Field and Laboratory Tests of Flow-Proportional Passive Samplers for Determining Average Phosphorus and Nitrogen Concentration in Rivers

Flow responsive passive samplers offer considerable potential in nutrient monitoring in catchments; bridging the gap between the intermittency of grab sampling and the high cost of automated monitoring systems. A commercially available passive sampler was evaluated in a number of river systems encapsulating a gradient in storm response, combinations of diffuse and point source pressures, and levels of phosphorus and nitrogen concentrations. Phosphorus and nitrogen are sequestered to a resin matrix in a permeable cartridge positioned in line with streamflow. A salt tracer dissolves in proportion to advective flow through the cartridge. Multiple deployments of different cartridge types were undertaken and the recovery of P and N compared with the flow-weighted mean concentration (FWMC) from high-resolution bank-side analysers at each site. Results from the passive samplers were variable and largely underestimated the FWMC derived from the bank-side analysers. Laboratory tests using ambient river samples indicated good replication of advective throughflow using pumped water, although this appeared not to be a good analogue of river conditions where flow divergence was possible. Laboratory tests also showed good nutrient retention but not elution and these issues appeared to combine to limit the utility in ambient river systems at the small catchment scale.

Trace Elements in Ambient Air at Porto Metropolitan Area—Checking for Compliance with New European Union (Eu) Air Quality Standards

Because of the scientific evidence showing that arsenic (As), cadmium (Cd), and nickel (Ni) are human genotoxic carcinogens, the European Union (EU) recently set target values for metal concentration in ambient air (As: 6 ng/m3, Cd: 5 ng/m3, Ni: 20 ng/m3). The aim of our study was to determine the concentration levels of these trace elements in Porto Metropolitan Area (PMA) in order to assess whether compliance was occurring with these new EU air quality standards. Fine (PM2.5) and inhalable (PM10) air particles were collected from October 2011 to July 2012 at two different (urban and suburban) locations in PMA. Samples were analyzed for trace elements content by inductively coupled plasma–mass spectrometry (ICP-MS). The study focused on determination of differences in trace elements concentration between the two sites, and between PM2.5 and PM10, in order to gather information regarding emission sources. Except for chromium (Cr), the concentration of all trace elements was higher at the urban site. However, results for As, Cd, Ni, and lead (Pb) were well below the EU limit/target values (As: 1.49 ± 0.71 ng/m3; Cd: 1.67 ± 0.92 ng/m3; Ni: 3.43 ± 3.23 ng/m3; Pb: 17.1 ± 10.1 ng/m3) in the worst-case scenario. Arsenic, Cd, Ni, Pb, antimony (Sb), selenium (Se), vanadium (V), and zinc (Zn) were predominantly associated to PM2.5, indicating that anthropogenic sources such as industry and road traffic are the main source of these elements. High enrichment factors (EF > 100) were obtained for As, Cd, Pb, Sb, Se, and Zn, further confirming their anthropogenic origin.

The impact of wine closure and packaging type, and light and temperature exposure on the concentration of 3-alkyl-2 -methoxypyrazines and other key constituents of wine

3-alkyl-2-methoxypyrazines (MPs) are grape- and insect-derived odor-active compounds responsible for vegetative percepts that are detrimental to wine quality when elevated. This study tested both the effect of closure/packaging types and light/temperature storage conditions on MPs (isopropyl-, secbutyl-, and isobutyl-MP) in wine. An MP-emiched wine rapidly (after 140 hours) and significantly decreased in MP concentration after natural and synthetic cork contact (immersion of closures in wine). This decrease was greatest with synthetic closures (70% - 89% reduction) and secbutyl-MP. Subsequently storage trials tested the effects of commercial closure/packaging options (natural cork, agglomerate cork, synthetic corks, screwcaps and TetraPak® cartons) on MPs in MP-emiched Riesling and Cabernet Franc over 18 months. Regardless of packaging, isobutyl-MP was the most altered from bottling. Notably, all MP levels tended to decrease to the greatest extent in TetraPak® cartons (~34% for all MPs) and there was evidence of contribution ofisoproyl- and secbutyl-MP from cork-based closures (i.e. ~30% increase in secbutyl-MP after 6 months) or from an unidentified wine constituent. To test the effects of various light/temperature conditions (light exposed at ambient temperature in three different bottle hues, light excluded at ambient temperature and light excluded at a "cellar" temperature (14°C)), MP-emiched Riesling and Cabernet Franc were also analyzed for MP concentrations over 12 months. MPs did not vary consistently with light or temperature. Other odorants and physico-chemical properties were tested in all wines during storage trials and closely agree with previous literature. These results provide novel insights into MPs during ageing, interactions with packaging and storage conditions, and assist in the selection of storage conditions/packaging for optimal wine quality.

