For widespread use of biochar in agriculture and horticulture, it must be ensured that application will neither adversely affect soil and plants, nor exceed legislated contaminant concentrations. The most relevant groups of contaminants in biochar are potentially toxic elements (PTEs), polycyclic aromatic hydrocarbons (PAHs) and volatile organic compounds (VOC). In this thesis, the concentrations of these groups of contaminants were analysed in 90 different biochars produced by slow pyrolysis. Subsequently, the concentrations were compared to legislation/guideline threshold values and linked to production conditions. The risk these contaminants pose to plant growth was also assessed, to give recommendations on production of safe biochar. PTEs can neither be formed nor destroyed, which means their presence in biochar is predominantly determined by feedstock type. However, significant levels of Cr, Fe and Ni were introduced into biochar from the furnace steel, whilst PTEs with low boiling points, such as As, Cd and Zn, partially evaporated during pyrolysis. PTEs were not responsible for phytotoxic effects observed for PTE-rich biochars despite biochar’s exceedance of available and total PTE threshold values for soil and soil amendments. Although initial tests were promising, the risk that PTE-rich biochars as amendment for soil and growing media pose, needs further investigation. The PAH concentration in biochar was markedly reduced by increasing carrier gas flow rate, and the type of feedstock also influenced the PAH content. However, there was no clear dependence of pyrolysis temperature on PAH concentrations, which was attributed to PAHs being increasingly formed and evaporated at higher pyrolysis temperatures. Ultimately, condensation of pyrolysis vapours and deposition on biochar was identified as the main risk for biochar contamination with PAHs, as this resulted in elevated concentrations of high-risk, higher molecular weight PAHs. Weaknesses in the pyrolysis unit design, such as cold zones, resulted in elevated concentrations of VOCs, as well as PAHs, in biochar. Comparing concentrations and phytotoxic potential of both compound groups, it was concluded that observed toxic effects were much more likely caused by VOCs in biochars containing both contaminants. Overall, formation of VOCs and PAHs cannot be prevented, but their presence in biochar resulting from retention and deposition can be minimised.

In this thesis, I describe experiments that were designed to provide a better understanding of polymer diffusion during latex film formation. This step leads to the improvement of film mechanical properties. Polymer diffusion in these films was monitored by fluorescence resonance energy transfer. Current paint formulations contain Volatile Organic Compounds (VOCs) as plasticizers to facilitate polymer diffusion. The drawback of this technology is the release of VOCs to the atmosphere. VOCs are deleterious to the environment and contribute to smog and ground level ozone formation. The propensity of water, an indispensible part of any latex dispersion, to promote polymer diffusion was studied. Copolymers of poly (butyl acrylate-co-methyl methacrylate) and poly(ethylhexyl acrylate-co-tertiary butyl methacrylate) with similar glass transition temperatures but different hydrophobicity were compared. Polymer diffusion was monitored for films aged at different relative humidities. Water absorbed by the hydrophobic copolymer film was less efficient in promoting polymer diffusion than in the hydrophilic polymer. Only the fraction of water which is molecularly dissolved in the film participate actively in plasticization. Although water has low solubility in most latex polymers, molecularly dissolved water is more efficient than many traditional plasticizers. The possibility of modifying film formation behavior of acrylic dispersions with oligomers was studied by synthesizing hybrid polymer particles consisting of a high molecular weigh (high-M) polymer and an oligomer with the same composition. Oligomers with lower molecular weight are more efficient as diffusion promoters and have less deleterious effect on high-M polymer viscosity. A different set of hybrid particles were prepared in which the oligomer contained methacrylic acid units. The composition of the oligomer was tuned to be miscible with the high-M polymer when the acid groups were protonated but to phase separate when the acid groups were deprotonated. At basic pH, these particles adopt a core-shell morphology, with a shell rich in neutralized oligomers. After film formation, the oligomer shell retarded polymer diffusion. This retardation is expected to expand the time window during which the paint surface can be altered without leaving brush marks (open time). Short open time is a pressing problem in current technology.

