The kinetics and reactivity of several polyatomic free radicals in reactions with NO2, O2, Cl2, and HCl

In this thesis, the kinetics of several alkyl, halogenated alkyl, and alkenyl free radical reactions with NO2, O2, Cl2, and HCl reactants were studied over a wide temperature range in time resolved conditions. Laser photolysis photoionisation mass spectrometer coupled to a flow reactor was the experimental method employed and this thesis present the first measurements performed with the experimental system constructed. During this thesis a great amount of work was devoted to the designing, building, testing, and improving the experimental apparatus. Carbon-centred free radicals were generated by the pulsed 193 or 248 nm photolysis of suitable precursors along the tubular reactor. The kinetics was studied under pseudo-first-order conditions using either He or N2 buffer gas. The temperature and pressure ranges employed were between 190 and 500 K, and 0.5 45 torr, respectively. The possible role of heterogeneous wall reactions was investigated employing reactor tubes with different sizes, i.e. to significantly vary the surface to volume ratio. In this thesis, significant new contributions to the kinetics of carbon-centred free radical reactions with nitrogen dioxide were obtained. Altogether eight substituted alkyl (CH2Cl, CHCl2, CCl3, CH2I, CH2Br, CHBr2, CHBrCl, and CHBrCH3) and two alkenyl (C2H3, C3H3) free radical reactions with NO2 were investigated as a function of temperature. The bimolecular rate coefficients of all these reactions were observed to possess negative temperature dependencies, while pressure dependencies were not noticed for any of these reactions. Halogen substitution was observed to moderately reduce the reactivity of substituted alkyl radicals in the reaction with NO2, while the resonance stabilisation of the alkenyl radical lowers its reactivity with respect to NO2 only slightly. Two reactions relevant to atmospheric chemistry, CH2Br + O2 and CH2I + O2, were also investigated. It was noticed that while CH2Br + O2 reaction shows pronounced pressure dependence, characteristic of peroxy radical formation, no such dependence was observed for the CH2I + O2 reaction. Observed primary products of the CH2I + O2 reaction were the I-atom and the IO radical. Kinetics of CH3 + HCl, CD3 + HCl, CH3 + DCl, and CD3 + DCl reactions were also studied. While all these reactions possess positive activation energies, in contrast to the other systems investigated in this thesis, the CH3 + HCl and CD3 + HCl reactions show a non-linear temperature dependency on the Arrhenius plot. The reactivity of substituted methyl radicals toward NO2 was observed to increase with decreasing electron affinity of the radical. The same trend was observed for the reactions of substituted methyl radicals with Cl2. It is proposed that interactions of frontier orbitals are responsible to these observations and Frontier Orbital Theory could be used to explain the observed reactivity trends of these highly exothermic reactions having reactant-like transition states.

Fen ecosystem carbon gas dynamics in changing hydrological conditions

Northern peatlands are thought to store one third of all soil carbon (C). Besides the C sink function, peatlands are one of the largest natural sources of methane (CH4) to the atmosphere. Climate change may affect the C gas dynamics as well as the labile C pool. Because the peatland C sequestration and CH4 emissions are governed by high water levels, changes in hydrology are seen as the driving factor in peatland ecosystem change. This study aimed to quantify the carbon dioxide (CO2) and CH4 dynamics of a fen ecosystem at different spatial scales: plant community components scale, plant community scale and ecosystem scale, under hydrologically normal and water level drawdown conditions. C gas exchange was measured in two fens in southern Finland applying static chamber and eddy covariance techniques. During hydrologically normal conditions, the ecosystem was a CO2 sink and CH4 source to the atmosphere. Sphagnum mosses and sedges were the most important contributors to the community photosynthesis. The presence of sedges had a major positive impact on CH4 emissions while dwarf shrubs had a slightly attenuating impact. C fluxes varied considerably between the plant communities. Therefore, their proportions determined the ecosystem scale fluxes. An experimental water level drawdown markedly reduced the photosynthesis and respiration of sedges and Sphagnum mosses and benefited shrubs. Consequently, changes were smaller at the ecosystem scale than at the plant group scale. The decrease in photosynthesis and the increase in respiration, mostly peat respiration, made the fen a smaller CO2 sink. CH4 fluxes were significantly lowered, close to zero. The impact of natural droughts was similar to, although more modest than, the impact of the experimental water level drawdown. The results are applicable to the short term impacts of the water level drawdown and to climatic conditions in which droughts become more frequent.