Desenvolupament de metodologia analítica per al seguiment d'herbicides fenoxiacètics i cafeïna en el medi ambient

El control d'herbicides i altres anàlits orgànics presents en el medi ambient constitueix una pràctica habitual en els laboratoris des de l'establiment de legislacions que limiten la seva concentració. Per aquesta raó, cal el desenvolupament de noves metodologies analítiques per al seguiment de compostos orgànics en el medi. Molt sovint aquests anàlits es troben a nivells traça en aigües i sòls, conjuntament amb un alt contingut de substàncies húmiques i fúlviques. Així, un dels reptes existents és el tractament de la mostra (extracció, concentració i "clean-up" d'aquests anàlits per a una bona quantificació). Aquests processos han de venir complementats per tècniques cromatogràfiques que permetin la mesura final dels anàlits. La investigació que es presenta en aquesta tesi es centra en el desenvolupament d'un mètode per a la determinació de 2,4-D i MCPA i els seus metabòlits fenòlics i d'un altre per a la determinació de cafeïna. El primer dels procediments desenvolupats s'ha aplicat al seguiment dels herbicides i els metabòlits fenòlics en sòls d'un camp de golf, mentre que el segon s'ha emprat per a la determinació de cafeïna en aigües naturals i, posteriorment, en aigües residuals.

Synthesis, structure and reactivity of novel CuI, CuII and CuIII complexes containing triaza and hexaaza macrocyclic ligands