In this thesis, I describe experiments that were designed to provide a better understanding of polymer diffusion during latex film formation. This step leads to the improvement of film mechanical properties. Polymer diffusion in these films was monitored by fluorescence resonance energy transfer. Current paint formulations contain Volatile Organic Compounds (VOCs) as plasticizers to facilitate polymer diffusion. The drawback of this technology is the release of VOCs to the atmosphere. VOCs are deleterious to the environment and contribute to smog and ground level ozone formation. The propensity of water, an indispensible part of any latex dispersion, to promote polymer diffusion was studied. Copolymers of poly (butyl acrylate-co-methyl methacrylate) and poly(ethylhexyl acrylate-co-tertiary butyl methacrylate) with similar glass transition temperatures but different hydrophobicity were compared. Polymer diffusion was monitored for films aged at different relative humidities. Water absorbed by the hydrophobic copolymer film was less efficient in promoting polymer diffusion than in the hydrophilic polymer. Only the fraction of water which is molecularly dissolved in the film participate actively in plasticization. Although water has low solubility in most latex polymers, molecularly dissolved water is more efficient than many traditional plasticizers. The possibility of modifying film formation behavior of acrylic dispersions with oligomers was studied by synthesizing hybrid polymer particles consisting of a high molecular weigh (high-M) polymer and an oligomer with the same composition. Oligomers with lower molecular weight are more efficient as diffusion promoters and have less deleterious effect on high-M polymer viscosity. A different set of hybrid particles were prepared in which the oligomer contained methacrylic acid units. The composition of the oligomer was tuned to be miscible with the high-M polymer when the acid groups were protonated but to phase separate when the acid groups were deprotonated. At basic pH, these particles adopt a core-shell morphology, with a shell rich in neutralized oligomers. After film formation, the oligomer shell retarded polymer diffusion. This retardation is expected to expand the time window during which the paint surface can be altered without leaving brush marks (open time). Short open time is a pressing problem in current technology.

L’objectif de notre travail, était l’étude de deux classes de catalyseurs dans la réaction d’oxydation totale de COV. L’application visée étant la destruction à basse température de ces traces de polluants dans l’air. Des oxydes mixtes Co3O4-CeO2 ont été préparés par co-précipitation. Avec l’oxyde mixte (% atomique Co/Ce = 1), nous avons obtenu les meilleures performances catalytiques et montré que la réactivité étaient exaltée par une forte mobilité des oxygènes de coeur. Des catalyseurs à base d’or (2wt%) et de palladium (1wt%) ont été déposés sur des supports oxydes comme la cérine et le titane afin de favoriser une interaction métal support, ou sur un support alumine. Des solides à base d’alumine dopée au cérium, manganèse, fer et titane ont également été préparés. Pour l’or, l’évolution des performances catalytiques en fonction du support ont été les suivantes: Au2%/Al2O3 < Au2%/TiO2 < Au2%/CeO2, alors que pour le palladium nous avons obtenu les tendances suivantes : Pd1%/CeO2 < Pd1%/Al2O3 < Pd1%/TiO2. Pour l’Au, l’interaction métal support a permis d’expliquer les différences de réactivité alors que pour le palladium, l’activité est liée aux sites actifs de palladium Pd0/PdO présents à la surface. Avec les systèmes dopés, les résultats ont montré que les meilleurs catalyseurs étaient le Au2%/Ce5%/Al2O3 et le Pd1%/Ce5%/Al2O3. Cette exaltation a été attribuée à la grande mobilité des oxygènes en raison d’un défaut de structure induit par l’insertion des ions Al3+ au sein du réseau de la cérine et une forte interaction des particules très bien dispersées / The aim of the work was to study two classes of catalysts for the complete oxidation of volatile organic compounds. The target application for air pollution control is the total abatement of VOC at low temperature. Mixed oxide Co3O4-CeO2, were