Traditional aerosol samplers are limited in their abilities to collect large quantities of particulate matter due to their low flow rates, high pressure drops, and are noise intrusiveness. The goal of this study was to develop an alternate aerosol sampler using electrostatic precipitation technology that was safe and not noise intrusive to be deployed in homes. The O-Ion B-1000 was selected as the most suitable electrostatic precipitator (ESP) for achieving the goal of this study because of its affordability, the design of its collection electrode and its high flow rate. The collection efficiency of the ESP was assessed for three aerosols; Arizona Road Dust (ARD), NaCl and diesel fumes. ARD was found to have the highest average collection efficiency (65%) followed by NaCl (43%) and lastly diesel fumes (41%). A method for recovering the particulate matter deposited on the collection electrode was developed. The dust collected on the electrode was recovered onto polyvinyl chloride (PVC) filters moistened with deionized water. Additionally, the recovery of the three test aerosols, ARD, NaCl, and diesel fumes, from the collection electrode was assessed. A gravimetric analysis was done to determine the amount of dust recovered. The collection efficiency was used to calculate the amount of mass expected on the filter for a particular aerosol. NaCl had the highest recovery at 95% recovery, followed by ARD (73%) and lastly diesel fumes (50%). Two identical ESPs were also deployed in an office and in a bedroom, 104.47 mg and 9.64 mg of particulate matter (PM) was recovered respectively. The noise and ozone level produced by the ESP was evaluated to determine the ESP’s viability as a household aerosol sampler. The ESP’s high setting had a noise level of 45.8 dB and ozone generation rate of 0.036 mg/min. The results of the calculation showed that in an averaged size unventilated room (6.10 m × 6.10 m × 2.44 m), it would take 6 hours and 53 minutes for the ozone levels to reach the recommended maximum exposure limits per National Ambient Air Quality Standards (NAAQS). Additionally, a ventilation of 230 L/min is needed in order to prevent the ozone levels generated by the ESP from exceeding maximum exposure limits per NAAQS. Overall, the O-Ion B-1000 met the criteria of collecting 1 mg of PM in a 24 hour sampling for ARD and NaCl. Diesel fumes however, required 30 hours to collect 1 mg of PM. The noise levels generated by the ESP set on high was one dB above the Environmental Protection Agency (EPA) standards for indoor noise limit. However, the noise is proportional to inverse distance squared; the ESP should not pose a problem during household deployment. Ozone generated by the ESP was also found to be below 0.07 ppm as set by the EPA with an average ventilation of 230 L/min. The average ventilation of a household is 1500 L/min, thus the ozone generated by the ESP would not surpass 0.07 ppm. However, the ESP should not be deployed in unventilated rooms for a period of more than 6 hours and 53 minutes.

Agricultural operations across the United States are encountering difficulties complying with current air pollution regulations for particulate matter (PM). PM is currently regulated in terms of particle diameters less than or equal to a nominal 10 μm (PM10); however, current legislation is underway to regulate PM with diameters less than or equal to a nominal 2.5 μm (PM2.5). The goals of this research were to determine the biases and uncertainties associated with current PM10 and PM2.5 sampling methods and to determine the extent to which these errors may impact the determination of cotton gin emission factors. Ideally, PM samplers would produce an accurate measure of the pollutant indicator; for instance, a PM10 sampler would produce an accurate measure of PM less than or equal to 10 μm. However, samplers are not perfect and errors are introduced because of the established tolerances associated with sampler performance characteristics and the interaction of particle size and sampler performance characteristics. Results of this research indicated that a source emitting PM characterized by a mass median diameter (MMD) of 20 μm and a geometric standard deviation (GSD) of 1.5 could be forced to comply with a 3.2 and 14 times more stringent regulation of PM10 and PM2.5, respectively, than a source emitting PM characterized by a MMD of 10 μm and a GSD of 1.5. These estimates are based on both sources emitting the same concentrations of true PM or concentrations corresponding to the particle diameters less than the size of interest. Various methods were used to estimate the true PM10 and PM2.5 emission factors associated with cotton gin exhausts and the extent to which the sampler errors impacted the PM regulation. Results from this research indicated that current cotton gin emission factors could be over-estimated by about 40%. This over-estimation is a consequence of the relatively large PM associated with cotton gin exhausts. These PM sampling errors are contributing to the misappropriation of source emissions in State Implementation Plans, essentially forcing Air Pollution Regulatory Agencies to require additional controls on sources that may be incorrectly classified has high emitters.