El treball de tesi s'emmarca dins del camp de la bioinorgànica, disciplina que estudia les propietats estructurals i de reactivitat dels centres actius dels enzims, servint-se de models síntètics de baix pes molecular per tal d'intentar reproduïr la reactivitat presentada per l'enzim i conèixer els mecanismes de reacció a nivell molecular que tenen lloc en els processos biològics.1 Més concretament el treball posa especial èmfasi en els processos d'activació d'oxigen molecular que tenen lloc en les metaloproteïnes de Coure del Tipus 3, com són l'hemocianina i la tirosinasa, ambdues presentant un complex dinuclear de Cu(I)) en el centre actiu de la forma reduïda, capaç d'activar l'O2 cap a espècies de tipus peròxid.2 Un altre camp d'interès ha estat l'estudi dels processos d'activació d'enllaços C-H no activats en hidrocarburs, tant per la seva importàcia a nivell industrial com per comprendre els mecanismes intrínsecs d'aquesta activació a través de metalls de trancisió.3,4 Durant el treball de tesi presentat s'ha desenvolupat la síntesi de nous complexes de Coure(I), Coure(II) y Cu(III) utilitzant lligands macrocíclics de tipus triaza i hexaaza, i s'han estudiat la seves propietats estructurals així com la seva reactivitat. La reacció dels lligands triazacíclics H32m, H2Me33m i H33m amb sals de coure(II) dóna lloc a una reacció de desproporció de Cu(II) per obtenir-se en quantitats equimolars un complex organometàl·lic de Cu(III) i un complex de Cu(I). La caracterizació estructural exhaustiva dels complexes del tipus aryl-Cu(III) evidencia la formació d'un enllaç organometàl·lic entre l'àtom de Cu(III) i el carboni més próxim de l'anell aromàtic del lligand. Aquesta reacció, a més de representar una nova forma de desproporció en la química del Cu, suposa l'activació d'un enllaç C-H aromàtic a temperatura ambient que, mitjançant l'estudi cinètic d'aquesta desproporció per espectroscòpia UV-Vis, dels càlcul de l'efecte cinètic isotòpic utilitzant el lligand deuterat en el C-H de l'anell, juntament amb el recolzament teòrics dels càlculs DFT per a la optimització de geometries d'intermedis de reacció, ens permeten proposar un mecanisme de reacció pel nostre sistema, on l'activació de l'enllaç C-H aromàtic transcorre per la formació d'un enllaç de tipus agòstic C-H ? Cu(II),5 seguit de la desprotonació del C-H aromàtic per acció d'una base i posterior transferència electrònica per obtenir el complex organometàlic de Cu(III) i el complex de de Cu(I). En quant a la reactivitat d'aquests complexes organometàl·lics aryl-Cu(III) s'ha observat que una base en medi aquós causa la inestabilitat d'aquests compostos, evolucionant cap a la inserció d'un àtom d'oxigen sobre la posició activada de l'anell aromàtic, per a donar lloc a un complex dinuclear de Cu(II) amb dos grups fenoxo actuant de pont entre els àtoms metàl·lics. La reacció transcorre per un intermedi colorejat, caracteritzat com el complex ayl-Cu(III) monodesprotonat en una de les seves amines benzíliques, els quals s'observen igualment en la reacció dels correponents complexos de Cu(I) amb oxigen molecular (O2). És en els nostres sistemes en els quals es descriu per primera vegada la participació d'intermedis organometàl·lics Cu(III)-C en processos d'hidroxilació aromàtica, tals com el desenvolupat per l'enzim tirosinasa o per alguns dels seus models químics de síntesi.6,7,8 S'han estudiat les propietats magnètiques dels quatre bis(fenoxo)complexes de Cu(II) descrits, obtenint-se uns acoplaments de tipus antiferromagnètic o ferromagnètic de diversa magnitud, depenent del solapament orbitalari a l'enllaç Cu-O, a través del qual es produeix el superintercanvi. Nous complexos de Cu(I) sintetitzats amb lligands hexaazamacrocíclics han estat estudiats, i posant especial èmfasi a la seva reactivitat respecta a l'activació d'oxigen molecular (O2). S'ha observat una reactivitat diferenciada segons la concentració de complex de Cu(I) utilitzada, de manera que a altes concentracions s'obté un carbonato complex tetranuclear de Cu(II) per fixació de CO2 atmosfèric, mentre que a baixes concentracions s'observa la hidroxilació aromàtica intramolecular d'un dels anells benzílics del lligand, reacció que presumiblement transcorre per atac electrofílic d'un peroxo complex intermedi sobre el sistema ? de l'anell.6 Els resultats obtinguts en aquest treball ens mostren la facilitat per activar enllaços C-H aromàtics per metalls de transició de la primera sèrie (Cu, Ni) quan aquests estan suficientment pròxims a l'enllaç C-H, en unes condicions de reacció molt suaus (1atm., temperatura ambient). Els nous complexos organometàl·lics Aryl-Cu(III) són el producte d'una nova reacció de desproporció de Cu(II), així com un posició aromàtica activada que podria ser el punt de partida per l'estudi de funcionalització selectiva d'aquests grups aromàtics.

