Calibration methods for quantitative on-site sampling using solid phase microextraction (SPME) were developed based on diffusion mass transfer theory. This was investigated using adsorptive polydimethylsiloxane/divinylbenzene (PDMS/DVB) and Carboxen/polydimethylsiloxane (CAR/PDMS) SPME fiber coatings with volatile aromatic hydrocarbons (BTEX: benzene, toluene, ethylbenzene, and o-xylene) as test analytes. Parameters that affected the extraction process (sampling time, analyte concentration, water velocity, and temperature) were investigated. Very short sampling times (10-300 s) and sorbents with a strong affinity and large capacity were used to ensure a 'zero sink' effect calibrate process. It was found that mass uptake of analyte changed linearly with concentration. Increase of water velocity increased mass uptake, though the increase is not linear. Temperature did not affect mass uptake significantly under typical field sampling conditions. To further describe rapid SPME analysis of aqueous samples, a new model translated from heat transfer to a circular cylinder in cross flow was used. An empirical correlation to this model was used to predict the mass transfer coefficient. Findings indicated that the predicted mass uptake compared well with experimental mass uptake. The new model also predicted rapid air sampling accurately. To further integrate the sampling and analysis processes, especially for on-site or <i>in-vivo</i> investigations where the composition of the sample matrix is very complicated and/or agitation of the sample matrix is variable or unknown, a new approach for calibration was developed. This involved the loading internal standards onto the extraction fiber prior to the extraction step. During sampling, the standard partially desorbs into the sample matrix and the rate at which this process occurs, was for calibration. The kinetics of the absorption/desorption was investigated, and the isotropy of the two processes was demonstrated, thus validating this approach for calibration. A modified SPME device was used as a passive sampler to determine the time-weighted average (TWA) concentration of volatile organic compounds (VOCs) in air. The sampler collects the VOCs by the mechanism of molecular diffusion and sorption on to a coated fiber as collection medium. This process was shown to be described by Fick's first law of diffusion, whereby the amount of analyte accumulated over time enable measurement of the TWA concentration to which the sampler was exposed. TWA passive sampling with a SPME device was shown to be almost independent of face velocity, and to be more tolerant of high and low analyte concentrations and long and short sampling times, because of the ease with which the diffusional path length could be changed. Environmental conditions (temperature, pressure, relative humidity, and ozone) had little or no effect on sampling rate. When the SPME device was tested in the field and the results compared with those from National Institute of Occupational Health and Safety (NIOSH) method 1501 good agreement was obtained. To facilitate the use of SPME for field sampling, a new field sampler was designed and tested. The sampler was versatile and user-friendly. The SPME fiber can be positioned precisely inside the needle for TWA sampling, or exposed completely outside the needle for rapid sampling. The needle is protected within a shield at all times hereby eliminating the risk of operator injury and fiber damage. A replaceable Teflon cap is used to seal the needle to preserve sample integrity. Factors that affect the preservation of sample integrity (sorbent efficiency, temperature, and sealing materials) were studied. The use of a highly efficient sorbent is recommended as the first choice for the preservation of sample integrity. Teflon was a good material for sealing the fiber needle, had little memory effect, and could be used repeatedly. To address adsorption of high boiling point compounds on fiber needles, several kinds of deactivated needles were evaluated. RSC-2 blue fiber needles were the more effective. A preliminary field sampling investigation demonstrated the validity of the new SPME device for field applications.

Calibration methods for quantitative on-site sampling using solid phase microextraction (SPME) were developed based on diffusion mass transfer theory. This was investigated using adsorptive polydimethylsiloxane/divinylbenzene (PDMS/DVB) and Carboxen/polydimethylsiloxane (CAR/PDMS) SPME fiber coatings with volatile aromatic hydrocarbons (BTEX: benzene, toluene, ethylbenzene, and o-xylene) as test analytes. Parameters that affected the extraction process (sampling time, analyte concentration, water velocity, and temperature) were investigated. Very short sampling times (10-300 s) and sorbents with a strong affinity and large capacity were used to ensure a 'zero sink' effect calibrate process. It was found that mass uptake of analyte changed linearly with concentration. Increase of water velocity increased mass uptake, though the increase is not linear. Temperature did not affect mass uptake significantly under typical field sampling conditions. To further describe rapid SPME analysis of aqueous samples, a new model translated from heat transfer to a circular cylinder in cross flow was used. An empirical correlation to this model was used to predict the mass transfer coefficient. Findings indicated that the predicted mass uptake compared well with experimental mass uptake. The new model also predicted rapid air sampling accurately. To further integrate the sampling and analysis processes, especially for on-site or <i>in-vivo</i> investigations where the composition of the sample matrix is very complicated and/or agitation of the sample matrix is variable or unknown, a new approach for calibration was