prepared by co-precipitation method. Among them, the mixed oxide corresponding to Co/Ce atomic ratio close to 1, was the best performing. The participation of surface oxygen species and high bulk mobile oxygen were the factors determining the high activity of Co30Ce in the total oxidation of propylene and toluene. Au (2wt%) and Pd (1wt%) catalysts were prepared over typical reducible oxides, such as CeO2 and TiO2. For comparison, catalysts over Al2O3, were also prepared. Moreover, the effect on the activity of Au and Pd supported over Al2O3 doped by cerium, manganese, iron and titanium was investigated. The so prepared Au and Pd catalysts were compared in the total oxidation of propylene. It was found that the activity of gold catalysts supported over un-doped oxides varied in the order: Au2%/Al2O3 < Au2%/TiO2 < Au2%/CeO2, while a different trend was observed for palladium catalysts: Pd1%/CeO2 < Pd1%/Al2O3 < Pd1%/TiO2. For Au catalysts, the nature of the support and the extent of interaction with the support are the key factors in determining the activity, whilst for the Pd supported ones, the activity seems to be governed by the nature of Pd species, Pd0/PdO, present in the catalyst. Au2%/Ce5%/Al2O3 and Pd1%/Ce5%/Al2O3 appear the best samples. The enhanced catalytic performances were attributed to high-oxygen mobility due to a defective ceria structure induced by the insertion of Al3+ ions into the lattice and also strong metal-support interaction between nanoparticles highly dispersed

Die vorliegende Arbeit beschäftigt sich mit der Modellerstellung und Technologie eines gravimetrischen Gassensors für organische Gase. Die Besonderheit liegt in dem verwendeten Resonatortyp. Es handelt sich um einen lateral elektrostatisch angeregten quadratischen Plattenresonator, der mit einer Rezeptorschicht versehen wird. Mit Hilfe von FEM-Berechnungen werden die Eigenfrequenzen und Eigenformen berechnet. Für die untersuchte Lamé- und Square-Mode wird die Sensorgüte unter Berücksichtigung des "Squeeze-Film-Damping" sowie der viskoelastischen Rezeptorschichteigenschaften bestimmt. Die Sensormoden werden durch ein Feder-Masse-Modell mit einem Freiheitsgrad modelliert und durch ein elektrisches Ersatzschaltbild repräsentiert. Die berechneten Nachweisgrenzen für Oktan und Toluol bei 6-facher Rauschgrenze liegen im zweistelligen ppb-Bereich. Für die technologische Umsetzung werden SOI-Wafer verwendet. Die &le; 100 nm betragenden Spaltbreiten zwischen Elektroden und Resonator werden durch das RIE-Ätzen von Siliziumgräben mit senkrechten Seitenwänden, der Abscheidung von SiO2 als Opferschicht und dem Füllen der Gräben mit hochdotiertem Polysilizium hergestellt. Die Kontaktierung der Resonatoren erfolgt über einen leitenden Stamm, der aufgrund von selbstjustierenden Prozessen die Resonatorplatte zentriert einspannt. / The following work is concerned with the modelling and fabrication technology of a gravimetric sensor for volatile organic compounds (VOC). Novelty is the combination of a lateral electrostatic driven square plate resonator with a gas sensitive detection layer. The eigenfrequencies and -modes are calculated with FEM simulations. Especially suited for gas sensors are the Lamé- and Square eigenmodes which are studied more closely. The quality factor is determined considering "squeeze film damping" and the viscoelastic properties of the gas sensitive detection layer. To present the sensor oscillation modes a spring mass model with one degree of freedom is determined and extended by an equivalent circuit diagram. The calculated limits of detections for octane and toluene are in the binary ppb-range, working with six times the limit of frequency noise. SOI-wafers are the base material for the sensor process flow. Electrode gaps &le;100 nm, essential for the electrostatic drive, are fabricated by RIE-etching vertical trenches into the device layer down to the buried oxide and by depositing a silicon dioxide as sacrifical layer and by refilling the trenches with highly doped polysilicon. The electrical contact of the resonator plate is ensured through an electrical conducting polysilicon stem. The developed process flow enables a self alignment ot the stem, clamping the plate centered.

