Les aérosols atmosphériques (par exemple les matières particulaires ou PM) sont une source majeure d’incertitude dans les modèles climatiques. Plusieurs études ont démontré que des concentrations élevées de PM réduisent l’espérance de vie. Les aérosols organiques secondaires (Secondary Organic Aerosols en anglais, SOA) sont formés dans l’atmosphère à partir des précurseurs gazeux à travers les réactions chimiques et les SOA représentent des composants majeurs de la masse des PM à l’échelle mondiale. Afin de mieux comprendre les processus chimiques responsables de la formation des SOA, un modèle en 0-D est élaboré pour simuler dynamiquement l’évolution des espèces organiques dans une parcelle d’air qui subit une oxydation photochimique produisant des SOA. Le modèle incorpore des paramètres récemment publiés pour la formation des SOA à partir des composés organiques volatiles (VOCs), ainsi que des composés organiques semi-volatiles et des composés organiques à volatilité intermédiaire (SVOCs et IVOCs). Le modèle est restreint par plusieurs mesures de précurseurs, incluant des mesures récemment développées qui fournissent des contraintes grandement améliorées sur les concentrations des précurseurs, et les prédictions sont comparées par rapport aux mesures des SOA prises au cours de la campagne CalNex. Lorsque les effets des pertes sur les parois des chambres à smog sont considérés pour les rendements des VOCs, la quantité et la vitesse de la formation des SOA dans le modèle sont plus en accord avec les observations. Les résultats de cette étude indiquent que les SVOCs et les IVOCs primaires sont responsables de la majorité (70 à 86 %) de la masse de SOA modélisée, accentuant leur grande contribution en tant que précurseurs des SOA. Cependant, la masse de SOA simulée est sous-estimée à des temps courts d’oxydation lorsque comparée aux données sur le terrain, mais à des temps plus longs, un accord modèle/mesures est observé. Cet écart peut être dû à un ΔIVOC/ΔCO ratio d’émission bas ou une sous-estimation basse des constantes d’oxydations des IVOCs, ce qui met en évidence la nécessité de poursuivre les études sur le terrain et dans les laboratoires de ces composés. / Atmospheric aerosols (i.e. particulate matter or PM) are a major source of uncertainty in climate models. Many studies have also shown that elevated concentrations of PM reduce life expectancies. Secondary organic aerosol (SOA) is formed in the atmosphere from gaseous precursors through chemical reactions and SOA represents a major component of PM mass globally. To better understand the chemical pathways responsible for SOA formation, a box model is designed to simulate dynamically the evolution of organic species in an air parcel as it undergoes photochemical oxidation producing SOA. The model incorporates recently published parameterizations for the formation of SOA from volatile organic compounds (VOCs), as well as from semi-volatile and intermediate-volatility organic compounds (SVOCs and IVOCs). The model is constrained by several measurements of precursors, including recently developed measurements that provide greatly improved constraints on precursor concentrations, and the predications are compared against measurements of SOA taken during the CalNex campaign. When accounting for the effect of chamber wall-losses on VOC yields, the amount and rate of SOA formation in the model is more consistent with observations. The results of this study also indicate that the primary SVOCs and IVOCs are responsible for a majority (70 – 86 %) of the model SOA mass, emphasizing their high contribution as SOA precursors. However, the SOA mass predicted is underestimated at shorter photochemical ages when compared to field measurements, but at longer ages, model/measurement agreement is observed. This bias may be due to low IVOC/CO emissions ratios or low estimated IVOC oxidation rate constants, which highlights the need for further field and laboratory studies of these compounds.

