Développement de méthodes d’analyse directe de polluants organiques volatils à l’état de traces dans l’air et les biogaz

Il est reconnu que le benzène, le toluène, l’éthylbenzène et les isomères du xylène, composés organiques volatils (COVs) communément désignés BTEX, produisent des effets nocifs sur la santé humaine et sur les végétaux dépendamment de la durée et des niveaux d’exposition. Le benzène en particulier est classé cancérogène et une exposition à des concentrations supérieures à 64 g/m3 de benzène peut être fatale en 5–10 minutes. Par conséquent, la mesure en temps réel des BTEX dans l’air ambiant est essentielle pour détecter rapidement un danger associé à leur émission dans l’air et pour estimer les risques potentiels pour les êtres vivants et pour l’environnement. Dans cette thèse, une méthode d’analyse en temps réel des BTEX dans l’air ambiant a été développée et validée. La méthode est basée sur la technique d’échantillonnage direct de l’air couplée avec la spectrométrie de masse en tandem utilisant une source d’ionisation chimique à pression atmosphérique (APCI-MS/MS directe). La validation analytique a démontré la sensibilité (limite de détection LDM 1–2 μg/m3), la précision (coefficient de variation CV < 10%), l’exactitude (exactitude > 95%) et la sélectivité de la méthode. Des échantillons d’air ambiant provenant d’un site d’enfouissement de déchets industriels et de divers garages d’entretien automobile ont été analysés par la méthode développée. La comparaison des résultats avec ceux obtenus par la technique de chromatographie gazeuse on-line couplée avec un détecteur à ionisation de flamme (GC-FID) a donné des résultats similaires. La capacité de la méthode pour l’évaluation rapide des risques potentiels associés à une exposition aux BTEX a été prouvée à travers une étude de terrain avec analyse de risque pour la santé des travailleurs dans trois garages d’entretien automobile et par des expériences sous atmosphères simulées. Les concentrations mesurées dans l’air ambiant des garages étaient de 8,9–25 µg/m3 pour le benzène, 119–1156 µg/m3 pour le toluène, 9–70 µg/m3 pour l’éthylbenzène et 45–347 µg/m3 pour les xylènes. Une dose quotidienne environnementale totale entre 1,46 10-3 et 2,52 10-3 mg/kg/jour a été déterminée pour le benzène. Le risque de cancer lié à l’exposition environnementale totale au benzène estimé pour les travailleurs étudiés se situait entre 1,1 10-5 et 1,8 10-5. Une nouvelle méthode APCI-MS/MS a été également développée et validée pour l’analyse directe de l’octaméthylcyclotétrasiloxane (D4) et le décaméthylcyclopentasiloxane (D5) dans l’air et les biogaz. Le D4 et le D5 sont des siloxanes cycliques volatils largement utilisés comme solvants dans les processus industriels et les produits de consommation à la place des COVs précurseurs d’ozone troposphérique tels que les BTEX. Leur présence ubiquitaire dans les échantillons d’air ambiant, due à l’utilisation massive, suscite un besoin d’études de toxicité. De telles études requièrent des analyses qualitatives et quantitatives de traces de ces composés. Par ailleurs, la présence de traces de ces substances dans un biogaz entrave son utilisation comme source d’énergie renouvelable en causant des dommages coûteux à l’équipement. L’analyse des siloxanes dans un biogaz s’avère donc essentielle pour déterminer si le biogaz nécessite une purification avant son utilisation pour la production d’énergie. La méthode développée dans cette étude possède une bonne sensibilité (LDM 4–6 μg/m3), une bonne précision (CV < 10%), une bonne exactitude (> 93%) et une grande sélectivité. Il a été également démontré qu’en utilisant cette méthode avec l’hexaméthyl-d18-disiloxane comme étalon interne, la détection et la quantification du D4 et du D5 dans des échantillons réels de biogaz peuvent être accomplies avec une meilleure sensibilité (LDM ~ 2 μg/m3), une grande précision (CV < 5%) et une grande exactitude (> 97%). Une variété d’échantillons de biogaz prélevés au site d’enfouissement sanitaire du Complexe Environnemental de Saint-Michel à Montréal a été analysée avec succès par cette nouvelle méthode. Les concentrations mesurées étaient de 131–1275 µg/m3 pour le D4 et 250–6226 µg/m3 pour le D5. Ces résultats représentent les premières données rapportées dans la littérature sur la concentration des siloxanes D4 et D5 dans les biogaz d’enfouissement en fonction de l’âge des déchets.

