Does fog chemistry in Switzerland change with altitude?

During two extended summer seasons in 2006 and 2007 we operated two battery driven versions of the Caltech active strand cloud water collector (MiniCASCC) at the Niesen mountain (2362 m a.s.l.) in the northern part of the Swiss Alps, and two devices at the Lägeren research tower (690 m a.s.l.) at the northern boundary of the Swiss Plateau. During these two field operation phases we gained weekly samples of fog water, where we analyzed the major anions and cations, and the isotope ratios of fog water (in form of δ2H and δ18O). Dominant ions in fog water at all sites were NH4+, NO3−, and SO42 −. Compared to precipitation, the enrichment factors in fog water were in the range 5–9 at the highest site, Niesen Kulm. We found considerably lower summertime ion loadings in fog water at the two Alpine sites than at lower elevations above the Swiss Plateau. The lowest ion concentrations were found at the Niesen Kulm site at 2300 m a.s.l., whereas the highest concentrations (a factor 7 compared to Niesen Kulm) were found in fog water at the Lägeren site. Occult nitrogen deposition was estimated from fog frequency and typical fog water flux rates. This pathway contributes 0.3–3.9 kg N ha− 1 yr− 1 to the total N deposition at the highest site on Niesen mountain, and 0.1–2.2 kg N ha− 1 yr− 1 at the lower site. These inputs are the reverse of ion concentrations measured in fog due to the 2.5 times higher frequency of fog occurrence at the mountain top (overall fog occurrence was 25% of the time) as compared to the lower Niesen Schwandegg site. Although fog water concentrations were on the lower range reported in earlier studies, fog water is likely to be an important N source for Northern Alpine ecosystems and might reach values up to 16% of the total N deposition and up to 75% of wet N deposition by precipitation.

Highlights in Analytical Chemistry in Switzerland: OMA & OPA - A Software Tool for Mass Spectrometric Sequencing of Nucleic Acids

Oligonucleotides comprising unnatural building blocks, which interfere with the translation machinery, have gained increased attention for the treatment of gene-related diseases (e.g. antisense, RNAi). Due to structural modifications, synthetic oligonucleotides exhibit increased biostability and bioavailability upon administration. Consequently, classical enzyme-based sequencing methods are not applicable to their sequence elucidation and verification. Tandem mass spectrometry is the method of choice for performing such tasks, since gas-phase dissociation is not restricted to natural nucleic acids. However, tandem mass spectrometric analysis can generate product ion spectra of tremendous complexity, as the number of possible fragments grows rapidly with increasing sequence length. The fact that structural modifications affect the dissociation pathways greatly increases the variety of analytically valuable fragment ions. The gas-phase dissociation of oligonucleotides is characterized by the cleavage of one of the four bonds along the phosphodiester chain, by the accompanying loss of nucleases, and by the generation of internal fragments due to secondary backbone cleavage. For example, an 18-mer oligonucleotide yields a total number of 272’920 theoretical fragment ions. In contrast to the processing of peptide product ion spectra, which nowadays is highly automated, there is a lack of tools assisting the interpretation of oligonucleotide data. The existing web-based and stand-alone software applications are primarily designed for the sequence analysis of natural nucleic acids, but do not account for chemical modifications and adducts. Consequently, we developed a software to support the interpretation of mass spectrometric data of natural and modified nucleic acids and their adducts with chemotherapeutic agents.

Combined Secondary Ion Mass Spectrometry Depth Profiling and Focused Ion Beam Analysis of Cu Films Electrodeposited under Oscillatory Conditions

The recrystallization behavior of Cu films electrodeposited under oscillatory conditions in the presence of plating additives was studied by means of secondary ion mass spectrometry (SIMS) and focused ion beam analysis. When combined with bis-(sodium-sulfopropyl)-disulfide (SPS), Imep levelers (polymerizates of imidazole and epichlorohydrin) show characteristic oscillations in the galvanostatic potential/time transient measurements. These are related to the periodic degradation and restoration of the active leveler ensemble at the interface. The leveler action relies on adduct formation between the Imep and MPS (mercaptopropane sulfonic acid)-stabilized CuI complexes that appear as intermediates of the copper deposition when SPS is present in the electrolyte. SIMS depth profiling proves that additives are incorporated into the growing film preferentially under transient conditions during the structural breakdown of the leveler ensemble and its subsequent restoration. In contrast, Cu films electrodeposited in the presence of a structurally intact Imep–CuI–MPS ensemble remain largely contamination free.