Στα κεφάλαια που ακολουθούν, αρχικά παρουσιάζεται μια σύντομη περιγραφή της περιοχής του Βελβιτσίου που ανήκει στην ευρύτερη περιοχή των Πατρών, όπου παρατηρούνται έντονα κατολισθητικά φαινόμενα. Σκοπός της συγκεκριμένης εργασίας είναι η ανάλυση και ο σχεδιασμός των γεωτεχνικών συνθηκών της κατολίσθησης που εκδηλώθηκε την 04-02-2009 στη δημοτική οδό του οικισμού Βελβιτσίου Δήμου Πατρών. Στη συνέχεια παρουσιάζονται αναλυτικά ο τρόπος και οι θέσεις γεωτρήσεων ενώ παρέρχονται και στοιχεία από την γεωλογία της περιοχής σε μια προσπάθεια να συγκεντρωθούν κατά το δυνατόν περισσότερα δεδομένα που σχετίζονται με τις κατολισθήσεις που παρατηρήθηκαν. Τέλος δίνονται τα αποτελέσματα των εργαστηριακών δοκιμών και παρουσιάζονται τα συμπεράσματα που προέκυψαν. Στα πλαίσια του στόχου της πλήρους ανάλυσης και της απόδοσης μια ολοκληρωμένης εικόνας του φαινομένου αυτού, εκτελέστηκαν οι ακόλουθες εργασίες: • Αποτύπωση όλων των πληροφοριών που σχετίζονται με την υφιστάμενη κατάσταση στην περιοχή έρευνας. • Τεχνικογεωλογική χαρτογράφηση, αποτύπωση της κατολίσθησης και των αστοχιών στην περιοχή έρευνας. • Ανόρυξη τριών δειγματοληπτικών γεωτρήσεων συνολικού μήκους 43,30μ. • Εκτέλεση επί-τόπου δοκιμών SPT και μετρήσεις στάθμης ύδατος. • Εκτέλεση εργαστηριακών δοκιμών για τον προσδιορισμό των φυσικο-μηχανικών ιδιοτήτων των γεωλογικών σχηματισμών που διατρήθηκαν. • Σύνταξη τεχνικής έκθεσης με παρουσίαση των αποτελεσμάτων των αναλύσεων ευστάθειας των πρανών και της οδού, πριν και μετά την κατασκευή των προτεινόμενων έργων. • Σχεδιασμός έργων αντιμετώπισης της κατολίσθησης και αντιστήριξης της οδού με τις ανάλογες τυπικές διατομές. / -

L’augmentation globale de la démographie couplée à une amélioration du niveau de vie conduit à l’augmentation de la pression anthropique pesant sur les ressources en eau. Cette pression passe entre autre par une consommation et donc un rejet de multiples molécules organiques, parmi lesquelles les pesticides représentent des contaminants emblématiques. Longtemps utilisés en agriculture afin d’en augmenter la productivité, ces substances sont aujourd’hui utilisées également de façon importante dans notre quotidien (traitements vétérinaires, protection des matériaux de construction, peintures, papier, textiles, etc.). Cela conduit à identifier les rejets urbains comme des vecteurs de pesticides au travers des effluents de station de traitement des eaux usées ou des effluents d’exutoires pluviaux, qui viennent s’ajouter aux apports induits par l’agriculture. Cette multiplicité de sources couplée à une toxicité intrinsèque avérée en font des molécules à fort enjeu environnemental dont il est essentiel de hiérarchiser les apports afin de pouvoir mettre en place des mesures de réduction.Dans ce cadre, un continuum péri-urbain situé sur la Métropole de Bordeaux (France) a permis de mettre en évidence des profils de contamination différents entre les eaux naturelles, les effluents urbains et les exutoires pluviaux, tant sur l’aspect qualitatif que sur l’aspect quantitatif. Si les eaux de surface sont principalement quantitativement marquées par des phytopharmaceutiques (métolachlore, glyphosate), les molécules identifiées comme potentiellement impactantes (en termes d’effets potentiels) proviennent d’avantage d’effluents urbains (fipronil, imidaclopride). En effet, les stations de traitement des eaux usées sont identifiées comme d’importants vecteurs en biocides et antiparasitaires à usages vétérinaires en raison de leur faible capacité de traitement vis-à-vis de ces contaminants. Toutefois, ces effluents ne sont que le reflet des utilisations en amont du réseau. L’investigation de ce dernier a conduit à identifier les usages domestiques comme responsables de l’introduction de certaines molécules préoccupantes tels les antiparasitaires à usages vétérinaires (fipronil et imidaclopride). En parallèle, bien que non majoritaires en ce qui concerne les apports en pesticides, les exutoires pluviaux ne sont toutefois pas négligeables et apportent en quantités conséquentes des biocides de protection (comme la carbendazime, le diuron, le propiconazole ou la terbutryne) de par le lessivage de surfaces traitées en zones urbaines. Le cas du glyphosate semble complexe puisque aucune des voie d’apport n’est clairement identifiée comme majoritaire. L’apport est très global, probablement du fait de sa multiplicité d’usages, tant