Particulate matter mass concentration (PM10) under different ventilation methods in classrooms

Recently, studies have shown that the classroom environment is very important for students' health and performance. Thus, the evaluation of indoor air quality (IAQ) in a classroom is necessary to ensure students' well-being. In this paper the emphasis is on airborne concentration of particulate matter (PM) in adult education rooms. The mass concentration of PM10 particulates was measured in two classrooms under different ventilation methods in the University of Reading, UK, during the winter period of 2008. In another study the measurement of the concentration of particles was accompanied with measurements of CO2 concentration in these classrooms but this study is the subject of another publication. The ambient PM10, temperature, relative humidity, wind speed and direction, and rainfall events were monitored as well. In general, this study showed that outdoor particle concentrations and outdoor meteorological parameters were identified as significant factors influencing indoor particle concentration levels. Ventilation methods showed significant effects on air change rate and on indoor/outdoor (I/O) concentration ratios. Higher levels of indoor particulates were seen during occupancy periods. I/O ratios were significantly higher when classrooms were occupied than when they were unoccupied, indicating the effect of both people presence and outdoor particle concentration levels. The concentrations of PM10 indoors and outdoors did not meet the requirements of WHO standards for PM10 annual average.

Radical cations of end-capped tetrathienoacenes and their p-dimerization controlled by the nature of a-substituents and counterion concentration

Radical cations of a soluble rigid tetrathienoacene are capable of forming stable p-dimer dications at ambient temperature when the short backbone becomes extended with conjugated thiophene-2-yl substituents in the a-positions. On the other hand, simple attachment of methyl groups on the a-carbon of the external thiophen-2-yl rings proved sufficient to inhibit the dimerization. Stable radical cationswere also exclusively formed for tetrathienoacene derivatives end-capped with bulky TIPS and phenyl substituents.

Exposure to ambient levels of particles emitted by traffic worsens emphysema in mice

Objectives: We investigated effects of chronic exposure (2 months) to ambient levels of particulate matter (PM) on development of protease-induced emphysema and pulmonary remodeling in mice. Methods: Balb/c mice received nasal drop of either papain or normal saline and were kept in two exposure chambers situated in an area with high traffic density. One of them received ambient air and the other had filters for PM. Results: mean concentration of PM10 was 2.68 +/- 0.38 and 33.86 +/- 2.09 mu g/m(3), respectively, in the filtered and ambient air chambers (p<0.001). After 2 months of exposure, lungs from papain-treated mice kept in the chamber with ambient air presented greater values of mean linear intercept, an increase in density of collagen fibers in alveolar septa and in expression of 8-isoprostane (p = 0.002, p < 0.05 and p = 0.002, respectively, compared to papain-treated mice kept in the chamber with filtered air). We did not observe significant differences between these two groups in density of macrophages and in amount of cells expressing matrix metalloproteinase-12. There were no significant differences in saline-treated mice kept in the two chambers. Conclusions: We conclude that exposure to urban levels of PM worsens protease-induced emphysema and increases pulmonary remodeling. We suggest that an increase in oxidative stress induced by PM exposure influences this response. These pulmonary effects of PM were observed only in mice with emphysema. (C) 2009 Elsevier Inc. All rights reserved.

Dietary electrolyte balance for broiler chickens under moderately high ambient temperatures and relative humidities

Cobb male broiler chicks (1,000) on new litter were used to evaluate effects of dietary electrolyte balance [DEB; Na+K-Cl, milliequivalents (mEq) per kilogram] under tropical summer conditions. Corn-soybean meal-based mash diets had salt (NaCl) alone or in combination with one or more supplements: sodium bicarbonate (NaHCO3), ammonium chloride (NH4Cl), or potassium bicarbonate (KHCO3). A completely randomized design, with five starter and grower feed treatments (control: 145, then 130 mEq/kg; or 0, 120, 240, or 360 mEq/kg throughout) and four replicate pens (1.5 x 3.2 m) per treatment (50 chicks per pen), was used. Diets were analyzed for Na, K, and Cl for confirmation. There were no significant (P < 0.05) effects of treatments on mortality or processing parameters. Water intake increased linearly with increasing DEB, giving higher litter moistures and lower rectal temperatures. Blood HCO3 and pH increased with the highest DEB (360 mEq/kg) causing respiratory alkalosis. The DEB of 240 mEg/kg gave best weight gain and feed conversion ratio, and ideal DEB predicted by regression analyses were 186 and 197 mEq/kg from 0 to 21 d of age and 236 and 207 mEq/kg of feed from 0 to 42 d, respectively. These DEB corresponded to estimated (interpolated) values in predicted optimal 186 to 197 mEq/kg starter of Na 0.38 to 0.40% and Cl 0.405 to 0.39% (K = 0.52%), in 207 to 236 mEq/kg starter, Na 0.409 to 0.445% and Cl 0.326 to 0.372% Cl (K = 0.52%), and in grower Na 0.41 to 0.445%, Cl 0.315 to 0.267% (K = 0.47%).