The research focuses on the environmental problem of volatile organic compounds in ambient air of petrol filling stations. The literature review of the issues, arising from petrol-related VOCs, with actual and proposed VOC emissions trends in Europe, have been performed. Besides petrol filling station’s typical technology layout, petrol nature and composition, applicable petrol vapour recovery solutions and their efficiency were examinated. The volatile organic compounds’ experimental research in two petrol stations of typical technology layout in Vilnius city under similar extreme meteorological conditions (VOC air pollution episodes with low winds, stable stratification and suspended photochemical removal) is done. The emitted from petrol stations VOC experiment is based on air pumped sampling in glass gas pipette and further determination using gas chromatography with flame ionization detector. The experimental results, presented by means of tables and diagrams, are analysed and discussed. The available results of the experiment are loaded into the environmental model “ALOHA” for air pollution evaluation and concentrations prediction in the ambient air under different meteorological conditions and technological emergency situations (petrol spillage) at petrol filling station. The research is summarized in conclusions and recommendations. / Tyrimas skirtas aplinkos oro taršos problemai lakiaisiais organiniais junginiais, išsiskiriančiais nuo benzino degalinių. Atlikta svarstomos aplinkosauginės problemos literatūros apžvalga. Apžvelgti oro taršos pasekmės skatinamos LOJ išsiskyrimų nuo benzino degalinių, aktualios ir numatomos LOJ emisijų tendencijos Europoje, tipinis benzino degalinės technologijos išsidėstymas, benzino sudėtis ir svarbiausios LOJ garų formavimui benzino savybės, taikomi garų grąžinimo sprendiniai ir jų efektyvumas. Detaliai aprašytas LOJ eksperimentinis tyrimas, atliktas dviejose Vilniaus miesto tipinės technologijos degalinėse esant panašioms kraštutinėms (LOJ taršos epizodai prie silpnų vėjų, stabilios stratifikacijos ir suspenduoto fotocheminio šalinimo) meteorologiniams sąlygoms. LOJ mėginių ėmimui panaudotas aktyvus metodas su aspiracija į dujines pipetes, LOJ koncentracijos nustatytos dujinės chromatografijos su liepsnos jonizacijos detektoriumi metodu. Tyrimo rezultatai, pateikti lentelių ir diagramų pavidalu, aptarti ir įvertinti. Eksperimento duomenys įkelti į oro kokybės modelį “ALOHA”, siekiant nustatyti LOJ pernašą ir sudaryti LOJ koncentracijų prognozė benzino degalinių aplinkos ore prie skirtingų meteorologinių parametrų ir avarinių technologinių situacijų (benzino išsiliejimas). Tiriamąjį darbą reziumuoja išvados ir rekomendacijos.

Die vorliegende Arbeit beschäftigt sich mit der Modellerstellung und Technologie eines gravimetrischen Gassensors für organische Gase. Die Besonderheit liegt in dem verwendeten Resonatortyp. Es handelt sich um einen lateral elektrostatisch angeregten quadratischen Plattenresonator, der mit einer Rezeptorschicht versehen wird. Mit Hilfe von FEM-Berechnungen werden die Eigenfrequenzen und Eigenformen berechnet. Für die untersuchte Lamé- und Square-Mode wird die Sensorgüte unter Berücksichtigung des "Squeeze-Film-Damping" sowie der viskoelastischen Rezeptorschichteigenschaften bestimmt. Die Sensormoden werden durch ein Feder-Masse-Modell mit einem Freiheitsgrad modelliert und durch ein elektrisches Ersatzschaltbild repräsentiert. Die berechneten Nachweisgrenzen für Oktan und Toluol bei 6-facher Rauschgrenze liegen im zweistelligen ppb-Bereich. Für die technologische Umsetzung werden SOI-Wafer verwendet. Die &le; 100 nm betragenden Spaltbreiten zwischen Elektroden und Resonator werden durch das RIE-Ätzen von Siliziumgräben mit senkrechten Seitenwänden, der Abscheidung von SiO2 als Opferschicht und dem Füllen der Gräben mit hochdotiertem Polysilizium hergestellt. Die Kontaktierung der Resonatoren erfolgt über einen leitenden Stamm, der aufgrund von selbstjustierenden Prozessen die Resonatorplatte zentriert einspannt. / The following work is concerned with the modelling and fabrication technology of a gravimetric sensor for volatile organic compounds (VOC). Novelty is the combination of a lateral electrostatic driven square plate resonator with a gas sensitive detection layer. The eigenfrequencies and -modes are calculated with FEM simulations. Especially suited for gas sensors are the Lamé- and