Phosphorus retention in forest soils and the functioning of buffer zones used in forestry

Phosphorus (P) retention properties of soils typical for boreal forest, i.e. podzolic soil and peat soils, vary significantly, but the range of this variation has not been sufficiently documented. To assess the usefulness of buffer zones used in forestry in removing P from the discharge by chemical sorption in soil, and to estimate the risk of P leaching after forestry operations, more data is needed on soil P retention properties. P retention properties of soils were studied at clear-cut areas, unharvested buffer zones adjoining the clear-cut and at peatland buffer zone areas. Desorption-sorption isotherms were determined for the humus layer, the mineral soil horizons E, B and C of the Podzol profile and for the surface layer peat (0-15 cm) and the subsurface layer peat (15-30 cm). The efficiency of buffer zones in retaining P was studied at six peatland buffer zone areas by adding P-containing solute in the inflow. A tracer study was conducted at one of the buffer zone areas to determine the allocation of the added P in soil and vegetation. Measured sorption or desorption rather than parameter values of fitted sorption equations described P desorption and sorption behaviour in soil. The highest P retention efficiency was in the B horizon and consequently, if contact occurred or was established between the soluble P in the water and the soil B horizon, the risk of P leaching was low. Humus layer was completely incapable of retaining P after clear-cutting. In the buffer zones, the decrease in P retention properties in the humus layer and the low amount of P sorbed by it indicated that the importance of the layer in the functioning of buffer zones is low. The peatland buffer zone areas were efficient in retaining soluble P from inflow. P sorption properties of the peat soil at the buffer zone areas varied largely but the contribution of P sorption in the peat was particularly important during high flow in spring, when the vegetation was not fully developed. Factors contributing to efficient P retention were large buffer size and low hydrological load whereas high hydrological load combined with the formation of preferential flow paths, especially during early spring or late autumn was disadvantageous. However, small buffer zone areas, too, may be efficient in reducing P load.

UV-induced NOy emissions in gas-exchange chambers enclosing Scots pine shoots: an analysis on their origin and significance

It is essential to have a thorough understanding of the sources and sinks of oxidized nitrogen (NOy) in the atmosphere, since it has a strong influence on the tropospheric chemistry and the eutrophication of ecosystems. One unknown component in the balance of gaseous oxidized nitrogen is vegetation. Plants absorb nitrogenous species from the air via the stomata, but it is not clear whether plants can also emit them at low ambient concentrations. The possible emissions are small and difficult to measure. The aim of this thesis was to analyse an observation made in southern Finland at the SMEAR II station: solar ultraviolet radiation (UV) induced NOy emissions in chambers measuring the gas exchange of Scots pine (Pinus sylvestris L.) shoots. Both measuring and modelling approaches were used in the study. The measurements were performed under noncontrolled field conditions at low ambient NOy concentrations. The chamber blank i.e. artefact NOy emissions from the chamber walls, was dependent on the UV irradiance and increased with time after renewing the Teflon film on chamber surfaces. The contribution of each pine shoot to the total NOy emissions in the chambers was determined by testing whether the emissions decrease when the shoots are removed from their chambers. Emissions did decrease, but only when the chamber interior was exposed to UV radiation. It was concluded that also the pine shoots emit NOy. The possible effects of transpiration on the chamber blank are discussed in the summary part of the thesis, based on previously unpublished data. The possible processes underlying the UV-induced NOy emissions were reviewed. Surface reactions were more likely than metabolic processes. Photolysis of nitrate deposited on the needles may have generated the NOy emissions; the measurements supported this hypothesis. In that case, the emissions apparently would consist mainly of nitrogen dioxide (NO2), nitric oxide (NO) and nitrous acid (HONO). Within studies on NOy exchange of plants, the gases most frequently studied are NO2 and NO (=NOx). In the present work, the implications of the emissions for the NOx exchange of pine were analysed with a model including both NOy emissions and NOy absorption. The model suggested that if the emissions exist, pines can act as an NOx source rather than a sink, even under relatively high ambient concentrations.