en agriculture que par certains professionnels ou par les particuliers.L’échantillonnage passif par les POCIS (Polar Organic Chemicals Integrative Sampler) a été appliqué avec succès afin de calculer des flux plus précis dans les eaux de surfaces, permettant ainsi une identification plus fine des sources majoritaires. Cet outil montre toutefois ses limites en ce qui concerne le suivi d’échantillons complexes telles que les eaux brutes, en présentant des cinétiques d’accumulation trop courtes pour permettre un suivi quantitatif du réseau d’assainissement sur de longues périodes. Ces observations ont été confirmées à l’occasion de calibrations in-situ en rivière et en entrée de station de traitement des eaux usées et qui ont donné lieu au développement de nouveaux outils. Les mini-POCIS et les POCIS-T, plus légers et plus petits ont été calibrés à la fois en laboratoire et en station de traitement des eaux usées. Ils se sont révélés plus adaptés que la forme classique pour suivre la contamination des eaux usées car ils permettent d’augmenter la durée du suivi. Ils représentent une alternative intéressante pour le suivi du réseau d’assainissement. / Global demographic increase coupled with standard of living increase drive water resources’ anthropic pressure. This phenomenon is linked with consumption habits and with chemicals dispersion in environment. Pesticides are part of the most concerning contaminants. They were firstly used to enhance agricultural productivity but nowadays these chemicals are used for our daily life needs (in building materials, veterinary treatments, papers, textile products, paints, etc.) and so urban effluents such as storm sewer or wastewater treatment plant effluents are identified as important vectors of pesticides which are added to agricultural inputs. The diversity of sources coupled to an intrinsic toxicity highlight pesticides as environmental concerning compounds and their sources have to be clearly identified and classified to consider source reduction actions.The study of an urban continuum in Bordeaux Metropolis (France) highlighted qualitative and quantitative differences in contamination profiles between river water, storm sewers and wastewater treatment plant effluents. River waters are contaminated with phytopharmaceuticals (metolachlor, glyphosate) but molecules of high ecotoxicological concern (fipronil, imidacloprid) are mostly brought by wastewater treatment plants. These structures are indeed not built for micropollutant treatment and biocides provided by wastewaters are discharged in surface water. Urban effluents reflect uses of wastewater network by private consumers and industries. Advanced investigations in the wastewater network allowed identifying them as providers of veterinary molecules such as fipronil and imidacloprid. In parallel, monitoring of rain effluents allowed to identify storm sewers as less important sources of pesticides that wastewaters but they have to be considered for some molecules. Indeed, they can locally increase contamination in natural water around the discharge site especially concerning biocides (carbendazime, diuron, propiconazole, terbutryne) because of runoff waters over treated surfaces. Case of glyphosate is much more complex because this molecule was found in every compartment and seemed to be introduced massively both by agriculture and urban effluents in link with its use by farmers but also private consumers and some professionals.Passive sampling of water resources with POCIS (Polar Organic Chemicals Integrative Sampler) was successfully applied, allowing to quantify pesticides at trace levels and to calculate precise fluxes leading to the confirmation of previous results. However, the usefulness of this tool is limited in the case of wastewater monitoring. Uptake kinetics are too rapid to allow a quantitative characterisation of raw wastewaters over long period of deployment. These observations were confirmed with the comparison of in-situ calibration performed both in river and in effluent of a wastewater treatment plant and leaded to the development of new version of POCIS. Mini-POCIS and POCIS-T (lighter and smaller than original ones) were calibrated both in laboratory and in real conditions. They are more adapted than classical devices to wastewater sampling allowing covering a much longer period of monitoring.