Square eigenmodes which are studied more closely. The quality factor is determined considering "squeeze film damping" and the viscoelastic properties of the gas sensitive detection layer. To present the sensor oscillation modes a spring mass model with one degree of freedom is determined and extended by an equivalent circuit diagram. The calculated limits of detections for octane and toluene are in the binary ppb-range, working with six times the limit of frequency noise. SOI-wafers are the base material for the sensor process flow. Electrode gaps &le;100 nm, essential for the electrostatic drive, are fabricated by RIE-etching vertical trenches into the device layer down to the buried oxide and by depositing a silicon dioxide as sacrifical layer and by refilling the trenches with highly doped polysilicon. The electrical contact of the resonator plate is ensured through an electrical conducting polysilicon stem. The developed process flow enables a self alignment ot the stem, clamping the plate centered.

La détection et l'identification de bactéries pathogènes revêt une grande importance dans de nombreux domaines tels que la santé et l’industrie agroalimentaire. Dans ce contexte, les travaux de thèse s’intéressent à détection non invasive de Salmonella via la fraction volatile de son métabolome dont les métabolites volatils caractéristiques sont le sulfure d’hydrogène et la cadavérine. Ils illustrent également le concept de substrats osmogènes libérant des mCOV exogènes sous l’action d’enzyme spécifique d’Escherichia coli. Un premier capteur colorimétrique capable de distinguer le sulfure d’hydrogène du méthanethiol a été préparé. Il s’agit d’une matrice de silicate nanoporeuse dopée avec les réactifs N,N-diméthyl-p-phénylènediamine et ions Fe3+. Une bonne stabilité de l’intermédiaire réactionnel issu de ces réactifs, la quinonediimine (QD), est obtenue pour une forte concentration d’acide chlorhydrique. La réaction entre QD et 1000 ppm de sulfure d’hydrogène et de méthanethiol entraîne l’apparition respective d’une coloration verte et rouge-marron du capteur. Le capteur fluorimétrique de cadavérine, basé sur la formation d’un complexe fluorescent entre le Naphthol AS-BI déméthylé (ArOH) et la cadavérine, permet de détecter 250 ppb de cadavérine. La preuve de concept de substrats osmogènes a été illustrée avec la détection de p-nitrophénol (pNP) et de β-naphthylamine (β-NA) libérés en présence d’enzymes de E. coli, β-D-glucuronidase et L-alanine- β-naphthylamidase. Les capteurs nanoporeux produits, de taille de pores contrôlée, peuvent détecter 100 ppm de pNP, composé coloré (jaune) et 100 ppm de β-NA, composé fluorescent, ou encore 100 ppm de β-NA par dérivation chimique de ce dernier avec le diméthyl-p-aminocinnamaldéhyde (formation d’un produit rouge). En milieu biologique, l’eau est un interférent majeur. / Microbial contamination of food and biological samples is a big issue in the industry as much as in the medical field. In that context, the present thesis brings innovative solutions. A first explored way is the identification of Salmonella by detecting and measuring the specific metabolomics volatile organic compounds (mVOC) released, H2S and cadaverine. Another new concept is the use of osmogenic substrates able to release mVOC under the action of specific enzyme of Escherichia coli.A first colorimetric sensor able to discriminate H2S from CH3SH was produced, using a nanoporous silicate matrix doped with N,N-dimethyl-p-phenylenediamine and Fe3+ ions. A very acidic medium is needed to stabilize the “key” intermediate of the reaction, the quinonediimine species (QD), which gives with H2S and CH3SH a green and red-brown product, respectively. The fluorimetric sensor of cadaverine is based on the formation of a fluorescent complex between AS-BI demethylated Naphthol and cadaverine and can detect 250 ppb of cadaverine. A proof of concept of osmogenic substrates is given with the detection of p-nitrophenol (pNP) et de β-naphthylamine (β-NA) released under the action of Escherichia coli enzymes, β-D-glucuronidase et L-alanine- β-naphthylamidase. Various nanoporous sensors are produced with tailored pore size, which can detect 100 ppm of the yellow pNP, 100 ppm of the fluorescent β-NA and 100 ppm of the red product issued from the derivation of β-NA with dimethyl-p-aminocinnamaldehyde. In biological media, water remains the major interfering agent.