developed. This involved the loading internal standards onto the extraction fiber prior to the extraction step. During sampling, the standard partially desorbs into the sample matrix and the rate at which this process occurs, was for calibration. The kinetics of the absorption/desorption was investigated, and the isotropy of the two processes was demonstrated, thus validating this approach for calibration. A modified SPME device was used as a passive sampler to determine the time-weighted average (TWA) concentration of volatile organic compounds (VOCs) in air. The sampler collects the VOCs by the mechanism of molecular diffusion and sorption on to a coated fiber as collection medium. This process was shown to be described by Fick's first law of diffusion, whereby the amount of analyte accumulated over time enable measurement of the TWA concentration to which the sampler was exposed. TWA passive sampling with a SPME device was shown to be almost independent of face velocity, and to be more tolerant of high and low analyte concentrations and long and short sampling times, because of the ease with which the diffusional path length could be changed. Environmental conditions (temperature, pressure, relative humidity, and ozone) had little or no effect on sampling rate. When the SPME device was tested in the field and the results compared with those from National Institute of Occupational Health and Safety (NIOSH) method 1501 good agreement was obtained. To facilitate the use of SPME for field sampling, a new field sampler was designed and tested. The sampler was versatile and user-friendly. The SPME fiber can be positioned precisely inside the needle for TWA sampling, or exposed completely outside the needle for rapid sampling. The needle is protected within a shield at all times hereby eliminating the risk of operator injury and fiber damage. A replaceable Teflon cap is used to seal the needle to preserve sample integrity. Factors that affect the preservation of sample integrity (sorbent efficiency, temperature, and sealing materials) were studied. The use of a highly efficient sorbent is recommended as the first choice for the preservation of sample integrity. Teflon was a good material for sealing the fiber needle, had little memory effect, and could be used repeatedly. To address adsorption of high boiling point compounds on fiber needles, several kinds of deactivated needles were evaluated. RSC-2 blue fiber needles were the more effective. A preliminary field sampling investigation demonstrated the validity of the new SPME device for field applications.

<p>DESCARTES is a light-weight, balloon-borne grab sampler for stratospheric long-lived tracers developed at the University of Cambridge. 33 flights have been performed with two versions of the instrument at northern latitudes by the DESCARTES team at the Swedish Institute of Space Physics (IRF) in Kiruna during the years 1997-2000.</p><p>The general interest in long-lived stratospheric tracers is to study the general global circulation of air in the stratosphere and the exchange between the stratosphere and troposphere. In the study of chemical ozone depletion in the stratosphere, long-lived tracers serve as an important reference to distinguish between the variations in ozone of dynamical and chemical origin.</p><p>This thesis focuses on calibrations and quality assessment of the measurements made with the third version of the DESCARTES instrument based at IRF. Two different general approaches to make calibrations are discussed. Uncertainty estimations for both of these methods are made and the results are tested by laboratory methods and by comparisons to other instruments, including comparisons between two versions of DESCARTES. Analyzed and calibrated flight data for all successful flights are presented.</p><p>The basic principle of the instrument is to chemically adsorb a number of tracers (in practice only CFC-11 is measured) in an adsorption bed of Carboxen in a micro trap through which the sampled air is driven by a pump. After recovery the adsorbed species in the trap is desorbed by electrical heating of the trap and analysed by gas chromatography.</p><p>The resulting estimated mixing ratios from the instrument are directly dependent on the adsorption of the sampled species being quantitative in the traps. Laboratory experiments are described using two traps in series, where the performance of the first is tested by sampling the breakthrough by the second. A model is developed to recreate these tests in order to be able to compensate for breakthrough during flights. The model showed that the adsorption in the traps is not explained by simple chromatographic theory and the results allow us only to give an estimation of the uncertainty due to breakthrough.</p> / <p>DESCARTES är ett lätt ballongburet provtagningsinstrument för stratosfäriska spårgaser. Det är utvecklat vid universitetet i Cambridge. DESCARTES-teamet vid Institutet för rymdfysik (IRF) i Kiruna har under åren 1997-2000 genomfört 33 flygningar med två olika versioner av instrumentet från nordliga latituder.</p><p>Det generella intresset av långlivade stratosfäriska spårgaser är att studera den globala cirkulationen i stratosfären och utbytet av luft mellan stratosfären och troposfären. För studier av den kemiska ozonnedbrytningen i stratosfären spelar långlivade spårgaser en avgörande roll som referens för att skilja mellan variation i ozonkoncentrationen av kemiskt och dynamiskt ursprung.</p><p>Denna avhandling fokuserar på kalibrering och kvalitetssäkring av mätningar gjorda med den tredje versionen av DESCARTES-instrumentet hemmahörande vid IRF. Två i grunden olika kalibreringsförfaranden för instrumentet behandlas. Osäkerhetsuppskattningar är gjorda för båda dessa metoder och resultaten är prövade i laboratorietester. Dessutom jämförs resultaten från två versioner av DESCARTES och andra instrument. Analyserade data från samtliga lyckade flygningar presenteras.