Submitted by Ana Hilda Fonseca (anahilda@ufba.br) on 2013-03-27T15:24:14Z No. of bitstreams: 1 Tese de Maria Andréa da Silva.pdf: 2665297 bytes, checksum: 5d7613a0f2ca73967ba58859bd84a7f5 (MD5) / Approved for entry into archive by Ana Hilda Fonseca(anahilda@ufba.br) on 2013-04-15T14:01:43Z (GMT) No. of bitstreams: 1 Tese de Maria Andréa da Silva.pdf: 2665297 bytes, checksum: 5d7613a0f2ca73967ba58859bd84a7f5 (MD5) / Made available in DSpace on 2013-04-15T14:01:43Z (GMT). No. of bitstreams: 1 Tese de Maria Andréa da Silva.pdf: 2665297 bytes, checksum: 5d7613a0f2ca73967ba58859bd84a7f5 (MD5) Previous issue date: 2012 / CAPES / Neste trabalho foram usados amostradores passivos POCIS e Chemcatcher com a técnica de Extração em Fase Sólida SPE e a Cromatografia Gasosa acoplada à Espectrometria de Massas, GC/MS. O objetivo geral do trabalho foi desenvolver uma metodologia para os amostradores passivos POCIS e Chemcatcher para a análise de agrotóxicos em água superficial e os objetivos específicos: estudar o desempenho dos amostradores passivos através de desenvolvimento de metodologia SPE e GC/MS, calibrar em laboratório, determinando as taxas de amostragem e implantar os amostradores na região do Vale do São Francisco, em Petrolina, Pernambuco. O sorvente usado na SPE foi à base de sílica modificada (C18) e os solventes foram metanol e diclorometano. A validação do método foi feita para disco e cartucho, onde, o LD para disco variou de 0,0080 a 0,096 μg L-1 e para cartucho 0,0070 a 0,43 μg L-1, o LQ de 0,026 a 0,32 μg L-1 e 0,024 a 1,4 μg L-1, respectivamente. Os percentuais de recuperação para o disco variaram de 70,0 a 119,9 para disco e 70,2 a 119,7 para cartucho. Os desvios-padrões para o disco variaram de 2,86 a 19,9 e para cartucho 1,89 a 19,8. A repetitividade com 95% de confiança para disco variou de 0,0070 a 0,089 e 0,0070 a 0,41 para cartucho. As taxas de amostragem para os dispositivos POCIS e Chemcatcher variaram, respectivamente: para 1 dia: sem membrana, 0,105 a 0,693 L dia-1 e 0,100 a 0,757 L dia-1; com membrana PES < 0,0080 a 0,069 L dia-1 e <0,0080 a 0,050 L dia-1; com malha de nylon 0,103 a 0,333 L dia-1 e 0,093 a 0,33 L dia-1. Para 3 dias com renovação de água: com membrana PES < 0,011 a 0,083 L dia-1 e < 0,011 a 0,042 Ldia-1; com malha de nylon 0,077 a 0,80 L dia-1 e 0,074 a 0,95 L dia-1. Durante três dias sem renovação de água: com malha de nylon 0,067 a 0,28 L dia-1 e 0,064 a 0,31 L dia-1. Taxas de amostragem teóricas foram calculadas em função dos coeficientes de difusão dos pesticidas em água e do desenho e configuração dos dois modelos de amostradores passivos. As taxas de amostragem para o POCIS e Chemcatcher variaram respectivamente de 0,11 a 0,23 L dia-1 e 0,077 a 0,16 L dia-1. Considerando-se um ambiente aquático com baixa contaminação (ao nível do LQ do método) o tempo de exposição dos amostradores para captar os pesticidas pode variar, a depender do composto, de 3 a 9 dias para o POCIS e de 4 a 10 dias para o Chemcatcher. O desempenho dos dois modelos pode ser considerado semelhante e seu uso com a técnica SPE e GC/MS é uma alternativa para a metodologia de determinação de pesticidas em água, uma vez que o procedimento é simples, rápido e econômico. / Salvador

Depuis 2001 et la création d'un observatoire de la qualité de l'air intérieur (OQAI), la qualité de l'air intérieur est devenue un enjeu majeur de santé publique et fait l'objet d'un cadre réglementaire qui continue d'évoluer au cours des dernières années. Deux décrets récents, en France, prévoient la mise en œuvre de l'étiquetage des matériaux de construction en fonction de leurs émissions de composés organiques volatils (COV) (décret n° 2011-321, 23/03/2011) et le contrôle de la concentration des polluants (benzène et formaldéhyde) avec un guide des valeurs pour les bâtiments ouverts au