<p>Sprovedeno istraživanje u okviru<br />disertacije obuhvata procenu distribucije<br />16 EPA primarnih policikličnih aromatičnih<br />ugljovodonika između gasovite i čvrste<br />faze u atmosferi, na selektovanim<br />lokalitetima urbanog, industrijskog i<br />ruralnog područja na teritoriji Zapadnog<br />Balkana. Rezultati eksperimentalnog<br />određivanja predstavljali su osnovu za<br />evaluaciju reprezentativnih modela<br />rasprostiranja poluisparljivih organskih<br />jedinjenja kroz povr&scaron;inski atmosferski sloj<br />i raspodele gas/suspendovane čestice,<br />čime je dat uvid u mehanizme koji<br />dominiraju atmosferskom distribucijom<br />policikličnih aromatičnih ugljovodonika.<br />Metodom dijagnostičkih odnosa<br />realizovana je kvalitativna karakterizacija<br />izvora emisije PAH u atmosferu.<br />Korekcijom postojećih empirijskih i<br />teorijskih izraza koji opisuju gas/čestičnu<br />particiju PAH, razvijen je matematički<br />model raspodele policikličnih aromatičnih<br />ugljovodonika u ambijentalnom vazduhu.</p> / <p>Gas-particle distribution of 16 EPA primary<br />polycyclic aromatic hydrocarbons in the<br />atmosphere at the selected sampling sites<br />in urban, industrial and rural area of the<br />Western Balkan countries has been<br />analyzed within the doctoral dissertation.<br />On the basis of obtained experimental<br />data, representative models of transport<br />through surface atmospheric layer and gasparticle<br />partitioning of the semivolatile<br />organic compounds have been evaluated,<br />giving the overview on mechanisms which<br />govern atmospheric distribution of<br />polycyclic aromatic hydrocarbons. Using<br />the method of diagnostic ratio, qualitative<br />characterization of emission sources of<br />PAHs in the atmosphere has been realized.<br />Through correction of actual empirical and<br />theoretical expressions, explaining gasparticle<br />partitioning of PAHs,<br />mathematical model of distribution of<br />polycyclic aromatic hydrocarbons in the<br />ambient air has been developed.</p>

Les matériaux actuellement utilisés comme capteurs passifs de polluants atmosphériques, la mousse de polyuréthane et la résine XAD®-2, ne sont optimisés ni pour l'adsorption de composés polaires ni pour le captage de particules. Pour remédier à ces limitations, la mousse de carbure de silicium (SiC) est proposée comme alternative. Plusieurs campagnes de mesures ont été mises en place pour comparer SiC et XAD®-2. Les composés recherchés étaient des HAP, des PCB et des pesticides.Une méthode d'analyse combinant ASE, SPE et SPME a été développée et optimisée pour ces polluants. Celle-ci permet d'atteindre de faibles limites de détection et quantification pour les composés recherchés.Les campagnes réalisées montrent que la mousse de SiC est toujours plus efficace que la résine XAD®-2 pour le piégeage de composés particulaires et polaires. De plus, la SiC peut être greffée avec du carbone ou des nanotubes de carbone pour augmenter sa surface spécifique, ce qui la rend également plus performante pour l'adsorption de composés volatils. Les débits d'échantillonnage moyens de la mousse ont été calculés et sont comparable aux valeurs rapportées dans la littérature pour la résine XAD®-2. / Materials currently used as passive samplers for atmospheric pollutants, polyurethane foam and XAD®-2 resin, are not suited ta trapping polar compounds nor particles. Ta overcome these limitations, silicon carbide (SiC) foam is presented as an alternative. Several sampling campaigns monitoring PAH, PCB and pesticides were done ta compare SiC and XAD®-2. An analytical method coupling ASE, SPE and SPME was developed and optimised for these pollutants. lt allowed low limits of detection and quantification ta be reached for all compounds of interest.Sampling campaigns showed that SiC foam is consistently more efficient than XAD®-2 resin at trapping particulate and polar compounds. Moreover, SiC foam can be grafted with carbon or carbon nanotubes ta increase its specific surface area, which also makes it better at adsorbing volatile compounds. Average sampling rates were calculated for SiC foam and they are comparable ta the values reported in the literature for XAD®-2 resin.