Elevated atmospheric CO2 concentration increases rice blast severity

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

A New and Simple Visual Technique Based on Indigo Dye for Determination of Ozone in Ambient Air

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Ambient levels of air pollution induce clinical worsening of blepharitis

Background: Even though air pollutants exposure is associated with changes in the ocular surface and tear film, its relationship to the clinical course of blepharitis, a common eyelid disease, had not yet been investigated. Our objective was to investigate the correlation between air pollution and acute manifestations of blepharitis. Method: We recorded all cases of changes in the eyelids and ocular surface, and rated clinical findings on a scale from zero (normal) to two (severe alterations). Daily values of carbon monoxide, particulate matter smaller than 10 mu m in diameter and nitrogen dioxide concentrations and meteorological variables (temperature and relative humidity) in the vicinity of the medical service were obtained. Specific linear regression models for each outcome were constructed including pollutants as independent variables (single pollutant models). Temperature and humidity were included as confounding variables. Results: increases of 28.8 mu g/m(3) in the concentration of particulate matter and 1.1 ppm in the concentration of CO were associated with increases in cases of blepharitis on the day of exposure (5 cases, 95% CI: 1-10 and 6 cases, 95% CI: 1-12, respectively). Conclusion: Exposure to usual air pollutants concentrations present in large cities affects, in a consistent manner, the eyes of residents contributing to the increasing incidence of diseases of the eyelid margin. (C) 2011 Elsevier Inc. All rights reserved.

Effect of blood haemoglobin concentration on V(O2,max) and cardiovascular function in lowlanders acclimatised to 5260 m

[EN] The principal aim of this investigation was to determine the influence of blood haemoglobin concentration ([Hb]) on maximal exercise capacity and maximal O(2) consumption (V(O(2),max)) in healthy subjects acclimatised to high altitude. Secondarily, we examined the effects of [Hb] on the regulation of cardiac output (CO), blood pressure and muscular blood flow (LBF) during exercise. Eight Danish lowlanders (three females and five males; 24 +/- 0.6 years, mean +/- S.E.M.) performed submaximal and maximal exercise on a cycle ergometer after 9 weeks at an altitude of 5260 m (Mt Chacaltaya, Bolivia). This was done first with the high [Hb] resulting from acclimatisation and again 2-4 days later, 1 h after isovolaemic haemodilution with Dextran 70 to near sea level [Hb]. After measurements at maximal exercise while breathing air at each [Hb], subjects were switched to hyperoxia (55 % O(2) in N(2)) and the measurements were repeated, increasing the work rate as tolerated. Hyperoxia increased maximal power output and leg V(O(2),max), showing that breathing ambient air at 5260 m, V(O(2),max) is limited by the availability of O(2) rather than by muscular oxidative capacity. Altitude increased [Hb] by 36 % from 136 +/- 5 to 185 +/- 5 g l(-1) (P < 0.001), while haemodilution (replacing 1 l of blood with 1 l of 6 % Dextran) lowered [Hb] by 24 % to 142 +/- 6 g l(-1) (P < 0.001). Haemodilution had no effect on maximal pulmonary or leg V(O(2),max), or power output. Despite higher LBF, leg O(2) delivery was reduced and maximal V(O(2)) was thus maintained by higher O(2) extraction. While CO increased linearly with work rate irrespective of [Hb] or inspired oxygen fraction (F(I,O(2))), both LBF and leg vascular conductance were systematically higher when [Hb] was low. Close and significant relationships were seen between LBF (and CO) and both plasma noradrenaline and K(+) concentrations, independently of [Hb] and F(I,O(2)). In summary, under conditions where O(2) supply limits maximal exercise, the increase in [Hb] with altitude acclimatisation does not improve maximal exercise capacity or V(O(2),max), and does not alter peak CO. However, LBF and vascular conductance are higher at altitude when [Hb] is lowered to sea level values, with both relating closely to catecholamine and potassium concentrations. This suggests that the lack of effect of [Hb] on V(O(2),max) may involve reciprocal changes in LBF via local metabolic control of the muscle vasculature.