Use of biomass fuels in the brick-making industries of Sudan: Implications for deforestation and greenhouse gas emission

The study focuses on the potential roles of the brick making industries in Sudan in deforestation and greenhouse gas emission due to the consumption of biofuels. The results were based on the observation of 25 brick making industries from three administrative regions in Sudan namely, Khartoum, Kassala and Gezira. The methodological approach followed the procedures outlined by the Intergovernmental Panel on Climate Change (IPCC). For predicting a serious deforestation scenario, it was also assumed that all of wood use for this particular purpose is from unsustainable sources. The study revealed that the total annual quantity of fuelwood consumed by the surveyed brick making industries (25) was 2,381 t dm. Accordingly, the observed total potential deforested wood was 10,624 m3, in which the total deforested round wood was 3,664 m3 and deforested branches was 6,961 m3. The study observed that a total of 2,990 t biomass fuels (fuelwood and dung cake) consumed annually by the surveyed brick making industries for brick burning. Consequently, estimated total annual emissions of greenhouse gases were 4,832 t CO2, 21 t CH4, 184 t CO, 0.15 t N20, 5 t NOX and 3.5 t NO while the total carbon released in the atmosphere was 1,318 t. Altogether, the total annual greenhouse gases emissions from biomass fuels burning was 5,046 t; of which 4,104 t from fuelwood and 943 t from dung cake burning. According to the results, due to the consumption of fuelwood in the brick making industries (3,450 units) of Sudan, the amount of wood lost from the total growing stock of wood in forests and trees in Sudan annually would be 1,466,000 m3 encompassing 505,000 m3 round wood and 961,000 m3 branches annually. By considering all categories of biofuels (fuelwood and dung cake), it was estimated that, the total emissions from all the brick making industries of Sudan would be 663,000 t CO2, 2,900 t CH4, 25,300 t CO, 20 t N2O, 720 t NOX and 470 t NO per annum, while the total carbon released in the atmosphere would be 181,000 t annually.

Plant species diversity of buffer zones in agricultural landscapes: in search of determinants from the local to regional scale

Buffer zones are vegetated strip-edges of agricultural fields along watercourses. As linear habitats in agricultural ecosystems, buffer strips dominate and play a leading ecological role in many areas. This thesis focuses on the plant species diversity of the buffer zones in a Finnish agricultural landscape. The main objective of the present study is to identify the determinants of floral species diversity in arable buffer zones from local to regional levels. This study was conducted in a watershed area of a farmland landscape of southern Finland. The study area, Lepsämänjoki, is situated in the Nurmijärvi commune 30 km to the north of Helsinki, Finland. The biotope mosaics were mapped in GIS. A total of 59 buffer zones were surveyed, of which 29 buffer strips surveyed were also sampled by plot. Firstly, two diversity components (species richness and evenness) were investigated to determine whether the relationship between the two is equal and predictable. I found no correlation between species richness and evenness. The relationship between richness and evenness is unpredictable in a small-scale human-shaped ecosystem. Ordination and correlation analyses show that richness and evenness may result from different ecological processes, and thus should be considered separately. Species richness correlated negatively with phosphorus content, and species evenness correlated negatively with the ratio of organic carbon to total nitrogen in soil. The lack of a consistent pattern in the relationship between these two components may be due to site-specific variation in resource utilization by plant species. Within-habitat configuration (width, length, and area) were investigated to determine which is more effective for predicting species richness. More species per unit area increment could be obtained from widening the buffer strip than from lengthening it. The width of the strips is an effective determinant of plant species richness. The increase in species diversity with an increase in the width of buffer strips may be due to cross-sectional habitat gradients within the linear patches. This result can serve as a reference for policy makers, and has application value in agricultural management. In the framework of metacommunity theory, I found that both mass effect(connectivity) and species sorting (resource heterogeneity) were likely to explain species composition and diversity on a local and regional scale. The local and regional processes were interactively dominated by the degree to which dispersal perturbs local communities. In the lowly and intermediately connected regions, species sorting was of primary importance to explain species diversity, while the mass effect surpassed species sorting in the highly connected region. Increasing connectivity in communities containing high habitat heterogeneity can lead to the homogenization of local communities, and consequently, to lower regional diversity, while local species richness was unrelated to the habitat connectivity. Of all species found, Anthriscus sylvestris, Phalaris arundinacea, and Phleum pretense significantly responded to connectivity, and showed high abundance in the highly connected region. We suggest that these species may play a role in switching the force from local resources to regional connectivity shaping the community structure. On the landscape context level, the different responses of local species richness and evenness to landscape context were investigated. Seven landscape structural parameters served to indicate landscape context on five scales. On all scales but the smallest scales, the Shannon-Wiener diversity of land covers (H') correlated positively with the local richness. The factor (H') showed the highest correlation coefficients in species richness on the second largest scale. The edge density of arable field was the only predictor that correlated with species evenness on all scales, which showed the highest predictive power on the second smallest scale. The different predictive power of the factors on different scales showed a scaledependent relationship between the landscape context and local plant species diversity, and indicated that different ecological processes determine species richness and evenness. The local richness of species depends on a regional process on large scales, which may relate to the regional species pool, while species evenness depends on a fine- or coarse-grained farming system, which may relate to the patch quality of the habitats of field edges near the buffer strips. My results suggested some guidelines of species diversity conservation in the agricultural ecosystem. To maintain a high level of species diversity in the strips, a high level of phosphorus in strip soil should be avoided. Widening the strips is the most effective mean to improve species richness. Habitat connectivity is not always favorable to species diversity because increasing connectivity in communities containing high habitat heterogeneity can lead to the homogenization of local communities (beta diversity) and, consequently, to lower regional diversity. Overall, a synthesis of local and regional factors emerged as the model that best explain variations in plant species diversity. The studies also suggest that the effects of determinants on species diversity have a complex relationship with scale.