A variety of methods exist to remove volatile organic compound (VOC) air pollutants from contaminated gas streams. As regulatory and public opinion pressures increase, companies are searching for more effective methods to control these emissions. This document is intended as a guide to help determine if existing systems are adequate and to provide additional information to improve the efficiency of the systems. It explores conventional methods of controlling VOC emissions, as well as innovative technologies including membrane separation, plasma destruction, and ozone catalytic oxidation. The conventional technologies covered include condensation, adsorption, absorption (or scrubbing), thermal incineration, flaring, catalytic incineration, and biofiltration. Each chapter includes a description of the technology, a discussion of the types of systems available, notes on the design of the system, economic estimates, an explanation of potential problems, and a list of considerations for installation and maintenance concerns. The final chapter is dedicated to the preparation and characterization of metal catalysts which were developed to improve the reaction rate of VOCs using ozone as an oxidant. / Ph. D.

Cette thèse a pour objet l’analyse de la cinétique de la conversion de l’acétaldéhyde, CH₃CHO, à des concentrations initiales inférieures ou égale à 5000 ppm dans un mélange de gaz à base d’azote et contenant jusqu’à 20% d’oxygène, à température ambiante. L’étude a été réalisée en utilisant trois réacteurs mettant en œuvre des décharges de qualités spatiales différentes. Il s’agit d’un réacteur (UV510) à décharge pré-ionisée (photo-déclenchée) par rayonnement UV produisant un plasma homogène, et de deux réacteurs à décharge à barrière diélectrique (DBD), de géométrie plane (plan-plan) et de géométrie cylindrique (tige-tube) alimentés par impulsion HT et produisant des plasmas non homogènes à faible (plan) ou forte (cylindre) filamentation ; un diagnostic d’imagerie rapide (ns) de la DBD de géométrie plane montre que le plasma peut être considéré quasi-homogène. En s’appuyant sur une modélisation 0D auto-cohérente de la décharge photo-déclenchée, l’étude de la cinétique du mélange N₂/CH₃CHO montre l’importance des états métastables de la molécule d’azote, triplet A³Σu⁺, et singlets (groupe a' ¹∑⁻u, a ¹∏g, et w ¹Δu) dans la dissociation de l’acétaldéhyde. Un coefficient minimum de 6.5×10⁻¹¹ cm³.s⁻¹ est estimé pour le quenching des singlets par l’acétaldéhyde. Le coefficient du triplet est estimé entre 4.2×10⁻¹¹ cm³.s⁻¹ et 6.5×10⁻¹¹ cm³.s⁻¹. Cette dissociation produit des radicaux (CH₃, CH₃CO, HCO, H, O) et des molécules (CH₄, CH₂CO, C₂H₄, C₂H₂, H₂, CO). Ainsi les sous-produits majoritaires mesurés à la fin de la post décharge temporelle sont le méthane, le dihydrogène, le monoxyde de carbone et l’éthane. Les minoritaires sont l’acétylène, l’éthène, l’acétone et l’acétonitrile. Dans les mélanges contenant de l’oxygène, l’importance de la dissociation de CH₃CHO par quenching des états métastables de N₂ diminue au profit des processus d’oxydation par le radical hydroxyle, OH, et l’oxygène atomique, O (³P). La mesure résolue en temps du radical OH dans la post-décharge du réacteur UV510 montre une très forte réactivité de ce radical avec les sous-produits de conversion de l’acétaldéhyde. Une densité maximum de OH égale à 3.5×10¹⁴ cm⁻³ a été mesurée pour 10 % d’oxygène et 5000 ppm d’acétaldéhyde. Le schéma cinétique adopté pour ces mélanges donne, par la modélisation auto-cohérente, une valeur de densité plus élevée. Toutefois, la conversion de l’acétaldéhyde dans N₂/O₂/CH₃CHO est bien expliquée par le modèle, de même que les concentrations produites de méthane et d’éthane. Enfin, la comparaison de l’efficacité énergétique des trois réacteurs étudiés montre que l’homogénéité de la décharge favorise, pour des milieux pauvres en oxygène (moins de 2 %), la conversion de l’acétaldéhyde. / The present study deals with the kinetics analysis of acetaldehyde (CH₃CHO) conversion in electrical discharges with different spatial qualities et at room temperature. Acetaldehyde concentrations up to 5000 ppm in nitrogen-based gas mixture containing up to 20% of oxygen have been investigated. Three different plasma reactors were used: an UV510 reactor producing a homogeneous