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No. of bitstreams: 1 rolisola_amcm_dr_rcla.pdf: 4377095 bytes, checksum: da8491d59c9f3875c68e364b6648d0cf (MD5) Previous issue date: 2018-05-02 / Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq) / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP) / Atualmente, cerca de 18 compostos são utilizados como biocidas de reforço (metálicos) em tintas anti-incrustantes, como por exemplo Piritionato de Zinco (Zn(PT)2), Zineb e Ziram. É relevante o desenvolvimento de um método analítico para determinação das concentrações ambientais de biocidas metálicos. O presente estudo teve como objetivos i)desenvolver uma metodologia de extração em fase sólida (SPE) e cromatografia líquida de alta eficiência acoplada (HPLC) ao espectrômetro de massas com plasma acoplado indutivamente (ICP-MS) para determinação de Zn(PT)2, Zineb e Ziram e ii) quantificar, in lab, a fração lábil total do Piritionato de Zinco, Zineb e Ziram e in situ, a fração lábil total do zinco, utilizando a técnica de difusão em filmes finos por gradiente de concentração (DGT) em solução padrão e água estuarina, respectivamente. Na técnica de SPE foi utilizado o sorbente de sílica funcionalizado com fenil apresentando excelente retenção para Zn(PT)2, Zineb e Ziram (94 ± 0,1%, 85 ± 0,04% e 93 ± 0,1%, respectivamente) e recuperações entre 85% e 110%. Na determinação dos biocidas de zinco utilizando o acoplamento HPLC-VGroove-ICP-MS com diluição pós coluna cromatográfica, a fase móvel composta por metanol e 0,006 mol L-1 de acetato de amônio (50:50, v v-1) apresentou o melhor desempenho na separação do Zn(PT)2, Zineb, Ziram. A curva analítica obtida para o Zn(PT)2 apresentou coeficiente de correlação, LD e LQ satisfatórios para os isótopos 64Zn (0,98, 0,575 mg L-1, 1,916 mg L-1), 66Zn(0,99, 0,480 mg L-1 , 1,600 mg L-1), 68Zn(0,98, 0,602 mg L-1, 2,007 mg L-1). Na técnica DGT foi utilizado o agente ligante resina Chelex® 100 para avaliar a labilidade do Zn(PT)2, Zineb e Ziram em água estuarina. Os resultados demonstraram que a fração lábil total do Zn ficou em torno de 100% para o Zineb (111%) e Ziram (109%), ou seja, estes biocidas formaram espécies totalmente lábeis na amostra de água estuarina e para Zn(PT)2 foi de 75% indicando espécies parcialmente lábeis. Os resultados obtidos na técnica SPE, no acoplamento HPLC-VGroove-ICP-MS e DGT demonstraram que os métodos apresentam desempenho satisfatório para a determinação de Piritionato de Zinco, Zineb e Ziram. / About 18 compounds are used as booster biocides (metal) in antifouling paints such as Zinc Pyrithione (Zn(PT)2), Zineb and Ziram. It is important to develop an analytical method for determining of the environmental concentrations of zinc biocides. The present study had as objectives i) to develop a solid phase extraction (SPE) and high performance liquid chromatography (HPLC) coupled to the inductively coupled plasma mass spectrometer (ICP-MS) for the determination of Zn(PT)2, Zineb and Ziram and ii) quantify in lab the total labile fraction of Zn(PT)2, Zineb and Ziram and in situ the total labile fraction of zinc using the diffusive gradient in thin films (DGT) technique in standard solution and estuarine water, respectively. In the SPE technique, the silica sorbent functionalized with phenyl presented excellent retention for Zn(PT)2, Zineb and Ziram (94 ± 0.1%, 85 ± 0.04% and 93 ± 0.1%, respectively) and recoveries between 85% and 110%. In the determination of zinc using the HPLC-VGroove-ICP-MS coupling with post-column chromatographic dilution, the mobile phase composed of methanol and 0.006 mol L-1 of ammonium acetate (50:50, v v-1) of presented the best performance in the separation of Zn(PT)2, Zineb and Ziram. The analytical curve obtained for Zn(PT)2 presented satisfactory correlation coefficient, LD and LQ for the isotopes 64Zn (0.98, 0.575 mg L -1, 1.916 mg L-1), 66Zn (0.99, 0.480 mg L-1, 1.600 mg L-1), 68Zn (0.98, 0.602 mg L-1, 2.007 mg L-1). In the DGT technique, the Chelex® 100 resin binder was used to evaluate the lability of the zinc biocides Zn(PT)2, Zineb and Ziram in estuarine water. The results showed that the total labile fraction of Zn was around 100% for Zineb (111%) and Ziram (109%), that is, these biocides formed totally labile species in the estuarine water sample and for Zn(PT)2 was 75% indicating partially labile species. The results obtained in the SPE technique in the HPLC-VGroove-ICP-MS coupling and DGT demonstrated that the methods present satisfactory performance for the determination of Zn(PT)2, Zineb and Ziram. / CNPq: 164326/2015. / FAPESP: 2015/03397-4.