Microclimate and gas emissions in dairy buildings : Instrumentation, theory and measurements

The aim of this thesis was to develop measurement techniques and systems for measuring air quality and to provide information about air quality conditions and the amount of gaseous emissions from semi-insulated and uninsulated dairy buildings in Finland and Estonia. Specialization and intensification in livestock farming, such as in dairy production, is usually accompanied by an increase in concentrated environmental emissions. In addition to high moisture, the presence of dust and corrosive gases, and widely varying gas concentrations in dairy buildings, Finland and Estonia experience winter temperatures reaching below -40 ºC and summer temperatures above +30 ºC. The adaptation of new technologies for long-term air quality monitoring and measurement remains relatively uncommon in dairy buildings because the construction and maintenance of accurate monitoring systems for long-term use are too expensive for the average dairy farmer to afford. Though the documentation of accurate air quality measurement systems intended mainly for research purposes have been made in the past, standardised methods and the documentation of affordable systems and simple methods for performing air quality and emissions measurements in dairy buildings are unavailable. In this study, we built three measurement systems: 1) a Stationary system with integrated affordable sensors for on-site measurements, 2) a Wireless system with affordable sensors for off-site measurements, and 3) a Mobile system consisting of expensive and accurate sensors for measuring air quality. In addition to assessing existing methods, we developed simplified methods for measuring ventilation and emission rates in dairy buildings. The three measurement systems were successfully used to measure air quality in uninsulated, semi-insulated, and fully-insulated dairy buildings between the years 2005 and 2007. When carefully calibrated, the affordable sensors in the systems gave reasonably accurate readings. The spatial air quality survey showed high variation in microclimate conditions in the dairy buildings measured. The average indoor air concentration for carbon dioxide was 950 ppm, for ammonia 5 ppm, for methane 48 ppm, for relative humidity 70%, and for inside air velocity 0.2 m/s. The average winter and summer indoor temperatures during the measurement period were -7º C and +24 ºC for the uninsulated, +3 ºC and +20 ºC for the semi-insulated and +10 ºC and +25 ºC for the fully-insulated dairy buildings. The measurement results showed that the uninsulated dairy buildings had lower indoor gas concentrations and emissions compared to fully insulated buildings. Although occasionally exceeded, the ventilation rates and average indoor air quality in the dairy buildings were largely within recommended limits. We assessed the traditional heat balance, moisture balance, carbon dioxide balance and direct airflow methods for estimating ventilation rates. The direct velocity measurement for the estimation of ventilation rate proved to be impractical for naturally ventilated buildings. Two methods were developed for estimating ventilation rates. The first method is applicable in buildings in which the ventilation can be stopped or completely closed. The second method is useful in naturally ventilated buildings with large openings and high ventilation rates where spatial gas concentrations are heterogeneously distributed. The two traditional methods (carbon dioxide and methane balances), and two newly developed methods (theoretical modelling using Fick s law and boundary layer theory, and the recirculation flux-chamber technique) were used to estimate ammonia emissions from the dairy buildings. Using the traditional carbon dioxide balance method, ammonia emissions per cow from the dairy buildings ranged from 7 g day-1 to 35 g day-1, and methane emissions per cow ranged from 96 g day-1 to 348 g day-1. The developed methods proved to be as equally accurate as the traditional methods. Variation between the mean emissions estimated with the traditional and the developed methods was less than 20%. The developed modelling procedure provided sound framework for examining the impact of production systems on ammonia emissions in dairy buildings.