public (n ° 2011-1728, 12/02/2012). De nos jours, la méthode analytique utilisée pour mesurer la concentration en formaldéhyde dans l'air consiste en un prélèvement sur cartouche de 2,4-dinitrophénylhydrazine (DNPH), qui est analysée par chromatographie en phase liquide après extraction. Cette méthode nécessite un équipement lourd et une étape en laboratoire est nécessaire. La société Ethera développe et commercialise des capteurs spécifiques pour la détection et la mesure du formaldéhyde avec des échantillonneurs passifs ou actifs. Ce capteur est basé sur des matrices nanoporeuses contenant du Fluoral-P (4-amino-3-pentène-2-one), qui réagit sélectivement avec le formaldéhyde pour produire un composé coloré de la 3,5-diacétyl-1,4-dihydrolutidine (DDL). La DDL est détectée à 420nm par lecture optique et la différence de densité optique mesurée avant et après l'exposition du capteur est directement proportionnelle à la concentration en formaldéhyde dans l'air intérieur. Le but de cette thèse est d'améliorer les performances des échantillonneurs passifs. Les différentes phases du développement des échantillonneurs passifs sont étudiées (conception, évaluation en chambre d’exposition) avec différentes approches et méthodologies. Deux axes d'étude sont considérés: une approche théorique et des essais en laboratoire. Une approche théorique a été mise en œuvre pour optimiser un échantillonneur passif ou dimensionner un nouveau préleveur. Les tests de laboratoire ont permis d'évaluer les paramètres métrologiques des échantillonneurs passifs (limite de détection, sensibilité, répétabilité, linéarité ...) et les effets des facteurs d'exposition (température, humidité relative, concentration). / Since 2001 and the creation of a French Indoor Air Quality Observatory (OQAI), indoor air quality has become a major public health issue. It is the subject of a regulatory framework that continues to evolve in recent years. Two recent decrees, in France, foresee the implementation of the labeling of building materials according to their emissions of volatile organic compounds (VOCs) (decree n°2011-321, 23/03/2011) and the survey of air concentration of two pollutants (benzene and formaldehyde) with guide values in public buildings (n°2011-1728, 2/12/2012). Today, the analytical method used to measure formaldehyde concentration in air consists in a 2,4-dinitrophenylhydrazine (DNPH) sampling cartridge which is analyzed by liquid chromatography after solvent extraction. This method is time consuming, expensive and complicated to perform. The company Ethera develops and markets specific, sensitive sensors for detection and measurement of formaldehyde with passive or active samplers. This sensor is based on a nanoporous matrix containing Fluoral-P (4-amino-3-penten-2-one), which selectively reacts with formaldehyde to produce a colored compound the 3,5-diacetyl-1,4-dihydrolutidine (DDL). DDL is detected at 420nm by optical reading and the difference of the optical density measured before and after exposition of the sensor is directly proportional to the concentration of formaldehyde in air. The purpose of this thesis is to improve the performance of passive samplers. The different phases of the development of passive samplers are studied (design, evaluation in environmental chamber) with different approaches and methodologies. In fact, two axis of study are considered: a theoretical approach and laboratory tests. Theoretical approach will be implemented to optimize a passive sampler or for sizing a new one based on the study of theoretical sampling rates. Laboratory tests will allow to assess metrological parameters of passive samplers (detection limit, sensitivity, repeatability, linearity…) and to estimate effects of exposure factors (temperature, relative humidity, concentration levels …).