The ability to rapidly detect and identify hazardous analytes in the field has become increasingly important. One of the most important analytical detection methods in the field is gas chromatography-mass spectrometry (GC-MS). In this work, a hand-portable GC-MS system is described that contains a miniature toroidal ion trap mass analyzer and a low thermal mass GC. The system is self-contained within the dimensions of 47 x 36 x 18 cm and weighs less than 13 kg. Because the instrument has a small footprint, it was used as the detector for an automated near-real-time permeation testing system. In permeation testing, materials that are used to make individual protective equipment such as gloves, masks, boots, and suits are exposed to hazardous analytes to determine how long the equipment can be worn safely. The system described herein could test five samples simultaneously. A multi-position valve rotated among the various sample streams and delivered time aliquots into the MS for quantitation. Current field air sampling techniques suffer from long desorption times, high pressure drops, artifact formation and water retention. These disadvantages can be avoided by concentrating the analytes in short open tubular traps containing thick films. There are several advantages to using polymer coated capillaries as traps, including fast desorption, inertness and low flow restriction. An air sampling trap was constructed utilizing open tubular traps for the concentration of semi-volatile organic compounds. The system consisted of multiple capillary traps bundled together, providing high sample flow rates. The analytes were desorbed from the multi-capillary bundle and refocused in a secondary trap. The simultaneous focusing and separation effect of a trap subjected to a negative temperature gradient was also explored. In this configuration, analytes were focused because the front of the peak was at a lower temperature than the rear of the peak and, hence, moved slower. In addition to the focusing effect, analytes with different volatilities focused at different temperatures within the gradient, allowing for separation.

<p>This thesis presents methods for air sampling and determination of isocyanates, amines, aminoisocyanates and anhydrides. These organic compounds are generated during thermal degradation of polymers such as polyurethane (PUR) or epoxy.</p><p>Isocyanates, amines and anhydrides are airway irritants known to cause occupational asthma. Some of the compounds are listed as human carcinogens. Many workers are exposed.</p><p>Isocyanates and anhydrides are reactive and needs to be immediately derivatized during sampling. Methods have been developed for determination of airborne isocyanates, aminoisocyanates and anhydrides using di-n-butylamine (DBA) as reagent to form stabile urea derivatives or amide derivatives. Liquid chromatography-tandem mass spectrometry (LC-MS/MS) enabled detection limits as low as 10 attomoles. A nitrogen-selective LC-detector enabled quantification of DBA-derivatives in reference solutions. </p><p>A novel sampler is presented. The sampler consists of a denuder in series with a three-stage cascade impactor and an end filter. The sampler made it possible to reveal the distribution of isocyanates between gas and different particle size fractions. During thermal degradation of PUR, isocyanates were associated to particle size fractions (<1 µm) that may penetrate to the lower airways. The distribution during 8 minutes changes noticeably. Aromatic isocyanates become associated to small particles (<1 µm). As a reference method, air-sampling was performed using an impinger filled with di-n-butylamine (DBA) in toluene, connected in series with a glass fiber filter. There was a good agreement between the denuder-impactor sampler and the reference method.</p>

This thesis presents methods for air sampling and determination of isocyanates, amines, aminoisocyanates and anhydrides. These organic compounds are generated during thermal degradation of polymers such as polyurethane (PUR) or epoxy. Isocyanates, amines and anhydrides are airway irritants known to cause occupational asthma. Some of the compounds are listed as human carcinogens. Many workers are exposed. Isocyanates and anhydrides are reactive and needs to be immediately derivatized during sampling. Methods have been developed for determination of airborne isocyanates, aminoisocyanates and anhydrides using di-n-butylamine (DBA) as reagent to form stabile urea derivatives or amide derivatives. Liquid chromatography-tandem mass spectrometry (LC-MS/MS) enabled detection limits as low as 10 attomoles. A nitrogen-selective LC-detector enabled quantification of DBA-derivatives in reference solutions. A novel sampler is presented. The sampler consists of a denuder in series with a three-stage cascade impactor and an end filter. The sampler made it possible to reveal the distribution of isocyanates between gas and different particle size fractions. During thermal degradation of PUR, isocyanates were associated to particle size fractions (&lt;1 µm) that may penetrate to the lower airways. The distribution during 8 minutes changes noticeably. Aromatic isocyanates become associated to small particles (&lt;1 µm). As a reference method, air-sampling was performed using an impinger filled with di-n-butylamine (DBA) in toluene, connected in series with a glass fiber filter. There was a good agreement between the denuder-impactor sampler and the reference method.