Application of comprehensive gas chromatography (GCxGC) to measurements of volatile organic species in ambient air

The focus of this thesis was the in-situ application of the new analytical technique "GCxGC" in both the marine and continental boundary layer, as well as in the free troposphere. Biogenic and anthropogenic VOCs were analysed and used to characterise local chemistry at the individual measurement sites. The first part of the thesis work was the characterisation of a new set of columns that was to be used later in the field. To simplify the identification, a time-of-flight mass spectrometer (TOF-MS) detector was coupled to the GCxGC. In the field the TOF-MS was substituted by a more robust and tractable flame ionisation detector (FID), which is more suitable for quantitative measurements. During the process, a variety of volatile organic compounds could be assigned to different environmental sources, e.g. plankton sources, eucalyptus forest or urban centers. In-situ measurements of biogenic and anthropogenic VOCs were conducted at the Meteorological Observatory Hohenpeissenberg (MOHP), Germany, applying a thermodesorption-GCxGC-FID system. The measured VOCs were compared to GC-MS measurements routinely conducted at the MOHP as well as to PTR-MS measurements. Furthermore, a compressed ambient air standard was measured from three different gas chromatographic instruments and the results were compared. With few exceptions, the in-situ, as well as the standard measurements, revealed good agreement between the individual instruments. Diurnal cycles were observed, with differing patterns for the biogenic and the anthropogenic compounds. The variability-lifetime relationship of compounds with atmospheric lifetimes from a few hours to a few days in presence of O3 and OH was examined. It revealed a weak but significant influence of chemistry on these short-lived VOCs at the site. The relationship was also used to estimate the average OH radical concentration during the campaign, which was compared to in-situ OH measurements (1.7 x 10^6 molecules/cm^3, 0.071 ppt) for the first time. The OH concentration ranging from 3.5 to 6.5 x 10^5 molecules/cm^3 (0.015 to 0.027 ppt) obtained with this method represents an approximation of the average OH concentration influencing the discussed VOCs from emission to measurement. Based on these findings, the average concentration of the nighttime NO3 radicals was estimated using the same approach and found to range from 2.2 to 5.0 x 10^8 molecules/cm^3 (9.2 to 21.0 ppt). During the MINATROC field campaign, in-situ ambient air measurements with the GCxGC-FID were conducted at Tenerife, Spain. Although the station is mainly situated in the free troposphere, local influences of anthropogenic and biogenic VOCs were observed. Due to a strong dust event originating from Western Africa it was possible to compare the mixing ratios during normal and elevated dust loading in the atmosphere. The mixing ratios during the dust event were found to be lower. However, this could not be attributed to heterogeneous reactions as there was a change in the wind direction from northwesterly to southeasterly during the dust event.

The formation of OH radicals from Criegee intermediates: a LIF-FAGE study from laboratory to ambient