plasma thanks to a pre-ionization by UV radiation (photo-triggered), a plane-to-plane and a rod-tube dielectric barrier discharges (DBDs) reactors, In both DBDs reactors discharges were driven by high voltage pulses allowing the production of weakly inhomogeneous plasma in the plane geometry and highly filamentary discharges in the cylindrical one. A high speed imaging diagnostic (ns range) of the plane-to-plane DBD shows that the plasma can be considered quasi-homogeneous. Based on a self-consistent 0D model, the kinetics study of the N₂/CH₃CHO mixture conversion in the photo-triggered discharge shows the importance of nitrogen molecule metastable states , i.e. the triplet A³Σu⁺ and the singlets group a' ¹∑⁻u, a ¹∏g, et w ¹Δu, in the acetaldehyde dissociation process. A minimum coefficient of 6.5×10⁻¹¹ cm³.s⁻¹ has been estimated for the quenching of N₂ singlets state by acetaldehyde. For the triplet states quenching the coefficient of has been evaluated between 4.2×10⁻¹¹ cm³.s⁻¹ and 6.5×10⁻¹¹ cm³.s⁻¹. This dissociation process produces radicals as CH₃, CH₃CO, HCO, H, O, and molecules like CH₄, CH₂CO, C₂H₄, C₂H₂, H₂, CO. Thus, the major by-products detected at the end of the post-discharge time are methane, hydrogen, carbon monoxide and ethane; smaller amounts of acetylene, ethene, acetone and acetonitrile were also detected. In containing oxygen mixtures, the importance of the CH3CHO dissociation processes due to N₂ metastable states quenching of decreases in favor of oxidation processes promoted by the hydroxyl radical, OH, and atomic oxygen, O (³P). Time-resolved measurements of the OH radical in the photo-triggered post-discharge show a very high reactivity of this radical with the by-products of acetaldehyde conversion. A maximum density of OH radical equal to 3.5×10¹⁴ cm⁻³ was measured for 10% oxygen and 5000 ppm of acetaldehyde. The kinetic scheme adopted in the self-consistent model for the same gas mixture gives a higher density value; by the way the model is in good agreement with the acetaldehyde conversion in N₂/O₂/CH₃CHO mixtures, as well as with the methane and ethane produced concentrations. Finally, the comparison of the three studied reactors energy efficiency shows that, for low oxygen content (less than 2%), the homogeneity of the discharge promotes the acetaldehyde conversion.

La recherche de solutions alternatives à l’usage de pesticides en production horticole est devenue une exigence de santé publique. Ainsi, l’introduction de plantes de service (PdS) est une méthode écologique qui peut contribuer à diminuer le recours à la lutte chimique contre Myzus persicae, le puceron vert du pêcher. L’intérêt de certaines de ces PdS réside dans leur capacité à perturber l’installation du puceron sur son hôte et/ou à diminuer ses performances grâce à l’émission des composés organiques volatils (COV). Cependant, un obstacle majeur à leur utilisation est que leur efficacité se limite à un périmètre restreint et que leur production olfactive est sensible à de nombreuses variables biotiques et abiotiques. Identifier les plantes les plus performantes, comprendre leur mode d’action et chercher à optimiser leur efficacité est donc une démarche propre à favoriser leur emploi en horticulture. L’analyse de l’environnement olfactif est une clé pour évaluer et comprendre les interactions PdS-plante hôte-puceron.Au laboratoire, un typage avec un olfactomètre en Y a permis de sélectionner deux PdS émettrices de mélanges de COV ayant un effet répulsif marqué sur M. persicae : le basilic (Ocimum basilicum) qui agit directement sur l’insecte, et l’œillet d’Inde (Tagetes patula) qui agit indirectement via la plante hôte. Ainsi, les COV émis par T. patula rendent la plante-hôte (le poivron, Capsicum annuum) répulsive. En effet, lors des tests de choix, les pucerons s’orientent vers les poivrons seuls mais évitent les COV émis par des poivrons précédemment mis en culture associée pendant 5 jours avec l’œillet d’inde. Deux composés, le (E)-β-farnésène (EBF) et l'eugénol ont de fortes propriétés répulsives envers M. persicae.Différents facteurs peuvent affecter l’efficacité répulsive de ces plantes (climat, conduite, génétique). Nous avons comparé les COV émis selon les espèces et les chémotypes et testé l’effet répulsif individuel des COV. Cet effet « génotype » a été examiné en étudiant le comportement olfactif de M. persicae en présence des COV individuels émis par différents clones de Romarin (Rosmarinus officinalis). Cinq composés sont répulsifs, l’acétate de bornyle, le camphre, l’α-terpinéol, le terpinène-4-ol et le géranyle acétone. Seul le clone de romarin Voltz Splindler s’est avéré répulsif, alors que les autres clones contiennent également ces 5 composés répulsifs mais dans des proportions différentes. On peut donc conclure que la présence de ces composés ne suffit pas à induire une perturbation du comportement olfactif du puceron et que la concentration, la proportion, voire l’association des COV présents dans les bouquets olfactifs libérés, sont à l’origine de ces résultats contrastés. Par la technique d’électropénétrographie (EPG), nous avons mis en évidence un deuxième effet des COV émis par O. basilicum au stade végétatif et par T. patula au stade floraison sur le puceron. Ils perturbent fortement son comportement alimentaire, en réduisant notamment la durée d’ingestion du phloème qui se traduit par une baisse des ressources nutritionnelles et aboutit à une diminution de sa fécondité. Un suivi de la fécondité sur organe détaché nous a permis de mettre en évidence l’importance du stade phénologique de la PdS sur la composition et l’efficacité du mélange olfactif libéré. Une dernière étape de mon travail a permis de confirmer dans des conditions de cultures sous tunnels, l’effet de COV émis par ces deux PdS sur la démographie de M. persicae liée à une baisse de sa fécondité.En conclusion, cette thèse a mis en évidence que les COV émis dans l’environnement d’une plante hôte par des plantes voisines peuvent fournir un service aux cultures en réduisant les performances de ravageurs tels que M. persicae. Nous avons montré que des variables comme le chémotype ou le stade phénologique de la PdS peuvent modifier son message olfactif et constituer un moyen d’optimiser ce service. / The search for alternatives to the use of pesticides in horticultural production has become a public health requirement. Thus, the introduction of Companion plants (CP) is an ecological method that can help reduce the use of chemical control against Myzus persicae, the green peach aphid. The interest of some of these CP lies in their ability to disturb the installation of the aphid on its host plant and/or to reduce its performance through the emission of volatile organic compounds (VOCs). However, a major obstacle to their use is that their effectiveness is limited to a limited scope and their olfactory production is sensitive to many biotic and abiotic variables. Identifying the most efficient plants, understanding their mode of action and seeking to optimize their effectiveness is therefore an appropriate approach to promote their use in horticulture. Olfactory environment analysis is a key to assessing and understanding CP-host plant -aphid interactions.In the laboratory, we selected with a Y-olfactometer two CP producing VOC mixtures with a marked repellent effect on M. persicae: basil (Ocimum basilicum) which acts directly on the insect, and french marigold (Tagetes patula) which acts indirectly via the host plant. Thus, the VOCs emitted by T. patula make the host plant (pepper, Capsicum annuum) repellent: during the choice tests, the aphids move towards the peppers alone but avoid the VOCs emitted by peppers previously grown intercropped for 5 days with the french marigold. Two compounds, (E)-β-farnesene (EBF) and eugenol have strong repellent properties against M. persicae.Different factors can affect the repellent effectiveness of these plants (climate, plant management, genetics). We compared the VOCs emitted by species and chemotypes and tested the individual repellent effect of VOCs. This "genotype" effect was examined by studying the olfactory behaviour of M. persicae in the presence of individual VOCs emitted by different clones of Rosemary (Rosmarinus officinalis). Five compounds are repellent, bornyl acetate, camphor, α-terpineol, terpinene-4-ol and geranyl acetone. Only the rosemary clone Voltz Splindler was found to be repellent, while the other clones also contain these 5 repellent compounds in varying proportions. It can therefore be concluded that the presence of these compounds is not