The work presented in this thesis concerns the development and evaluation of new methods of sampling and analysis of organic pollutants in the indoor and outdoor environment. In Paper I, the development of a new method was reported for the determination of the brominated flame retardant tetrabromobisphenol A (TBBPA) in air using sampling with glass fiber filter and polyurethane foam (PUF), ultrasonic solvent extraction and liquid chromatography coupled to electrospray ionisation mass spectrometry (LC-ESI/MS). The MS fragmentation mechanism of TBBPA was thoroughly investigated and different acquisition modes were evaluated to achieve the most sensitive and selective detection. In Papers II and III, the potential use of Empore SPE membranes was evaluated for air sampling of volatile, semi-volatile and particle-associated organic compounds. Breakthrough studies conducted for 24h at air flows of 10- 20 L/min showed that the SPE membranes efficiently retains volatile and semi-volatile organophosphate esters and particles &gt;10 nm. Effort was invested in the development of fast and environmental friendly methods, with low cost, for sample clean up and analysis. In Paper II, the sample preparation technique was dynamic solvent extraction with methanol coupled to LC-ESI/MS. The total run time per sample, including both extraction and separation, was less than 34 min, consuming only 1.6mL methanol. In Paper III, efficiency of selective extraction of polycyclic aromatic hydrocarbons from particulate matter sampled with Empore SPE membranes, using dynamic subcritical water extraction (DSWE) was investigated. Acceptable recoveries of the investigated compounds from reference material (SRM 1649a) were achieved. In Paper IV, the application of dynamic solid phase micro-extraction (SPME) air sampling was evaluated using, gas chromatography/positive ion chemical ionisation (GC/PICI) and tandem-MS detection for the determination of organophosphate esters in work environment.

Cette thèse se consacre à la mise au point de techniques d’échantillonnage suivies d’analyses réalisées au laboratoire pour mettre en évidence les espèces majoritaires en air intérieur et caractériser leurs variations temporelles. Le développement analytique a été effectué pour 52 COVs et pour 16 HAPs associés à la phase particulaire de l’air. Les prélèvements des COVs ont été réalisés au moyen d’un préleveur automatique permettant d’échantillonner l’air sur des tubes extraits par désorption thermique et analysés par chromatographie gazeuse couplée à la détection FID. Pour la quantification des HAPs, le prélèvement des particules est effectué par un impacteur à cascade à trois étages permettant de fractionner l’aérosol en fonction de leur diamètre aérodynamique. Les HAPs sont quantifiés par chromatographie liquide haute performance couplée à la détection par fluorescence. Ces deux techniques ont été mises en application dans le cadre de la 1ère campagne intensive du projet MERMAID. / This work aims at developing rapid and simple air sampling techniques followed by laboratory analyses to highlight the occurrence of the main species in indoor air and to describe their temporal variations. The analytical development was focused on 52 VOCs belonging to a wide variety of chemical families to determine their concentrations. The sampling step was performed using an automatic sampler allowing the sampling of air on adsorbent tubes. These tubes were then thermally desorbed and analyzed by gas chromatography coupled to FID. Another analytical development was conducted to determine the particle bound PAHs concentrations. The sampling of particles was realized by the mean of a 3-stages cascade impactor allowing an aerosol fractionation depending on their aerodynamic diameter. Finally, quantification of PAHs was realized by liquid chromatography coupled to fluorescence detection. These two techniques were applied in a field campaign in the frame of the MERMAID program.

