En nyligen genomförd studie visade att reaktioner mellan vissa radikaler och omättade alkener är snabbare vid rumstemperatur än vad man tidigare har trott. Dessa reaktioner är viktiga för atmosfäriska oxidationscykler och följaktligen var syftet med detta masterprojekt att beräkna hastighetskonstanterna för dessa reaktioner mellan metyljodid och 1-jodidpentan med tetrametyletylen, isopren och limonen vid rumstemperatur genom att kvantifiera respektive epoxid; tetrametyloxiran, isoprenmonoxid och limonen 1,2 epoxid, som producerades. För att uppfylla syftet utfördes experiment på referensföreningarna tetrametyletylen, isoprenmonoxid, limonen och limonen 1,2 epoxid och på prover tagna från en kolonnflödesreaktor. Dessa experiment genomfördes för att kunna utveckla en lämplig provtagningsmetod och analysmetod med termisk desorptionsenhet samt gaskromatografi och masspektrometri (TD-GCMS). Slutsatsen som drogs var att Tenax® TA adsorbentrör är kompatibla med dessa ämnen och att den föreslagna TD-GCMS metoden är effektiv. Dessutom drogs slutsatsen att tetrametyloxiran inte hittades i reaktorproverna (varken i alkenproverna eller reaktorproverna), vilket resulterade i att hastighetskonstanten inte kunde beräknas. Dessutom var kvantifiering av reaktorproverna inte möjlig. / A recent study has shown that the reaction between some radicals and unsaturated alkenes is faster at room temperature than previously believed. These reactions are important for atmospheric oxidation cycles and therefore the purpose of this master project was to measure the rate coefficients for the reactions between methyl iodine and 1-iodopentane with tetramethylethylene, isoprene and limonene at room temperature by quantifying the respective epoxide; tetramethyloxirane, isoprene monoxide and limonene 1,2 epoxide, produced. In order to fulfill the purpose, experiments were conducted using the reference compounds of tetramethylethylene, isoprene monoxide, limonene and limonene 1,2 epoxide and on column flow reactor samples produced in the above mentioned reactions. These were performed in order to be able to develop an appropriate sampling method, and analysis method using thermal desorption unit gas chromatography and mass spectrometry (TD-GCMS). It was concluded that Tenax® TA adsorbent tubes are compatible with these substances and that the TD-GCMS method suggested is appropriate. It was also concluded that no tetramethyloxirane was found in the reactor samples (neither in alkene samples nor after the reactions), resulting in that it was not possible to calculate the rate coefficient. Moreover, the quantification of the reactor samples was not possible.

Microelectromechanical systems (MEMS) technology allows the realization of mechanical parts, sensors, actuators and electronics on silicon substrate. An attractive utilization of MEMS is to develop micro instruments for chemical analysis. An example is gas chromatography (GC) which is widely used in food, environmental, pharmaceutical, petroleum/refining, forensic/security, and flavors and fragrances industries. A MEMS-based micro GC (µGC) provides capabilities for quantitative analysis of complex chemical mixtures in the field with very short analysis time and small amounts of consumables. The aim of this research effort is to enhance the sensitivity and selectivity of µGC instruments by implementing chemical amplification method known as preconcentration. A micro preconcentrator (µPC) extracts the target analytes from the sample matrix, concentrates them, and injects them into the separation column for analysis. This work resulted in the development of silicon-glass bonded chips consisting of 7 mm x 7 mm x 0.38 mm multiport cavity with thousands of embedded 3D microstructures (to achieve high surface-to-volume ratio) coated with polymeric thin film adsorbents. Deep reactive ion etching (DRIE) was the enabling technology for the realization of µPCs. Several coating methods, such as inkjet printing of polymers and polymer precipitation from solution have been utilized to coat complex geometrical structures. One major outcome was the development of cobweb adsorbent structure. Moreover, the porous polymeric adsorbent Tenax TA in the film form was characterized, for the first time, for μPC application and shown to have similar properties to that of the granular form. Several μPC designs were experimentally evaluated for their performance in concentrating volatile organic compounds, including cancer biomarkers, Propofol (anesthetic agent), environmental pollutants, and chemical warfare simulants. The possibility of utilizing the μPCs in practical applications such breath analysis was also demonstrated. / Ph. D.