Cette étude s'est concentrée sur la performance d'un filtre antimicrobien en fibres de polypropylène contenant de la pyrithione de zinc (PP/ZPT) au laboratoire et comparée à celle d'un filtre similaire (PP) avec la même classification F7 (EN779:2002). La performance de filtration à l'échelle du laboratoire des 2 filtres testés pendant le colmatage avec des particules PM10 a été quantifiée dans un dispositif expérimental avec mesure de la perte de charge du filtre et comptage des particules en amont et en aval des filtres. La croissance microbienne sur des filtres neufs et usagés, tous deux contaminés par aérosolisation avec un consortium microbien composé de deux bactéries (Staphylococcus epidermidis Gram positif, Serratia marcescens Gram négatif et spores fongiques (Penicillium chrysogenum). L'influence de trois paramètres sur la survie microbienne sur les filtres a été examinée : l'humidité relative de l'air, la présence ou l'absence de pyrithione de zinc (ZPT) en tant que substances antimicrobiennes et la présence de particules organiques. Des analyses quantitatives par unité formant colonies ont été utilisées pour déterminer la survie après 8 jours du consortium bactéries-champignons collecté par le filtre. Les deux filtres ont présenté des performances de filtration similaires en termes de variation de perte de charge et d'efficacité de collecte des particules pendant leur colmatage avec des particules PM10, ce qui signifie que le traitement antimicrobien n'a pas dégradé les performances de filtration du filtre. A faible valeur d'humidité de conditionnement (50% RH), avec des filtres neufs ou usagés, avec ou sans traitement antimicrobien, la population microbienne sur les filtres diminue et éventuellement ne survivra pas (Serratia). Lorsque l'humidité relative du conditionnement est élevée (90% RH), les bactéries ne se développent pas sur les filtres neufs, et seuls les champignons ont pu se développer. L'effet du traitement antimicrobien avec la pyrithione de zinc est confirmé pour les filtres neufs, en particulier en ce qui concerne les champignons Penicillium. Pour les filtres usagés, les résultats indiquent que le traitement antimicrobien n'est pas plus efficace avec une croissance significative du Penicillium, l'espèce endémique des particules de riz micronisées (PM10) collectées par les filtres ; les deux populations de bactéries diminuent significativement avec ou sans traitement antimicrobien.Dans une deuxième étape, les performances de filtration des 2 filtres testés précédemment ont été étudiées dans des conditions réalistes avec un air extérieur semi-urbain sur une période de 7 mois. Le comportement des microorganismes extérieurs sur les filtres (croissance/mortalité) a été observé. Deux unités de filtration fonctionnaient à IMT Atlantique, l'une contenant le filtre PP/ZPT et l'autre le filtre PP. Chaque unité filtrait le même air semi-urbain. Les deux unités de filtration ont fonctionné en continu et plusieurs paramètres ont été surveillés tout au long de la période d'exploitation : température, humidité relative, chute de pression du filtre, efficacité de collecte des particules du filtre, concentration massique des particules à l'entrée et concentrations microbiennes ; en outre, la concentration microbienne sur les filtres a été quantifiée 3 fois (tous les 2 mois) à partir d'une méthodologie innovante basée sur des coupons de média. Les performances de filtration des deux filtres testés en termes de changement de perte de charges et d'efficacité de collecte de particules étaient différentes de celles obtenues à l'échelle du laboratoire. La méthodologie des coupons a permis d'étudier le comportement des micro-organismes tout au long de l'étude. L'effet antimicrobien de la pyrithione de zinc a été confirmé concernant l'inhibition des champignons sans influence du niveau d'encrassement du filtre (dépôt de masse de particules). / This study focused on the performance of a marketed antimicrobial polypropylene fibers filter containing zinc pyrithione (PP/ZPT) at the laboratory and compared to those of a similar filter (PP) with same classification F7 (EN779:2002). The filtration performance at laboratory scale of the 2 tested filters during clogging with PM10 particles was quantified in an experimental set-up with filter pressure drop measurement and particle counting up and downstream of the filters. The microbial growth onto new and used filters, both contaminated by aerosolization with a microbial consortium composed of two bacteria (Staphylococcus epidermidis Gram positive, Serratia marcescens Gram negative and fungal spores (Penicillium chrysogenum). The influence of three parameters on the microbial survival onto filters was examined: the air relative humidity, the presence or absence of Zinc pyrithione (ZPT) as antimicrobial substances and the presence of organic particles. Quantitative analyses by colony forming unit were used to determine the survival after 8 days of the bacteria–fungi consortium collected by the filter. The two filters revealed similar filtration performance in terms of change in pressure drop and particle collection efficiency during their clogging with PM10 particles, meaning that the antimicrobial treatment did not degrade the filtration performance of the filter. At low humidity value of conditioning (50% RH), with new or used filters, with or without antimicrobial treatment, the microbial population onto the filters decreases and possibly will not survive (Serratia). At high humidity value of conditioning (90% RH), the bacteria do not grow onto the new filters, and only the fungi was able to develop. The effect of the antimicrobial treatment with zinc pyrithione is confirmed for new filters in particular regarding the fungi Penicillium. For used filters, the results indicate that the antimicrobial treatment is no more efficient with a significant growth of the Penicillium, the endemic species of the micronized rice particles (PM10) collected by the filters; the two populations of bacteria significantly decrease with or without antimicrobial treatment. In a second step, the filtration performances of the 2 filters tested previously was investigated in realistic conditions with a semi-urban outdoor air over a 7 months period. The behavior of the outdoor microorganisms onto the filters (growth/mortality) was observed. Two filtration units were operating at IMT Atlantique location, one containing the PP/ZPT filter and the second the PP filter. Each unit filtered the same semi-urban air. Both filtration units operated continuously and several parameters were monitored throughout the operating period: temperature, relative humidity, filter pressure drop, filter particle collection efficiency, inlet particle mass concentration, and microbial concentrations; in addition, the microbial concentration onto the filters was quantified for 3 times (every 2 months) from an innovative methodology based on media coupons. The filtration performances of the two tested filters in terms of changes in pressure drop and particle collection efficiency were different than those obtained in the Laboratory scale. The methodology of coupons permitted to study the behavior of the microorganisms throughout the study. The antimicrobial effect of the zinc pyrithione was confirmed regarding the inhibition of the fungi cultivated on the DRBC agar with no influence of the level of clogging of the filter (mass of particles deposit).