Influence of ambient gas on the temperature and density of laser produced carbon plasma

The effect of ambient gas on the dynamics of the plasma generated by laser ablation of a carbon target using 1.06 μm radiation from a Q-switched Nd:YAG laser has been investigated using a spectroscopic technique. The emission characteristics of the carbon plasma produced in argon, helium and air atmospheres are found to depend strongly on the nature and pressure of the surrounding gas. It has been observed that hotter and denser plasmas are formed in an argon atmosphere rather than in helium or air as an ambient.

Prompt electron emission and collisional ionization of ambient gas during pulsed laser ablation of silver

A silver target kept under partial vacuum conditions was irradiated with focused nanosecond pulses at 1:06 mm from a Nd:YAG laser. The electron emission monitored with a Langmuir probe shows a clear twin-peak distribution. The first peak which is very sharp has only a small delay and it indicates prompt electron emission with energy as much as 60 5 eV. Also the prompt electron emission shows a temporal profile with a width that is same as that for the laser pulse whereas the second peak is broader, covers several microseconds, and represents the low-energy electrons (2 0:5 eV) associated with the laser-induced silver plasma as revealed by time-of-flight measurements. It has been found that prompt electrons ejected from the target collisionally excite and ionize ambient gas molecules. Clearly resolved rotational structure is observed in the emission spectra of ambient nitrogen molecules. Combined with time-resolved spectroscopy, the prompt electrons can be used as excitation sources for various collisional excitation–relaxation experiments. The electron density corresponding to the first peak is estimated to be of the order of 1017 cm?--3 and it is found that the density increases as a function of distance away from the target. Dependence of probe current on laser intensity shows plasma shielding at high laser intensities.

High power N2 laser with a modified gas flow system and discharge geometry

A high power Nz laser of the double-Blumlein type having a modified gas flow system, electrode configuration, and discharge geometry with minimum inductance is described. By incorporating a triggere’d-pressurized spark gap switch, arc-free operation was achieved for a wide E/P range. The device gives a peak power in excess of 700 kW with a FWHM of 3 ns and an efficiency of 0.51%, which is remarkably high for a pulsed nitrogen laser system. The dependence of output power on parameters such as operating pressure, voltage, and repetition rate are discussed.

Effect of ambient gas on the expansion dynamics of plasma plume formed by laser blow off of thin film

A study has been carried out to understand the influence of ambient gases on the dynamics of laser-blow-off plumes of multi-layered LiF–C thin film. Plume images at various time intervals ranging from 100 to 3000 ns have been recorded using an intensified CCD camera. Enhancement in the plume intensity and change in size and shape occurs on introducing ambient gases and these changes are highly dependent on the nature and composition of the ambient gas used. Velocity of the plume was found to be higher in helium ambient whereas intensity enhancement is greater in argon environment. The plume shapes have maximum size at 10−2 and 10−1 Torr of Ar and He pressures, respectively. As the background pressure increases further (>10−2 Torr: depending on the nature of gas), the plume gets compressed/focused in the lateral direction. Internal structure formation and turbulences are observed at higher pressures (>10−1 Torr) in both ambient gases.

Systematics of properties of the electron gas in deep-etched quantum wires

An efficient method is developed for an iterative solution of the Poisson and Schro¿dinger equations, which allows systematic studies of the properties of the electron gas in linear deep-etched quantum wires. A much simpler two-dimensional (2D) approximation is developed that accurately reproduces the results of the 3D calculations. A 2D Thomas-Fermi approximation is then derived, and shown to give a good account of average properties. Further, we prove that an analytic form due to Shikin et al. is a good approximation to the electron density given by the self-consistent methods.

Edge excitations and topological order in rotating Bose gas

The edge excitations and related topological orders of correlated states of a fast rotating Bose gas are studied. Using exact diagonalization of small systems, we compute the energies and number of edge excitations, as well as the boson occupancy near the edge for various states. The chiral Luttinger-liquid theory of Wen is found to be a good description of the edges of the bosonic Laughlin and other states identified as members of the principal Jain sequence for bosons. However, we find that in a harmonic trap the edge of the state identified as the Moore-Read (Pfaffian) state shows a number of anomalies. An experimental way of detecting these correlated states is also discussed.

Polyconductivity in polypyrrole: The correlated electron gas

p-toluensulfonate doped polypyrrole (PPy), undergoes an electric-field induced reversible transition from an insulating state to a highly conductive one. The spatially average field can be as small as 200 V/cm, when the temperature of the sample is below 20 K. The applied electric field leads to a sharp jump in the value of the current to a value which is nearly five orders of magnitude higher than before. When the applied electric field is reduced to below a critical value, the system switches back to a low conductive state. The effect is reversible, symmetric in voltage, and reproducible for different samples. The switching is, we believe, an electronic glass melting transition and it is due to the disordered, highly charged granular nature of PPy.