Off-gassing of hazardous compounds is, together with self-heating and dust explosions, the main safety hazards within large-scale biomass storage and handling. Formation of CO, CO2, and VOCs with concurrent O2 depletion can occur to hazardous levels in enclosed stored forest products. Several incidents of CO poisoning and suffocation of oxygen depletion have resulted in fatalities and injuries during cargo vessel discharge of forest products and in conjunction with wood pellet storage rooms and silos. Technologies for torrefaction and steam explosion for thermal treatment of biomass are under development and approaching commercialization, but their off-gassing behavior is essentially unknown. The overall objective of this thesis was to provide answers to one main question: “What is the off-gassing behaviour of thermally treated lignocellulosic biomass during storage?”. This was achieved by experimental studies and detailed analysis of off-gassing compounds sampled under realistic conditions, with special emphasis on the VOCs. Presented results show that off-gassing behavior is influenced by numerous factors, in the following ways. CO, CO2 and CH4 off-gassing levels from torrefied and stream-exploded biomass and pellets, and accompanying O2 depletion, are comparable to or lower than corresponding from untreated biomass. The treatments also cause major compositional shifts in VOCs; emissions of terpenes and native aldehydes decline, but levels of volatile cell wall degradation products (notably furans and aromatics) increase. The severity of the thermal treatment is also important; increases in torrefaction severity increase CO off-gassing from torrefied pine to levels comparable to emissions from conventional pellets, and increase O2 depletion for both torrefied chips and pellets. Both treatment temperature and duration also influence degradation rates and VOC composition. The product cooling technique is influential too; water spraying in addition to heat exchange increased CO2 and VOCs off-gassing from torrefied pine chips, as well as O2 depletion. Moreover, the composition of emitted gases co-varied with pellets’ moisture content; pellets of more severely treated material retained less moisture, regardless of their pre-conditioning moisture content. However, no co-variance was found between off-gassing and pelletization settings, the resulting pellet quality, or storage time of torrefied chips before pelletization. Pelletization of steam-exploded bark increased subsequent VOC off-gassing, and induced compositional shifts relative to emissions from unpelletized steam-exploded material. In addition, CO, CO2 and CH4 off-gassing, and O2 depletion, were positively correlated with the storage temperature of torrefied softwood. Similarly, CO and CH4 emissions from steam-exploded softwood increased with increases in storage temperature, and VOC off-gassing from both torrefied and steam-exploded softwood was more affected by storage temperature than by treatment severity. Levels of CO, CO2 and CH4 increased, while levels of O2 and most VOCs decreased, during storage of both torrefied and steam-exploded softwood.CO, CO2 and O2 levels were more affected by storage time than by treatment severity. Levels of VOCs were not significantly decreased or altered by nitrogen purging of storage spaces of steam-exploded or torrefied softwood, or controlled headspace gas exchange (intermittent ventilation) during storage of steam-exploded bark. In conclusion, rates of off-gassing of CO and CO2 from thermally treated biomass, and associated O2 depletion, are comparable to or lower than corresponding rates for untreated biomass. Thermal treatment induces shifts in both concentrations and profiles of VOCs. It is believed that the knowledge and insights gained provide refined foundations for future research and safe implementation of thermally treated fuels as energy carriers in renewable energy process chains.

