Abstract: The chemical characterization of particulate matter inside and outside of confined bus shelters has been discerned for the first time. Transit patrons are at risk due to the close vicinity of densely trafficked areas resulting in elevated pollution footprints. Incomplete combustion processes, as well as exhaust and wear and tear emissions from public and personal transportation vehicles, are key contributors to degraded urban air quality and are often implicated as causal to various diseases in humans. Urban planning, therefore, includes efficient public transport systems to mitigate the effect. The bus rapid transit system was inaugurated in Curitiba to ensure dedicated traffic lanes, major bus interchanges and semi-confined bus stops called tube stations. To assess the chemical risk that the passengers are exposed to, an investigation of the aerosol inside and outside five of these tube stations was launched. Electron probe X-ray micro-analysis and X-ray fluorescence were used to determine the elemental composition of individual and of bulk particle samples. An aethalometer quantified the black carbon. Elemental concentrations inside the shelters were in general higher than outside, especially for traffic-related elements. The lead concentration exceeded the NAAS standard at times, although the average was below the guideline. The biogenic, organic and soot clusters showed the highest abundance for the city centre sites. The overall carcinogenic risk could be classed as moderate, and the risk was significant at two sites during one of the sampling campaigns. The non-carcinogenic risk is well below the significant value.

Abstract: The contamination of ground samples by a commercially available Lovibond McCrone Micronizing Mill is discussed. Tracer and weighing experiments showed that abrasion of corundum grinding elements was important, introducing 620 mg of abrasion products per minute of wet grinding. Agate grinding elements were abraded at ⩽6 mg min-1. The abrasion products and grinding elements were analyzed by x-ray fluorescence, spark-source mass spectrometry and neutron activation analysis. Contamination in trace element analysis of geological materials is likely to be negligible for agate grinding elements and, except for a few transition metals, also for corundum grinding elements. Contamination of typical biological samples is significant for a few elements even when agate elements are used, and is absolutely prohibitive for trace analysis when corundum elements are used.

Abstract: Increasingmass tourismcan generate importantmicroclimatic perturbations and also elevate indoor pollution by the transport of fine particulatematter. The purpose of this researchwas to study the indoor air conditions in the RoyalMuseum ofWawel Castle in Cracow, Poland, displaying amongst other valuable works of art also a unique collection of Flemish tapestries. The investigation involved in the determination of transport and deposition of particulate matter brought in by visitors. The microclimate inside the exhibition rooms was also monitored. Samples of suspended particulateswere collected inside and outside themuseuminwinterand summer2006.On days with intensive tourist visits the concentration of total suspended particulates was significantly higher (i.e., 130 µg/m3 inwinter and 49 µg/m3 in summer) than on those days without tourists (i.e., 73 µg/m3 and 22 µg/m3 in winter and summer, respectively). The concentrations of all investigated elementswere also considerably higher during the tourist flow. This was especially valid for soil dust associated elements (Si, K, Ca, Al, and Ti), with considerably higher levels in summer than winter. This could be linked with much more frequent tourist activity in the summer period. Also, the concentration of Clwasmuch higher inwinter than summer, due to the use of deicing salts on the roads and pavements.

Abstract: The tetravalent and hexavalent selenium content of water samples can be determined by conventional energy-dispersive X-ray fluorescence after different preconcentration steps. Selenium values of nearly three-hundred different environmental and drinking water samples in Belgium are reported. The results are quite low, ranging from the detection limits up to 1 μg l−1. The concentration levels are compared to literature data and the speciation is discussed. The contribution of drinking water to the daily intake of selenium in Belgium ranges from less than 0.2 to 5%.

Abstract: Data obtained by atomic absorption spectroscopy showed a selenium concentration of only 0.11 ppm as an average value for the most representative agricultural soils in Belgium. The selenium content in rye-grass grown on different soil types was between 0.05 and 0.11 ppm, and positively correlated with the soil selenium level. Addition of selenium in the form of selenite to the different soil types resulted in an increased selenium uptake by the plant. The ultimate concentration in the plant depended on the structural and chemical composition of the soil. Twelve other elements were determined in the soils by energy-dispersive X-ray fluorescence; none showed a strong correlation with the soil selenium content or with the selenium uptake by ryegrass.

Abstract: Aptamers are short, synthetic DNA or RNA molecules that are characterized by a specific 3D conformation which enables specific target recognition. Aptamers are promising tools in many application fields from sensing to therapeutics. One of the major challenges in the aptamer field is understanding the relationship between the sequence and what determines the higher-order structure and specific interactions with targets. Therefore, this PhD thesis focuses on the use of different mass spectrometry (MS) based approaches to characterize aptamers and their interactions. Several of these approaches are already widely applied to study other biomolecules, such as proteins, but are still largely unexplored for aptamers and oligonucleotides in general. A first focus was put on obtaining information on the higher-order structure and conformational stability of aptamers using a combination of MS and with ion mobility (IM) spectrometry by performing collision-induced unfolding (CIU) experiments. CIU was shown to hold great promise to analyze the conformational dynamics and gas-phase stabilities of aptamers. Next, the capabilities and limitations of native IM-MS for the analysis of noncovalent interactions of aptamers were demonstrated. The conformational behavior and interactions of cocaine-binding aptamers were studied and it was found that relative binding affinities of aptamers that only differ slightly in sequence and structure can be determined using native MS. Moreover, native IM-MS allowed the detection of small conformational changes upon binding of a target, which were found to be dependent on the binding mode of the aptamer. An adaptive binding mechanism was suggested for flexible aptamers that require more reorganization upon binding. In the final part of this thesis, the importance of thoroughly characterizing and validating aptamer-target interactions before using them in an application was emphasized. Moreover, the gathered insights were applied in our own development of a proof-of-concept aptamer-based sensor. This was shown by investigating the interactions of ampicillin aptamers which were found to not bind the target they were selected for in the first place. A multi-analytical approach combining complementary techniques was used for this purpose since no single technique is generally applicable to characterize all aptamers and their interactions and to obtain a comprehensive picture of the aptamer-target interactions. Furthermore, such multi-analytical approach was used to characterize a testosterone-binding aptamer while developing an aptamer-based electrochemiluminescent sensing strategy for this target. This shows the importance of native MS, in combination with other techniques, to thoroughly understand the aptamer-target interactions in the development of a designed application.

Abstract: A fast (10 min), non-destructive simultaneous determination of silicon and phosphorus in cast iron and steel by 14 MeV neutron activation was developed. The 1.78 MeV28Al activity (T=2.24 min) induced by the reaction28Si(n, p)28Al is counted on a NaI(Tl) detector. Two measurements are made to correct for the 1.81 MeV56Mn activity (T=2.58 hr) from the iron matrix. However,28Al is also produced via31P(n, α)28Al. By (n, 2n) reaction, phosphorus yields also30P (T=2.6 min), the 0.511 MeV annihilation radiation of which is counted by two opposite NaI(Tl) detectors in coincidence. Again, two successive coincidence measurements are carried out in order to take into account the53Fe activity (β+; T=8.9 min) from54Fe(n, 2n)53Fe. The28Al measurement is appropriately corrected via the computed phosphorus content. An oxygen flux monitor was used to normalize to the same flux. Nuclear interferences have been examined. Special attention has been paid to the presence of copper. The standard deviation for phosphorus being as high as ca. 0.09% P for a single determination, this technique can only be practical as an independent phosphorus analysis for high phosphorus cast irons. The precision on the28Al measurement is 5% relative for 0.2% Si and 2.5% above 1% Si.