Novel Organo-Noble-Gas Hydrides

Noble gases are mostly known as inert monatomic gases due to their limited reactivity with other elements. However, the first predictions of noble-gas compounds were suggested by Kossel in 1916, by von Antropoff in 1924, and by Pauling in 1930. It took many decades until the first noble-gas compound, XePtF6, was synthesized by Neil Bartlett in 1962. This was followed by gradual development of the field and many noble-gas compounds have been prepared. In 1995, a family of noble-gas hydride molecules was discovered at the University of Helsinki. These molecules have the general formula of HNgY, where H is a hydrogen atom, Ng is a noble-gas atom (Ar, Kr, or Xe), and Y is an electronegative fragment. The first molecular species made include HXeI, HXeBr, HXeCl, HKrCl and HXeH. Nowadays the total number of prepared HNgY molecules is 23 including both inorganic and organic compounds. The first and only neutral ground-state argon compound, HArF, was synthetized in 2000. Helium and neon are the only elements in the periodic table that do not form neutral, ground-state molecules. In this Thesis, experimental preparation of eight novel xenon- and krypton-containing organo-noble-gas hydrides made from acetylene (HCCH), diacetylene (HCCCCH) and cyanoacetylene (HCCCN) are presented. These novel species include the first organic krypton compound, HKrCCH, as well as the first noble-gas hydride molecule containing two Xe atoms, HXeCCXeH. Other new compounds are HXeCCH, HXeCC, HXeC4H, HKrC4H, HXeC3N, and HKrC3N. These molecules are prepared in noble-gas matrices (krypton or xenon) using ultraviolet photolysis of the precursor molecule and thermal mobilization of the photogenerated H atoms. The molecules were identified using infrared spectroscopy and ab initio calculations. The formation mechanisms of the organo-noble-gas molecules are studied and discussed in this context. The focus is to evidence experimentally the neutral formation mechanisms of HNgY molecules upon global mobility of H atoms. The formation of HXeCCXeH from another noble-gas compound (HXeCC) is demonstrated and discussed. Interactions with the surrounding matrix and molecular complexes of the HXeCCH molecule are studied. HXeCCH was prepared in argon and krypton solids in addition to a Xe matrix. The weak HXeCCH∙∙∙CO2 complex is prepared and identified. Preparation of the HXeCCH∙∙∙CO2 complex demonstrates an advanced approach to studies of HNgY complexes where the precursor complex (HCCH∙∙∙CO2) is obtained using photolysis of a larger molecule (propiolic acid).

Computational studies on new chemical species in the gas-phase and the solid-state.