sufficient to induce a disturbance of the aphid's olfactory behaviour and that the concentration, proportion or even association of VOCs present in the released olfactory bouquets are at the origin of these contrasting results. By the electropenetrography (EPG) technique, we have demonstrated a second effect of the VOCs emitted by O. basilicum in the vegetative stage and by T. patula in the flowering stage on the aphid. They strongly disrupt its feeding behaviour, in particular by reducing the duration of phloem ingestion, which results in a decrease in nutritional resources and leads to a decrease in its fertility. A fertility monitoring on detached organs has allowed us to highlight the importance of the phenological stage of the CP on the composition and efficacy of the olfactory mixture released. A final step in my work confirmed, under tunnel conditions, the effect of VOCs emitted by these two CP on the demographics of M. persicae due to a decrease in its fertility. In conclusion, this thesis highlighted that VOCs emitted into the environment of a host plant by neighbouring plants can provide a service to crops by reducing the performance of pests such as M. persicae. We have shown that variables such as chemotype or phenological stage of the CP can modify its olfactory message and provide a way to optimize this service. We have thus identified disruptive CP and VOCs repellent to M. persicae, the first step towards the development of the push component of a stimulodissuasive diversion strategy to reduce the use of synthetic pesticides against M. persicae.

D.L. A 792-2008 / Ministerio de Educación y Ciencia; Programa FEDER; Generalitat Valenciana; Universidad de Alicante.

A quantificação de 11 compostos carbonílicos (formaldeído, acetaldeído, acetona, acroleína, propionaldeído, crotonaldeído, butiraldeído, benzaldeído, isovaleraldeído, valeraldeído e 2,5-dimetilbenzaldeído) e a identificação de outros 43 compostos orgânicos voláteis (alcanos, alcenos, aromáticos, halogenados e nitrogenados) foram feitas em 9 ambientes diferentes de trabalho localizados em áreas internas do Hospital Universitário, USP, São Paulo. Dentre os compostos carbonílicos, os mais abundantes em ordem decrescente foram formaldeído, acetona, acetaldeído e acroleína. As maiores razões de mistura de formaldeído foram observadas nas salas de Macroscopia (169,9 e 90,2 ppbv) e Técnicas Histológicas (11,7 e 58,7 ppbv), em decorrência da atividade desenvolvida nos locais. Na sala de Macroscopia, os níveis de formaldeído encontrados foram acima do limite (100 ppbv) estabelecido por órgãos internacionais que controlam a qualidade do ar em ambientes internos não industriais. As razões de mistura entre o ambiente interno e o ambiente externo, razões I/E, permitiram indicar a predominância dos compostos carbonílicos nos ambientes internos. A acroleína foi encontrada na faixa de 6,4 a 9,3 ppbv nos ambientes internos estudados. Na área externa, entretanto, foram encontrados valores similares (6,4 e 6,8 ppbv) aos dos ambientes internos obtendo razões I/E próximas de 1. Os compostos podem ter sido emitidos por materiais de construção e acabamento, fumaça do tabaco, adesivos, via metabolismo microbiano e bacteriano ou podem ter sido transportados por correntes de ar do ambiente externo para o ambiente interno / The quantification of 11 carbonyl compounds (formaldehyde, acetaldehyde, acrolein, acetone, propionaldehyde, crotonaldehyde, butiraldehyde, benzaldehyde, isovaleraldehyde, valeraldehyde and 2,5-dimethylbenzaldehyde) and the identification of another 43 volatile organic compounds (alkanes, alkenes, aromatic, halogenated and nitrogenated compounds) have been done with samples of 9 different indoor places inside the University Hospital at USP in São Paulo. Among the carbonyl compounds, there where found higher quantities of formaldehyde, acetone, acetaldehyde and acrolein in this order. The highest ratios of formaldehyde mixture have been observed at the Macroscopic room (169.88 and 90.2 ppbv) and Histological Techniques (11.7 and 58.7 ppbv), due to the routine activities of these places. At the Macroscopy room, the level of formaldehyde identified (100 ppbv) was above the international limits established to non-industrial internal places. The ratios of the mixture of indoor and outdoor places, I/O, indicate the biggest presence of carbonyl compounds in internal places. Acrolein has been identified (6.4 to 9.3 ppbv) at indoor places. At the external area, there where found similar values (6,4 to 6,8 ppbv), and the ratio I/O obtained is near to 1. The origin of these compounds is possibly construction materials, smoke of cigarettes, adhesives, metabolism of microorganisms or they may have come from the outdoor to the indoor