Dans le but d’évaluer la contamination des atmosphères intérieures et extérieures induite par les usages non agricoles de pesticides, deux approches complémentaires ont été mises en oeuvre : l’utilisation de capteurs passifs de type Tenax TA pour réaliser des prélèvements d’air, et l’utilisation de cheveux employés comme biomarqueurs d’exposition. Des campagnes de mesures ont été menées sur plusieurs sites à la suite de traitements de désherbage ou de désinsectisation ainsi quedans des logements. Les échantillons d’air et de cheveux ont été extraits respectivement par thermodésorption et par extraction solide-liquide, avant d’être analysés en chromatographie gazeuse couplée à la spectrométrie de masse (GC-MS). Une augmentation du niveau de contamination de l’air extérieur et intérieur et l’existence de transferts entre ces deux milieux ont pu être observées après l’application de pesticides. Dans les logements, des pesticides actuellement employés mais aussi des pesticides interdits et persistants ont été détectés. Plusieurs pesticides ont également été détectés dans les cheveux, mais l’exposition humaine à ces derniers n’a pas pu toujours être corrélée à une contamination de l’air. / In order to evaluate indoor and outdoor air contamination resulting from non-agricultural uses of pesticides, two complementary approaches were applied: passive samplers based on Tenax TA used for air sampling and hair used as biomarkers of exposure. Sampling campaigns were conducted on several sites after weeding and pest control treatments as well as in accommodations. Air samples and hair samples were respectively extracted by thermal desorption and solid-liquid extraction prior to their analysis by gas chromatography combined with mass spectrometry (GC-MS). An increase of the indoor and outdoor air contamination levels and the existence of transfers between these two environments could be observed after pesticides applications. In accommodations, pesticides currently used and banned but persistent ones were detected. Several pesticides were also detected in hair samples but human exposure to these pesticides cannot be correlated with air contamination in all cases.

The history of surgery is nearly as old as the human race. Control of wound infection has always been an essential part of any surgical procedure, and is still an important challenge in hospital operating rooms today. For patients undergoing surgery there is always a risk that they will develop some kind of postoperative complication. It is widely accepted that airborne bacteria reaching a surgical site are mainly staphylococci released from the skin flora of the surgical staff in the operating room and that even a small fraction of those particles can initiate a severe infection at the surgical site.  Wound infections not only impose a tremendous burden on healthcare resources but also pose a major threat to the patient. Hospital-acquired infection ranks amongst the leading causes of death within the surgical patient population. A broad knowledge and understanding of sources and transport mechanisms of infectious particles may provide valuable possibilities to control and minimize postoperative infections. This thesis contributes to finding solutions, through analysis of such mechanisms for a range of ventilation designs together with investigation of other factors that can influence spread of infection in hospitals, particularly in operating rooms. The aim of this work is to apply the techniques of computational fluid dynamics in order to provide better understanding of air distribution strategies that may contribute to infection control in operating room and ward environments of hospitals, so that levels of bacteria-carrying particles in the air can be reduced while thermal comfort and air quality are improved.  A range of airflow ventilation principles including fully mixed, laminar and hybrid strategies were studied. Airflow, particle and tracer gas simulations were performed to examine contaminant removal and air change effectiveness. A number of further influential parameters on the performance of airflow ventilation systems in operating rooms were examined and relevant measures for improvement were identified. It was found that airflow patterns within operating room environments ranged from laminar to transitional to turbulent flows. Regardless of ventilation system used, a combination of all airflow regimes under transient conditions could exist within the operating room area. This showed that applying a general model to map airflow field and contaminant distribution may result in substantial error and should be avoided. It was also shown that the amount of bacteria generated in an operating room could be minimized by reducing the number of personnel present. Infection-prone surgeries should be performed with as