Development of semiconductor metal oxide gas sensors for the detection of NO2 and H2S gases

One of the main challenges in the development of metal-oxide gas sensors is enhancement of selectivity to a particular gas. Currently, two general approaches exist for enhancing the selective properties of sensors. The first one is aimed at preparing a material that is specifically sensitive to one compound and has low or zero cross-sensitivity to other compounds that may be present in the working atmosphere. To do this, the optimal temperature, doping elements, and their concentrations are investigated. Nonetheless, it is usually very difficult to achieve an absolutely selective metal oxide gas sensor in practice. Another approach is based on the preparation of materials for discrimination between several analyte in a mixture. It is impossible to do this by using one sensor signal. Therefore, it is usually done either by modulation of sensor temperature or by using sensor arrays. The present work focus on the characterization of n-type semiconducting metal oxides like Tungsten oxide (WO3), Zinc Oxide (ZnO) and Indium oxide (In2O3) for the gas sensing purpose. For the purpose of gas sensing thick as well as thin films were fabricated. Two different gases, NO2 and H2S gases were selected in order to study the gas sensing behaviour of these metal oxides. To study the problem associated with selectivity the metal oxides were doped with metals and the gas sensing characteristics were investigated. The present thesis is entitled “Development of semiconductor metal oxide gas sensors for the detection of NO2 and H2S gases” and consists of six chapters.

Water relations, growth and gas exchange in Acacia auriculiformis under experimental and natural conditions

Investigations on the water relations and gas exchange of/tcacia aun'culiji_2rmis were carried out in natural and controlled environments. The experiments were performed in both seedlings and five year old trees. Different sets of experiments were conducted in Acacia plantations, at Kothachira, Palakkad District and in .seedlings, at KFRI campus nursery mainly during the summer months. Investigations were also extended to seedlings of A.mangium, Aaulacocarpa and /Lholocericea, which are also phyllodinous species with the intention of comparing their physiology with Acacia auriculifomus. Potted seedlings of four species of Acacia viz., A. auriculi/E)/7r:i.r, /I. aulacocarpa, A. holocericea and A. mangium were used for the study. Measurements of relative water content (RWC), water potential, photosynthetic rate, transpiration, stomatal conductance, water use efficiency etc. of phyllodes were measured diumally in plants subjected to three stress conditions namely, drought, salinity and flooding

Studies on laser induced optogalvanic effect in certain gas discharges

Electrical gas discharges have been the subject of numerous investigations from the last century due to their growing interest in technological and fundamental applications. Absorption of electromagnetic radiation by a gas discharge result into a change in electrical impedance due to a significant perturbations in the steady state population of excited levels and the degree of ionization. This change in impedance produced by resonant absorption of radiation is known as optogalvanic COG) effect. where as that is produced by injecting electrons in to the discharge by photoelectric emission is usually known as photoemission optogalvanic (FOG) effect. With the development of lasers and sophisticated electronic equipment. these effects have established their importance in analytical and spectroscopic measurements. The present thesis deals with the work carried out by the author in the field optogalvanic effect during the past few years at the Department of Physics in Cochin University of Science| and "Fechnology. The results and the observation are summarized in nine chapters and the references to the literature is made at the end of each chapter

Studies on Landfill Leachate Transportation and Its Impact on Soil Characteristics

Leachate from an untreated landfill or landfill with damaged liners will cause the pollution of soil and ground water. Here an attempt was made to generate knowledge on concentrations of all relevant pollutants in soil due to municipal solid waste landfill leachate and its migration through soil and also to study the effect of leachate on the engineering properties of soil. To identify the pollutants in soil due to the leachate generated from municipal solid waste landfill site, a case study on an unlined municipal solid waste landfill at Kalamassery has been done. Soil samples as well as water samples were collected from the site and analysed to identify the pollutants and its effect on soil characteristics. The major chemicals in the soil were identified as Ammonia, Chloride, Nitrate, Iron, Nickel, Chromium, Cadmium etc.. Engineering properties of field soil samples show that the chemicals from the leachate of landfill may have effect on the engineering properties of soil. Laboratory experiments were formulated to model the field around an unlined MSW landfill using two different soils subjected to a synthetic leachate. The Maximum change in chemical concentration and engineering property was observed on soil samples at a radial distance of 0.2 m and at a depth of 0.3 m. The pollutant (chemicals) transport pattern through the soil was also studied using synthetic leachate. To establish the effect of pollutants (chemicals) on engineering properties of soil, experiments were conducted on two types soils treated with the synthetic chemicals at four different concentrations. Analyses were conducted after maturing periods of 7, 50, 100 and 150 days. Test soils treated with maximum chemical concentration and matured for 150 days were showing major change in the properties. To visualize the flow of pollutants through soil in a broader sense, the transportation of pollutants through soil was modeled using software ‘Visual MODFLOW’. The actual field data collected for the case study was used to calibrate the modelling and thus simulated the flow pattern of the pollutants through soil around Kalamassery municipal solid waste landfill for an extent of 4 km2. Flow was analysed for a time span of 30 years in which the landfill was closed after 20 years. The concentration of leachate beneath the landfill was observed to be reduced considerably within one year after closure of landfill and within 8 years, it gets lowered to a negligible level. As an environmensstal management measure to control the pollution through leachate, permeable reactive barriers are used as an emerging technology. Here the suitability of locally available materials like coir pith, rice husk and sugar cane bagasse were investigated as reactive media in permeable reactive barrier. The test results illustrates that, among these, coir pith was showing better performance with maximum percentage reduction in concentration of the filtrate. All these three agricultural wastes can be effectively utilized as a reactive material. This research establishes the influence of leachate of municipal solid waste landfill on the engineering properties of soil. The factors such as type of the soil, composition of leachate, infiltration rate, aquifers, ground water table etc., will have a major role on the area of influence zone of the pollutants in a landfill. Software models of the landfill area can be used to predict the extent and the time span of pollution of a landfill, by inputting the accurate field parameters and leachate characteristics. The present study throws light on the role of agro waste materials on the reduction of the pollution in leachate and thus prevents the groundwater and soil from contamination