Les composés organiques volatiles (COVs) sont les polluants organiques atmosphériques les plus abondants. Parmi les différentes solutions pour combattre cette pollution, l'utilisation d'adsorbants moléculaires tels que les zéolithes semble être efficace. Cependant les synthèses classiques de zéolithes aboutissent généralement à des tailles de cristaux de l'ordre de plusieurs dizaines de micromètres. Les capacités et les cinétiques de piégeage, sensibles aux phénomènes de diffusion et de surface pourraient potentiellement être améliorées par l'utilisation de nanocristaux ou de produits zéolithiques hiérarchisés (micro/mésoporeux). Dans ce travail de thèse, nous avons synthétisé des zéolithes aluminosiliciques ou purement siliciques de type structural FAU, MFI et *BEA. Ces dernières sont synthétisées avec différentes morphologies et tailles de particules telles que les nanocristaux et les zéolithes hiérarchisées (nanofeuillets et/ou nanoéponges en utilisant des agents structurants bifonctionnels). Ces matériaux sont comparés aux zéolithes conventionnelles, afin d'étudier l'influence de la morphologie sur la cinétique et la capacité de piégeage de COVs. Les caractéristiques structurales et texturales des zéolithes synthétisées ont été étudiées par ORX, MEB, manométrie d'adsorption/désorption de diazote, ATG-ATD, RMN du solide. Enfin, la capacité d'adsorption d'une molécule modèle, le n-hexane, au sein de ces zéolithes a été étudiée par thermogravimétrie. Dans le cas des zéolithes de type MFI et *BEA, les zéolithes hiérarchisées ont montré une augmentation de la capacité de piégeage en n-hexane par rapport aux zéolithes conventionnelles. La capacité de piégeage en n-hexane a été multipliée par 7 dans le cas des nanoéponges de type *BEA et par 6 dans le cas des nanocristaux de type *BEA comparés aux microcristaux de type *BEA (693 mg/g vs 103 mg/g et 591 mg/g vs 103 mg/g, respectivement). / Volatile organic compounds (VOCs) are the most abundant organic pollutants. Among the various solutions to fight against this pollution, the use of molecular adsorbents appears as a potential alternative for the control of contamination. The porous materials have many advantages due to their low cost, their physical characteristics and their useful properties related to their structure and their large surface area. However, conventional synthesis of zeolites generally lead to micrometer size crystals. The capacity and the kinetics of adsorption that are sensitive to the diffusion and the surface phenomena could be potentially improved by the use of zeolite nanocrystals or hierarchical products (micro / mesoporous). These nanomaterials have high potential due to their small size and their exalted outer surface that promote access of pollutants and improve the adsorption capacity. ln the thesis work, we synthesized zeolites with different structural types such as FAU, MFI and *BEA. Each structure type was synthesized in different morphologies such as nanosponges and /or nanosheets using a bifunctional structuring agent, as well as nanocrystals by the clear solution method. These materials were compared with conventional micrometer-sized zeolites. The purity and the porous texture have been characterized by using XRD, SEM, nitrogen adsorption/desorption techniques, TGA-DTA and solid state NMR. Finally, the adsorption capacity of a model molecule, the n-hexane, in these zeolites have been studied by thermogravimetry. In the case of *BEA and MFI-type zeol ites, the hierarchical zeolites showed an increase of the adsorption capacity of n-hexane compared to conventional zeolites. The adsorption capacity of n-hexane was multiplied by 7 in the case of *BEA-type nanosponges and by 6 in the case of the *BEA-type nanocrystals compared to *BEA_type microcrystals (693 mg / g vs 103 mg / g and 591 mg / g vs 103 mg / g, respectively).