No description available.

La présence de microorganismes peut être révélée par des métabolites volatils caractéristiques. Cette approche est particulièrement intéressante pour la détection non-invasive de pathogènes dans des échantillons complexes comme les matrices alimentaires, les échantillons sanguins, ou encore les plaies chroniques. Des capteurs nanoporeux à grande surface spécifique ont été préparés par voie sol-gel (xérogels) ; leur rôle est à la fois de capturer, concentrer et permettre une détection optique des Composés Organiques Volatils (COV) microbiens. Des capteurs dopés avec une molécule sonde, l'acide 5,5′ dithiobis 2 nitrobenzoïque, ont été développés pour mettre en évidence le sulfure d'hydrogène (H2S) produit par Salmonella, un pathogène d'intérêt dans le domaine de l'agroalimentaire. La capture d'H2S provoque un changement de couleur du capteur dès 5 ppm. Une partie du travail de recherche porte également sur la détection de métabolites dits « exogènes », libérés suite à l'hydrolyse d'un substrat enzymatique. C'est alors l'activité enzymatique qui est spécifique du micro-organisme ciblé. Deux COV exogènes sont envisagés : la β naphthylamine (β NA) et le 2 nitrophénol (2 NP). La première est issue d'activités enzymatiques peptidases, le second est issu d'activités glycosidases ou estérases. Pour ce dernier, une détection directe est possible dès 14 ppb grâce à son absorbance intrinsèque dans le visible. Après un travail sur la composition chimique des xérogels, une mise en forme originale par moulage des gels en forme de coin de cube permet une lecture de l'absorbance des xérogels en réflexion. Enfin, les capteurs obtenus ont été testés vis-à-vis de COV générés par 3 pathogènes: Salmonella, Escherichia coli et Staphylococcus aureus dans des matrices complexes (sang et échantillons alimentaires). / The presence of micro-organisms can be revealed by specific volatile metabolites. This approach is interesting for the non-invasive detection of pathogenic species in complex samples, such as food, blood or exudate. Nanoporous materials developing a high surface area have been prepared by sol-gel process (xerogels). They trap, concentrate and reveal the presence of microbial Volatile Organic Compounds (VOC) by means of an optical detection. Sensors have been doped with a probe molecule (5,5′ dithiobis 2 nitrobenzoic acid) in order to detect hydrogen sulfide emitted by foodborne pathogen Salmonella. The colour of sensor changes in the presence of 5 ppm of H2S. Another detection method is the use of enzymatic substrates which release exogenous VOCs. In this approach, the enzymatic activity is specific to the targeted pathogenic bacteria. Sensors have been developed for two exogenous VOCs: β naphthylamine (β NA) and 2 nitrophenol (2-NP). β NA is issued from peptidase activity, whereas 2 NP is produced by glycosidase or esterase activity. The latter can be detected above 14 ppb through absorbance in the visible region. The work focused both on the chemical composition of the xerogels and on their shape. After molding the xerogels into a trihedral prism (“corner reflector”), the absorbance can be easily monitored using the reflected light. VOCs produced by 3 pathogenic bacteria, Salmonella, Escherichia coli and Staphylococcus aureus, in complex media (blood and food samples) have been monitored with the obtained sensors.