few personnel as possible. The initial source strength (amount of colony forming units that a person emits per unit time) of staff members can also be substantially reduced, by using clothing systems with high protective capacity. Results indicated that horizontal laminar airflow could be a good alternative to the frequently used vertical system. The horizontal airflow system is less sensitive to thermal plumes, easy to install and maintain, relatively cost-efficient and does not require modification of existing lighting systems. Above all, horizontal laminar airflow ventilation does not hinder surgeons who need to bend over the surgical site to get a good view of the operative field. The addition of a mobile ultra-clean exponential laminar airflow screen was also investigated as a complement to the main ventilation system in the operating room. It was concluded that this system could reduce the count of airborne particles carrying microorganisms if proper work practices were maintained by the surgical staff. A close collaboration and mutual understanding between ventilation experts and surgical staff would be a key factor in reducing infection rates. In addition, effective and frequent evaluation of bacteria levels for both new and existing ventilation systems would also be important. / Tidigt i mänsklighetens utveckling har kirurgin funnits med i bilden. Hantering av infektioner har genom tiderna varit en oundviklig del av alla kirurgiska ingrepp, och finns kvar ännu idag som en viktig utmaning i operationssalar på sjukhus. För patienter som genomgår kirurgi finns alltid en risk att de efter ingreppet utvecklar någon behandlingsrelaterad komplikation. Allmänt accepterat är att de luftburna bakterier som når operationsområdet huvudsakligen består av stafylokocker frigjorda från hudfloran av operationspersonalen i operationssalen, och att endast en liten del av dessa partiklar behövs för att initiera en allvarlig infektion i det behandlade området. Sårinfektioner innebär inte bara en enorm börda för hälso- och sjukvårdsresurser, utan utgör också en betydande risk för patienten. På sjukhus förvärvad infektion finns bland de främsta dödsorsakerna i kirurgiska patientgrupper.. En bred kunskap och förståelse av spridningsmekanismer och källor till infektionsspridande partiklar kan ge värdefulla möjligheter att kontrollera och minimera postoperativa infektioner. Denna avhandling bidrar till lösningar genom analys av en rad olika ventilationssystem tillsammans med undersökning av andra faktörer som kan påverka infektionsspridningen på sjukhus, främst i operationssalar. Syftet med arbetet är att med hjälp av CFD-teknik (Computational Fluid Dynamics) få bättre förståelse för olika luftspridningsmekanismers betydelse vid ventilation av operationssalar och vårdinrättningar på sjukhus, så att halten av bacteriebärande partiklar i luften kan minskas samtidigt som termisk komfort och luftkvalité förbättras.  Flera luftflödesprinciper för ventilation inklusive omblandade strömning, riktad (laminär) strömning och hybridstrategier har studerats. Simuleringar av luft-, partikel- och spårgasflöden gjordes för alla fallstudier för att undersöka partikelevakuering och luftomsättning i rummet. Flera viktiga parametrar som påverkar detta undersöktes och relevanta förbättringar  föreslås i samarbete med industrin. Av resultaten framgår att mängden genererade bakterier i en operationssal  kan begränsas genom att minska antalet personer i operationsteamet. Infektionsbenägna operationer skall utföras med så lite personal som möjligt. Den initiala källstyrkan (mängden kolonibildande enheter som en person avger per tidsenhet) från operationsteamet kan avsevärt minskas om högskyddande kläder används. Av resultaten framgår också att ett horisontellt (laminärt) luftflöde kan vara ett bra alternativ till det ofta använda vertikala luftflödet. Ett horisontellt luftflöde är mindre känsligt för termisk påverkan från omgivningen, enkelt att installera och underhålla, relativt kostnadseffektivt och kräver vanligen ingen förändring av befintlig belysningsarmatur. Framför allt begränsar inte denna ventilationsprincip kirurgernas rörelsemönster. De kan luta kroppen över operationsområdet utan att hindra luftflödet. En flyttbar flexibel skärm för horisontell spridning av ultraren ventilationsluft i tillägg till ordinarie ventilation undersöktes också. Man fann att denna typ av tilläggsventilation kan minska antalet luftburna partiklar som bär mikroorganismer om operationspersonalen följer en strikt arbetsordning. Bra samarbete och förståelse mellan ventilationsexperter och operationsteamet på sjukhuset är nyckeln till att få ner infektionsfrekvensen. Det är också viktigt med effektiva och frekventa utvarderingar av bakteriehalten i luften, för såväl nya  som befintliga ventilationssystem. / <p>QC 20160129</p>