There is intense activity in the area of theoretical chemistry of gold. It is now possible to predict new molecular species, and more recently, solids by combining relativistic methodology with isoelectronic thinking. In this thesis we predict a series of solid sheet-type crystals for Group-11 cyanides, MCN (M=Cu, Ag, Au), and Group-2 and 12 carbides MC2 (M=Be-Ba, Zn-Hg). The idea of sheets is then extended to nanostrips which can be bent to nanorings. The bending energies and deformation frequencies can be systematized by treating these molecules as an elastic bodies. In these species Au atoms act as an 'intermolecular glue'. Further suggested molecular species are the new uncongested aurocarbons, and the neutral Au_nHg_m clusters. Many of the suggested species are expected to be stabilized by aurophilic interactions. We also estimate the MP2 basis-set limit of the aurophilicity for the model compounds [ClAuPH_3]_2 and [P(AuPH_3)_4]^+. Beside investigating the size of the basis-set applied, our research confirms that the 19-VE TZVP+2f level, used a decade ago, already produced 74 % of the present aurophilic attraction energy for the [ClAuPH_3]_2 dimer. Likewise we verify the preferred C4v structure for the [P(AuPH_3)_4]^+ cation at the MP2 level. We also perform the first calculation on model aurophilic systems using the SCS-MP2 method and compare the results to high-accuracy CCSD(T) ones. The recently obtained high-resolution microwave spectra on MCN molecules (M=Cu, Ag, Au) provide an excellent testing ground for quantum chemistry. MP2 or CCSD(T) calculations, correlating all 19 valence electrons of Au and including BSSE and SO corrections, are able to give bond lengths to 0.6 pm, or better. Our calculated vibrational frequencies are expected to be better than the currently available experimental estimates. Qualitative evidence for multiple Au-C bonding in triatomic AuCN is also found.

Intermolecular Interactions of Noble-Gas-Containing Species

The importance of intermolecular interactions to chemistry, physics, and biology is difficult to overestimate. Without intermolecular forces, condensed phase matter could not form. The simplest way to categorize different types of intermolecular interactions is to describe them using van der Waals and hydrogen bonded (H-bonded) interactions. In the H-bond, the intermolecular interaction appears between a positively charged hydrogen atom and electronegative fragments and it originates from strong electrostatic interactions. H-bonding is important when considering the properties of condensed phase water and in many biological systems including the structure of DNA and proteins. Vibrational spectroscopy is a useful tool for studying complexes and the solvation of molecules. Vibrational frequency shift has been used to characterize complex formation. In an H-bonded system A∙∙∙H-X (A and X are acceptor and donor species, respectively), the vibrational frequency of the H-X stretching vibration usually decreases from its value in free H-X (red-shift). This frequency shift has been used as evidence for H-bond formation and the magnitude of the shift has been used as an indicator of the H-bonding strength. In contrast to this normal behavior are the blue-shifting H-bonds, in which the H-X vibrational frequency increases upon complex formation. In the last decade, there has been active discussion regarding these blue-shifting H-bonds. Noble-gases have been considered inert due to their limited reactivity with other elements. In the early 1930 s, Pauling predicted the stable noble-gas compounds XeF6 and KrF6. It was not until three decades later Neil Bartlett synthesized the first noble-gas compound, XePtF6, in 1962. A renaissance of noble-gas chemistry began in 1995 with the discovery of noble-gas hydride molecules at the University of Helsinki. The first hydrides were HXeCl, HXeBr, HXeI, HKrCl, and HXeH. These molecules have the general formula of HNgY, where H is a hydrogen atom, Ng is a noble-gas atom (Ar, Kr, or Xe), and Y is an electronegative fragment. At present, this class of molecules comprises 23 members including both inorganic and organic compounds. The first and only argon-containing neutral chemical compound HArF was synthesized in 2000 and its properties have since been investigated in a number of studies. A helium-containing chemical compound, HHeF, was predicted computationally, but its lifetime has been predicted to be severely limited by hydrogen tunneling. Helium and neon are the only elements in the periodic table that do not form neutral, ground state molecules. A noble-gas matrix is a useful medium in which to study unstable and reactive species including ions. A solvated proton forms a centrosymmetric NgHNg+ (Ng = Ar, Kr, and Xe) structure in a noble-gas matrix and this is probably the simplest example of a solvated proton. Interestingly, the hypothetical NeHNe+ cation is isoelectronic with the water-solvated proton H5O2+ (Zundel-ion). In addition to the NgHNg+ cations, the isoelectronic YHY- (Y = halogen atom or pseudohalogen fragment) anions have been studied with the matrix-isolation technique. These species have been known to exist in alkali metal salts (YHY)-M+ (M = alkali metal e.g. K or Na) for more than 80 years. Hydrated HF forms the FHF- structure in aqueous solutions, and these ions participate in several important chemical processes. In this thesis, studies of the intermolecular interactions of HNgY molecules and centrosymmetric ions with various species are presented. The HNgY complexes show unusual spectral features, e.g. large blue-shifts of the H-Ng stretching vibration upon complexation. It is suggested that the blue-shift is a normal effect for these molecules, and that originates from the enhanced (HNg)+Y- ion-pair character upon complexation. It is also found that the HNgY molecules are energetically stabilized in the complexed form, and this effect is computationally demonstrated for the HHeF molecule. The NgHNg+ and YHY- ions also show blue-shifts in their asymmetric stretching vibration upon complexation with nitrogen. Additionally, the matrix site structure and hindered rotation (libration) of the HNgY molecules were studied. The librational motion is a much-discussed solid state phenomenon, and the HNgY molecules embedded in noble-gas matrices are good model systems to study this effect. The formation mechanisms of the HNgY molecules and the decay mechanism of NgHNg+ cations are discussed. A new electron tunneling model for the decay of NgHNg+ absorptions in noble-gas matrices is proposed. Studies of the NgHNg+∙∙∙N2 complexes support this electron tunneling mechanism.