Part I: Successful transition of polymer coated, ATR-FTIR sensor devices from a laboratory environment to real world field applications for detecting and quantifying VOCs in water is shown. Simultaneous, quantitative detection of BTX mixtures in water during enrichment into polymer coated ZnSe ATR elements has been performed. The obtained results showed accurate detection and quantification to the low ppb concentration region. Fiber-optic evanescent field measurement campaigns have been conducted at simulated field conditions during which concentration gradients of various VOCs in the mg/L range have been monitored successfully. The first test of an ATR based, polymer coated sensor system under real world field conditions, the chlorobenzene concentration in groundwater at mg/L levels was determined. An interesting aspect of these measurements was the experimental proof for the dependence of analyte extraction dynamics on the flow conditions of the sample matrix surrounding the extractive polymer membrane. The obtained results demonstrate that MIR evanescent field sensors are suitable for in-situ analysis at real world field conditions for environmental monitoring applications. PART II: Recently, measurements of disturbed soils have shown different spectral contrast in comparison to undisturbed soils. In this work first measurements at controlled laboratory conditions have been performed to investigate individual minerals of the soil matrix and their spectral characteristics under various environmental conditions. ATR spectroscopy has been applied to investigate multi-disperse quartz sand and mono-disperse soda lime glass spheres samples. For the investigation of spectral differences between pristine and disturbed quartz sand, a wetting/drying procedure with subsequent sample aerating has been developed. In addition to established differences in spectral contrast of disturbed and undisturbed soil, a strong spectral shift of absorption features was observed. When probed with s- or p-polarized light, both samples showed strong LO-TO mode splitting. The studies also reveal that the main reason for spectral differences of pristine and disturbed soils is caused by water facilitated changes of the particle size distribution in the probed volume. The presented results advance the variety of spectral characteristics useful for the detection of disturbed soils (i.e. possible landmine sites) with MIR imaging systems.

Neighboring northern Kaohsiung with a dense population of petrochemical and petroleum industrial complexes included China Petroleum Company (CPC) refinery plant, Renwu and Dazher petrochemical industrial plants. In recent years, although many scholars have conducted regional studies, but are still limited by the lack of relevant information evidences (such as odorous matters identification and VOCs fingerprint database), while unable to clearly identify the causes of poor ambient air quality. By sampling and analyzing VOCs, we will be able to understand the major sources of VOCs in northern Kaohsiung and their contribution, and to provide the air quality management and control countermeasures for local environmental protection administration. In this study, we sampled and analyzed the speciation of VOCs and sulfur-containing odorous matters (SOMs) in the CPC refinery plants, Renwu and Dazher petrochemical complexes simultaneously with stack sampling. The sampling of VOCs and SOMs were conducted on January 7th, 14th, and 19th, 2011 (dry season) and May 6th, 13rd, and 23rd, 2011 (wet season). We established the emission source database, investigated the characteristics of VOC fingerprints, and estimate the emission factor of each stack. It helps us understand the temporal and spatial distribution of VOCs and ascertain major sources and their contribution of VOCs. Major VOCs emitted from the stacks of the CPC refinery plant were toluene and acetone. It showed that petroleum refinery processes had similar VOCs characteristics and fingerprints. The fingerprints of stack emissions at Renwu and Dashe industrial complexes varied with their processes. Hydrogen sulfide was the major sulfur-containing odorous matter in all petrochemical plants. Compared to other petrochemical complexes, Renwu industrial complex emitted a variety of SOMs species as well as relatively high concentrations of sulfur-containing odorous matters. The