Profile simulations of gas chopping etching processes : model development and comparison with experiments

The progress in microsystem technology or nano technology places extended requirements to the fabrication processes. The trend is moving towards structuring within the nanometer scale on the one hand, and towards fabrication of structures with high aspect ratio (ratio of vertical vs. lateral dimensions) and large depths in the 100 µm scale on the other hand. Current procedures for the microstructuring of silicon are wet chemical etching and dry or plasma etching. A modern plasma etching technique for the structuring of silicon is the so-called "gas chopping" etching technique (also called "time-multiplexed etching"). In this etching technique, passivation cycles, which prevent lateral underetching of sidewalls, and etching cycles, which etch preferably in the vertical direction because of the sidewall passivation, are constantly alternated during the complete etching process. To do this, a CHF3/CH4 plasma, which generates CF monomeres is employed during the passivation cycle, and a SF6/Ar, which generates fluorine radicals and ions plasma is employed during the etching cycle. Depending on the requirements on the etched profile, the durations of the individual passivation and etching cycles are in the range of a few seconds up to several minutes. The profiles achieved with this etching process crucially depend on the flow of reactants, i.e. CF monomeres during the passivation cycle, and ions and fluorine radicals during the etching cycle, to the bottom of the profile, especially for profiles with high aspect ratio. With regard to the predictability of the etching processes, knowledge of the fundamental effects taking place during a gas chopping etching process, and their impact onto the resulting profile is required. For this purpose in the context of this work, a model for the description of the profile evolution of such etching processes is proposed, which considers the reactions (etching or deposition) at the sample surface on a phenomenological basis. Furthermore, the reactant transport inside the etching trench is modelled, based on angular distribution functions and on absorption probabilities at the sidewalls and bottom of the trench. A comparison of the simulated profiles with corresponding experimental profiles reveals that the proposed model reproduces the experimental profiles, if the angular distribution functions and absorption probabilities employed in the model is in agreement with data found in the literature. Therefor the model developed in the context of this work is an adequate description of the effects taking place during a gas chopping plasma etching process.

Delocalization of a hole in van der Waals clusters: Ionization potential of rare-gas and small Hg_n clusters

The size dependence of the ionization potential I_p(n) of van der Waals (vdW) bound clusters has been calculated by using a model Hamiltonian, which includes electron hopping, vdW interactions, and charge-dipole interactions. The charge-density and dipole-density distributions for both neutral and ionized n-atom clusters are determined self-consistently. The competition between the polarization energy of the neutral atoms surrounding a partially localized hole and the tendency toward hole delocalization in the ionized clusters is found to dominate the size dependence of I_p(n). To test our theory, we culculate I_p(Xe_n) and I_p(Kr_n) for n \le 300. Good quantitative agreement with experiment is obtained. The theory is also applied to calculate I_p(Hg_n). Comparison with experiments suggests that in Hg_n^+ clusters with n \le 20 the positive charge is mainly distributed within a trimer which is situated at the center of the cluster and which polarizes the n - 3 surrounding neutral atoms.

On the localization of electrons and holes in Hg_n and rare-gas clusters

We have used a microscopic theory to study the size dependence of the degree of localization of the valence electrons and holes in neutral an ionized rare-gas and Hg_n clusters. We discuss under which circumstances localization of the electrons and holes is favoured. We have calculated the ionization potential of Xe_n, Kr_n and small Hg_n clusters. Good agreement with experiments is obtained. We have also determined the dependence of the ionization potential on cluster structure.