Comprehensive Two-Dimensional Gas Chromatography: Instrumental and Methodological Development

Comprehensive two-dimensional gas chromatography (GC×GC) offers enhanced separation efficiency, reliability in qualitative and quantitative analysis, capability to detect low quantities, and information on the whole sample and its components. These features are essential in the analysis of complex samples, in which the number of compounds may be large or the analytes of interest are present at trace level. This study involved the development of instrumentation, data analysis programs and methodologies for GC×GC and their application in studies on qualitative and quantitative aspects of GC×GC analysis. Environmental samples were used as model samples. Instrumental development comprised the construction of three versions of a semi-rotating cryogenic modulator in which modulation was based on two-step cryogenic trapping with continuously flowing carbon dioxide as coolant. Two-step trapping was achieved by rotating the nozzle spraying the carbon dioxide with a motor. The fastest rotation and highest modulation frequency were achieved with a permanent magnetic motor, and modulation was most accurate when the motor was controlled with a microcontroller containing a quartz crystal. Heated wire resistors were unnecessary for the desorption step when liquid carbon dioxide was used as coolant. With use of the modulators developed in this study, the narrowest peaks were 75 ms at base. Three data analysis programs were developed allowing basic, comparison and identification operations. Basic operations enabled the visualisation of two-dimensional plots and the determination of retention times, peak heights and volumes. The overlaying feature in the comparison program allowed easy comparison of 2D plots. An automated identification procedure based on mass spectra and retention parameters allowed the qualitative analysis of data obtained by GC×GC and time-of-flight mass spectrometry. In the methodological development, sample preparation (extraction and clean-up) and GC×GC methods were developed for the analysis of atmospheric aerosol and sediment samples. Dynamic sonication assisted extraction was well suited for atmospheric aerosols collected on a filter. A clean-up procedure utilising normal phase liquid chromatography with ultra violet detection worked well in the removal of aliphatic hydrocarbons from a sediment extract. GC×GC with flame ionisation detection or quadrupole mass spectrometry provided good reliability in the qualitative analysis of target analytes. However, GC×GC with time-of-flight mass spectrometry was needed in the analysis of unknowns. The automated identification procedure that was developed was efficient in the analysis of large data files, but manual search and analyst knowledge are invaluable as well. Quantitative analysis was examined in terms of calibration procedures and the effect of matrix compounds on GC×GC separation. In addition to calibration in GC×GC with summed peak areas or peak volumes, simplified area calibration based on normal GC signal can be used to quantify compounds in samples analysed by GC×GC so long as certain qualitative and quantitative prerequisites are met. In a study of the effect of matrix compounds on GC×GC separation, it was shown that quality of the separation of PAHs is not significantly disturbed by the amount of matrix and quantitativeness suffers only slightly in the presence of matrix and when the amount of target compounds is low. The benefits of GC×GC in the analysis of complex samples easily overcome some minor drawbacks of the technique. The developed instrumentation and methodologies performed well for environmental samples, but they could also be applied for other complex samples.