petrochemical industrial complexes in the industrial ambient of VOCs analysis results showed that isobutane, butane, isopentane, pentane, propane of alkanes, propene of alkenes, toluene, ethylbenzene, xylene, styrene of aromatics, 2-Butanone (MEK), acetone, of carbonyls are major species of VOCs. In addition, ethene+acetylene+ethane (C2), 1,2-dichloroethane, chloromethane, dichloromethane, MTBE were also occasionally found. Sulfur-containing odorous matter (SOMs) analytical results showed that major odorous matters included hydrogen sulfide, methanethiol, dimethyl sulfide, and carbon disulfide. The highest hydrogen sulfide concentration went up to 5.5 ppbv. In this study, the species of VOCs were divided into alkanes, alkenes, aromatics, carbonyls, and others. The temporal and spatial distribution of various types of VOCs strongly correlated with near-surface wind direction. The most obvious contaminants were alkanes, aromatics, and carbonyls of the dispersion to the downwind. Generally, the ambient air surrounding the petrochemical industrial complexes was influenced by various pollutants in the case of high wind speeds. It showed that stack emission and fugitive sources had an important contribution to ambient air quality. TSOMs and hydrogen sulfide emitting mainly from local sources resulted in high concentration of TSOMs and hydrogen sulfide surrounding the petrochemical industrial complex. Principal component analysis (PCA) results showed that the surrounding areas of petrochemical industrial complexes, regardless of dry or wet seasons, were mainly influenced by the process emissions and solvent evaporation. The impact of traffic emission sources ranked the second. Chemical mass balance receptor modeling showed that stack emissions from the CPC refinery plants contributed about 48 %, while fugitive emission sources and mobile sources contributed about 30 % and 11%, respectively. The stack emissions from Renwu industrial complex contributed about 75 %, while fugitive emission sources and mobile sources contributed about 17 % and 5 %, respectively. The stack emissions from Dazher industrial complex contributed about 68 %, while fugitive emission sources and mobile sources contributed about 21 % and 2 %, respectively.

A wide range of organic compounds are released from building and furnishing products and these have the potential to adversely affect indoor air quality. There are growing international requirements for testing and controlling these emissions for the protection of public health. The test methods require specialist analytical chemistry facilities based on thermal desorption/gas chromatography/mass spectrometry (TD/GC/MS). This project has addressed the need for better performance and greater automation of the analysis, as well as development of simpler screening tests. A variety of products were tested using screening techniques, with an emission cell method being used as a reference test. Short duration tests, using a micro-scale chamber at slightly elevated temperature, were shown to have the potential to predict emissions occurring during longer term reference tests. Multi-sorbent air sampling tubes, that have the potential to extend the volatility range of compounds determined by a single TD/GC/MS analysis, were compared with Tenax TA tubes specified by current standard methods. This showed no difference in performance for the range of compounds for which Tenax is optimal, with improved performance for a number of more volatile compounds. The determination of formaldehyde was investigated using 2-hydroxymethylpiperidine as a derivatising agent, followed by TD/GC/MS. The results showed the possibility of this method being developed as an alternative to the current standard method that involves solvent elution and liquid chromatography. The performance of a newly developed time-of-flight mass spectrometer was compared with a standard quadrupole instrument. This showed its potential, with the use of re-collection, to extend the concentration range of compounds quantified from a single air sample, of particular benefit for the determination of carcinogens. New compound identification software was applied to increase automation of analysis of the TD/GC/MS data. Good correlation with manual processing was achieved, demonstrating the possibility of routine application to material emissions testing.