In this thesis the oxidation of monoterpenes by O3 and NO2 and factors that influenced the oxidation were studied. In the environment both ozone (O3) and nitrogen dioxide (NO2) are present as oxidising gases, which causes sampling artefacts when using Tenax TA as an adsorbent to sample organic compounds in the air. A scrubber was developed to remove O3 and NO2 prior to the sampling tube, and artefacts during sampling were minimised when using the scrubber. The main organic compounds sampled in this thesis were two monoterpenes, alfa-pinene and delta-3-carene, due to their presence in both indoor and outdoor air. The recovery of the monoterpenes through the scrubber varied between 75-97% at relative humidities of 15-75%. The reactions of alfa-pinene and delta-3-carene with O 3, NO2 and nitric oxide (NO) at different relative humidities (RHs) and reaction times were studied in a dark reaction chamber. The experiments were planned and performed according to an experimental design were the factors influencing the reaction (O3, NO2, NO, RH and reaction times) were varied between high and low levels. In the experiments up to 13% of the monoterpenes reacted when O3, NO2, and reaction time were at high levels, and NO, and RH were at low levels. In the evaluation eight and seven factors (including both single and interaction factors) were found to influence the amount of alfa-pinene and delta-3-carene reacted, respectively. The three most influencing factors for both of the monoterpenes were the O 3 level, the reaction time, and the RH. Increased O3 level and reaction time increased the amount of monoterpene reacted, and increased RH decreased the amount reacted. A theoretical model of the reactions occurring in the reaction chamber was created. The amount of monoterpene reacted at different initial settings of O3, NO2, and NO were calculated, as well as the influence of different reaction pathways, and the concentrations of O3 and NO2, and NO at specific reaction times. The results of the theoretical model were that the reactivity of the gas mixture towards alfa-pinene and delta-3-carene was underestimated. But, the calculated concentrations of O3, NO2, and NO in the theoretical model were found to correspond to a high degree with experimental results performed under similar conditions. The possible associations between organic compounds in indoor air, building variables and the presence of sick building syndrome were studied using principal component analysis. The most complex model was able to separate 71% of the “sick” buildings from the “healthy” buildings. The most important variables that separated the “sick” buildings from the “healthy” buildings were a more frequent occurrence or a higher concentration of compounds with shorter retention times in the “sick” buildings. The outcome of this thesis could be summarised as follows; - - - -

<p>In this thesis the oxidation of monoterpenes by O3 and NO2 and factors that influenced the oxidation were studied. In the environment both ozone (O3) and nitrogen dioxide (NO2) are present as oxidising gases, which causes sampling artefacts when using Tenax TA as an adsorbent to sample organic compounds in the air. A scrubber was developed to remove O3 and NO2 prior to the sampling tube, and artefacts during sampling were minimised when using the scrubber. The main organic compounds sampled in this thesis were two monoterpenes, alfa-pinene and delta-3-carene, due to their presence in both indoor and outdoor air. The recovery of the monoterpenes through the scrubber varied between 75-97% at relative humidities of 15-75%.</p><p>The reactions of alfa-pinene and delta-3-carene with O 3, NO2 and nitric oxide (NO) at different relative humidities (RHs) and reaction times were studied in a dark reaction chamber. The experiments were planned and performed according to an experimental design were the factors influencing the reaction (O3, NO2, NO, RH and reaction times) were varied between high and low levels. In the experiments up to 13% of the monoterpenes reacted when O3, NO2, and reaction time were at high levels, and NO, and RH were at low levels. In the evaluation eight and seven factors (including both single and interaction factors) were found to influence the amount of alfa-pinene and delta-3-carene reacted, respectively. The three most influencing factors for both of the monoterpenes were the O 3 level, the reaction time, and the RH. Increased O3 level and reaction time increased the amount of monoterpene reacted, and increased RH decreased the amount reacted.</p><p>A theoretical model of the reactions occurring in the reaction chamber was created. The amount of monoterpene reacted at different initial settings of O3, NO2, and NO were calculated, as well as the influence of different reaction pathways, and the concentrations of O3 and NO2, and NO at specific reaction times. The results of the theoretical model were that the reactivity of the gas mixture towards alfa-pinene and delta-3-carene was underestimated. But, the calculated concentrations of O3, NO2, and NO in the theoretical model were found to correspond to a high degree with experimental results performed under similar conditions. The possible associations between organic compounds in indoor air, building variables and the presence of sick building syndrome were studied using principal component analysis. The most complex model was able to separate 71% of the “sick” buildings from the “healthy” buildings. The most important variables that separated the “sick” buildings from the “healthy” buildings were a more frequent occurrence or a higher concentration of compounds with shorter retention times in the “sick” buildings.</p><p>The outcome of this thesis could be summarised as follows;</p><p>-</p><p>-</p><p>-</p><p>-</p>