The aim of this study was to investigate a potential impact of the old polychlorinated biphenyls (PCBs) dump on their occurrence in Bezdrevsky stream basin. Wastes, containing PCBs, were illegally stored in the area of ex-agrochemical factory in Lhenice village. Six localities were chosen for sampling by the method of integrative passive samplers SPMD, which provides more valuable information about contamination than commonly used grab samples. Passive samplers were exponated for 18 days in June 2017. The samples extraction was performed at the Laboratory of environmental chemistry and biochemistry (Faculty of fisheries and protection of waters), followed by clean up and preparation of these extracts for analysis with gas chromatograph coupled to tandem mass spectrometer (GC-MS/MS). Obtained data on PCBs amount in the samples were recalculated to their concentration in water. Concentration of seven indicator PCBs congeners (PCB 28 + 31, PCB 52, PCB 101, PCB 118, PCB 138, PCB 153 a PCB 180) was determined. These congeners are typical for technical PCBs mixtures which were produced in Czechoslovakia in the past. From their relative abundance, the potential source and an age of the contamination were estimated. Their total sum indicated significant exceedance of the limit only for the first locality, in the reservoir draining the dump area. There was found the concentration of 100 ng.l-1 of the 7 indicator PCBs sum. Concentrations at other localities complied with required limits and varied between hundredths to tenths of ng.l-1. In comparison with older data acquired from this area, the concentration at the first locality did not change, whereas PCBs concentration at the second and third locality downstream is currently lower than in past. Our data were compared to the latest data of PCBs concentrations in selected localities in CZ, which were received from Czech hydrometeorological intitute. From measured values can be stated, that the basin of Bezdrevsky stream and its fish pond system are not endangered by the presence of PCBs. Only two localities situated near the source of PCBs are comparable with localities in CZ which are influenced by the long term industry presence.

Made available in DSpace on 2014-10-09T12:35:09Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T14:00:32Z (GMT). No. of bitstreams: 0 / Dissertação (Mestrado) / IPEN/D / Instituto de Pesquisas Energeticas e Nucleares - IPEN-CNEN/SP

Made available in DSpace on 2014-10-09T12:35:21Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T14:06:18Z (GMT). No. of bitstreams: 0 / Dissertação (Mestrado) / IPEN/D / Instituto de Pesquisas Energeticas e Nucleares - IPEN-CNEN/SP

Made available in DSpace on 2014-10-09T12:35:09Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T14:00:32Z (GMT). No. of bitstreams: 0 / Neste trabalho foi realizada a investigação de interações hiperfinas em amostra nano estruturadas e filmes finos de dióxido de háfnio por meio da técnica de correlação angular gama-gama perturbada (CAP), com o intuito de realizar um estudo sistemático do comportamento dos parâmetros quadrupolares com a temperatura de tratamento térmico. Para a realização destas medidas foi utilizada a ponta de prova 181Hf -> 181Ta que foi produzida na própria amostra por irradiação, no reator IEA-R1 do IPEN. As amostras foram obtidas através do processo químico sol-gel e as análises dos compostos realizadas por difração de raios-X, EDS e MEV. As amostras em forma de pó foram todas produzidas pelo Laboratório de Interações Hiperfinas do IPEN, no entanto o filme fino com espessura de 10nm foi produzido pelo Centro de Lasers e Aplicações (CLA) do IPEN e o filme fino de espessura de 409nm foi produzido pelo Laboratório de Interações Hiperfinas da Universidade de Lisboa. As medidas foram realizadas todas à temperatura ambiente e os resultados mostraram que a fase monoclínica encontra-se presente em todas as amostras e sua fração tende a aumentar sempre com o aumento da temperatura de tratamento térmico na qual foram submetidas às amostras. A impurificação de algumas amostras com elementos Co e Fe foi realizada com a intenção de se observar o comportamento da amostra em função da temperatura de tratamento térmico e também verificar a existência de ferromagnetismo à temperatura ambiente. / Dissertação (Mestrado) / IPEN/D / Instituto de Pesquisas Energeticas e Nucleares - IPEN-CNEN/SP