atmospheric dynamics. By studying the short-term variability of vertical water vapor profiles recorded within a day, we come to the conclusion that the contribution of long-range transport and the advection of heterogeneous layer structures may exceed the impact of local convection by 1 order of magnitude even in the altitude range between 3 and 5 km.

The molecular recognition of carbohydrates plays a fundamental role in many biological processes. However, the development of carbohydrate-binding reagents for biomedical research and use poses a challenge due to the generally poor affinity of proteins toward sugars in aqueous solution. Here, we describe the effective molecular recognition of pyranose monosaccharides (in particular, galactose and mannose) by a rationally designed protein receptor based on the human lipocalin scaffold (Anticalin). Complexation relies on reversible covalent cis-diol boronate diester formation with a genetically encoded l-boronophenylalanine (Bpa) residue which was incorporated as a non-natural amino acid at a sterically permissive position in the ligand pocket of the Anticalin, as confirmed by X-ray crystallography. Compared with the metal-ion and/or avidity-dependent oligovalent lectins that prevail in nature, our approach offers a novel and promising route to generate tight sugar-binding reagents both as research reagents and for biomedical applications.

Abstract.A method for quantification of sun-pointing inaccuracies in solar absorption spectrometry is presented along with a correction scheme for the resulting errors in trace gas vertical column or profile retrievals. A posteriori correction of pointing errors requires knowledge of both coordinates of the mispointing vector on the solar disk. In principle, quantitative information on the mispointing can be retrieved from Doppler shifts of solar lines derived from measured spectra. However, this yields only one component of the mispointing vector, namely the one which is perpendicular to the solar rotation axis. Missing information on the second vector component has hindered a posteriori correction of mispointing errors so far. Our idea of how to overcome this problem is to obtain estimates of both coordinates of the mispointing by combining subsequent measurements with differing orientations of the solar rotation axis relative to the zenith direction. The proposed concept is suitable in the case of systematic mispointing, i.e