Das Hydroxyl Radikal ist, auf globalem Maßstab, das bedeutendste Oxidant in der Atmosphäre. Es initiiert den Abbauprozess vieler, teilweise schädlicher, Spurengase und insbesondere den von flüchtigen Kohlenwasserstoffen (VOC). Die OH Konzentration ist somit ein gutes Maß für die augenblickliche Selbstreinigungskapazität der Atmosphäre. Messungen zu nächtlicher Zeit mit LIF-FAGE-Instrumenten (engl.: laser-induced fluorescence - fluorescence assay by gas expansion) haben Konzentrationen des Hydroxylradikals (OH) ergeben, die signifikant höher waren, als sich mit der bekannten Chemie erklären ließ. Um herauszufinden, ob ein solches Signal wirklich atmosphärisches OH ist oder von einer störenden Spezies stammt, die im Messinstrument OH produziert, wurde das LIF-FAGE-Instrument des Max-Planck-Instituts für Chemie (MPIC) im Rahmen dieser Doktorarbeit modifiziert und getestet. Dazu wurde ein so genannter Inlet Pre-Injector (IPI) entwickelt, mit dem in regelmäßigen Abständen ein OH-Fänger in die Umgebungsluft abgegeben werden kann, bevor das OH vom Instrument erfasst wird. Mit dieser Technik ist es möglich, ein Hintergrund-OH (OHbg), d. h. ein im Instrument erzeugtes OH-Signal, vom gemessenen OH-Gesamtsignal (OHtot) zu trennen. Die Differenz zwischen OHtot und OHbg ist die atmosphärische OH-Konzentration (OHatm). Vergleichsmessungen mit der hier entwickelten Technik, dem IPI, in zwei verschiedenen Umgebungen mit Instrumenten basierend auf Massenspektrometrie mit chemischer Ionisation (CIMS, engl.: chemical ionization mass spectrometry) als alternativer Methode des OH-Nachweises, zeigten eine weitgehende Übereinstimmung. Eine umfassende Beschreibung des Systems zur Ermittlung der Ursache des OHbg hat ergeben, dass es weder von einem Artefakt des Instruments noch von hinlänglich bekannten und beschriebenen LIF-FAGE-Interferenzen stammt. Zur Bestimmung der Spezies, die das OHbg-Signal verursacht, wurden verschiedene Laborstudien durchgeführt. Die Arbeit im Rahmen dieser Doktorarbeit hat ergeben, dass das LIF-FAGE-Instrument leicht auf OH reagiert, das beim monomolekularen Zerfall stabilisierter Criegee-Intermediate (SCI) im Niederdruckbereich des Instruments gebildet wird. Criegee-Intermediate oder Carbonyloxide entstehen bei der Ozonolyse ungesättigter flüchtiger Kohlenwasserstoffverbindungen (VOC, engl.: volatile organic compounds) und können daher in der Umgebungsluft vorkommen. Anhand von Tests mit verschiedenen Verweilzeiten der SCI im Niederdruckbereich des Instruments in Verbindung mit einem detaillierten Modell mit der neuesten SCI-Chemie wurde die monomolekulare Zerfallsgeschwindigkeit von 20  10 s-1 für den syn-Acetaldehyd-Oxykonformer bestimmt. Der in Feldkampagnen gemessene OHbg-Wert wurde dahingehend untersucht, ob SCI die Quelle des beobachteten Hintergrund-OH im Feld sein könnten. Das Budget für die SCI-Konzentration, das für die Kampagnen HUMPPA-COPEC 2010 und HOPE 2012 berechnet wurde, ergab eine SCI-Konzentration zwischen ca. 103 und 106 Molekülen pro cm3. In der Kampagne HUMPPA-COPEC 2010 ergab die Schwefelsäurekonzentration, dass die OH-Oxidation von SO2 allein die gemessene H2SO4-Konzentration nicht erklären konnte. In dieser Arbeit konnte gezeigt werden, dass das Hintergrund-OH mit dieser ungeklärten Produktionsrate von H2SO4 korreliert und somit die Oxidation von SO2 durch SCI als mögliche Erklärung in Frage kommt. Ferner korreliert das Hintergrund-OH in der Kampagne HOPE 2012 mit dem Produkt aus Ozon und VOC und konnte mit SO2 als SCI Fänger entfernt werden. Qualitativ zeigen wir somit, dass das in der Umgebungsluft gemessene Hintergrund-OH wahrscheinlich durch den monomolekularen Zerfall von SCI verursacht wird, doch sind weitere Studien notwendig, um die quantitativen Beziehung für diese Spezies und dem Hintergrund-OH in unserem Instrument zu bestimmen.