</p><p>Den grundläggande principen för instrumentet är att pumpa luftprover genom en fälla som innehåller en bädd av det kemiska adsorptionsmaterialet Carboxen, som adsorberar ett antal spårgaser. När instrumentet hämtats tillbaka efter en flygning gasas de adsorberade ämnena i fällan ut genom att fällan upphettas på elektrisk väg. De utgasade ämnena analyseras med gaskromatografi. I praktiken kan endast CFC-11 analyseras.</p><p>Den slutgiltiga bestämningen av blandningsförhållandet från instrumentet är direkt beroende av att adsorptionen i fällorna för de ämnen man vill undersöka är fullständig. En serie laboratorieexperiment har genomförts där två likadana fällor kopplats efter varandra. På så sätt har tillförlitligheten av den första fällan kunnat studeras genom att uppmäta hur mycket som bryter igenom till den andra fällan. En modell har utvecklats för att förstå resultatet av dessa tester och kunna kompensera för eventuella genombrott vid provtagning under flygningar. Modellen visade att adsorptionen i fällorna inte kan förklaras med enkel kromatografisk teori. Resultaten ger endast möjlighet att bedöma osäkerheten i mätningarna till följd av risken för genombrott.</p>

DESCARTES is a light-weight, balloon-borne grab sampler for stratospheric long-lived tracers developed at the University of Cambridge. 33 flights have been performed with two versions of the instrument at northern latitudes by the DESCARTES team at the Swedish Institute of Space Physics (IRF) in Kiruna during the years 1997-2000. The general interest in long-lived stratospheric tracers is to study the general global circulation of air in the stratosphere and the exchange between the stratosphere and troposphere. In the study of chemical ozone depletion in the stratosphere, long-lived tracers serve as an important reference to distinguish between the variations in ozone of dynamical and chemical origin. This thesis focuses on calibrations and quality assessment of the measurements made with the third version of the DESCARTES instrument based at IRF. Two different general approaches to make calibrations are discussed. Uncertainty estimations for both of these methods are made and the results are tested by laboratory methods and by comparisons to other instruments, including comparisons between two versions of DESCARTES. Analyzed and calibrated flight data for all successful flights are presented. The basic principle of the instrument is to chemically adsorb a number of tracers (in practice only CFC-11 is measured) in an adsorption bed of Carboxen in a micro trap through which the sampled air is driven by a pump. After recovery the adsorbed species in the trap is desorbed by electrical heating of the trap and analysed by gas chromatography. The resulting estimated mixing ratios from the instrument are directly dependent on the adsorption of the sampled species being quantitative in the traps. Laboratory experiments are described using two traps in series, where the performance of the first is tested by sampling the breakthrough by the second. A model is developed to recreate these tests in order to be able to compensate for breakthrough during flights. The model showed that the adsorption in the traps is not explained by simple chromatographic theory and the results allow us only to give an estimation of the uncertainty due to breakthrough. / DESCARTES är ett lätt ballongburet provtagningsinstrument för stratosfäriska spårgaser. Det är utvecklat vid universitetet i Cambridge. DESCARTES-teamet vid Institutet för rymdfysik (IRF) i Kiruna har under åren 1997-2000 genomfört 33 flygningar med två olika versioner av instrumentet från nordliga latituder. Det generella intresset av långlivade stratosfäriska spårgaser är att studera den globala cirkulationen i stratosfären och utbytet av luft mellan stratosfären och troposfären. För studier av den kemiska ozonnedbrytningen i stratosfären spelar långlivade spårgaser en avgörande roll som referens för att skilja mellan variation i ozonkoncentrationen av kemiskt och dynamiskt ursprung. Denna avhandling fokuserar på kalibrering och kvalitetssäkring av mätningar gjorda med den tredje versionen av DESCARTES-instrumentet hemmahörande vid IRF. Två i grunden olika kalibreringsförfaranden för instrumentet behandlas. Osäkerhetsuppskattningar är gjorda för båda dessa metoder och resultaten är prövade i laboratorietester. Dessutom jämförs resultaten från två versioner av DESCARTES och andra instrument. Analyserade data från samtliga lyckade flygningar presenteras. Den grundläggande principen för instrumentet är att pumpa luftprover genom en fälla som innehåller en bädd av det kemiska adsorptionsmaterialet Carboxen, som adsorberar ett antal spårgaser. När instrumentet hämtats tillbaka efter en flygning gasas de adsorberade ämnena i fällan ut genom att fällan upphettas på elektrisk väg. De utgasade ämnena analyseras med gaskromatografi. I praktiken kan endast CFC-11 analyseras. Den slutgiltiga bestämningen av blandningsförhållandet från instrumentet är direkt beroende av att adsorptionen i fällorna för de ämnen man vill undersöka är fullständig. En serie laboratorieexperiment har genomförts där två likadana fällor kopplats efter varandra. På så sätt har tillförlitligheten av den första fällan kunnat studeras genom att uppmäta hur mycket som bryter igenom till den andra fällan. En modell har utvecklats för att förstå resultatet av dessa tester och kunna kompensera för eventuella genombrott vid provtagning under flygningar. Modellen visade att adsorptionen i fällorna inte kan förklaras med enkel kromatografisk teori. Resultaten ger endast möjlighet att bedöma osäkerheten i mätningarna till följd av risken för genombrott.