Objetivo. Demonstrar que a ocorrência de episódios críticos de poluição por ozônio na região de Cubatão-Centro é influenciada pelo aporte externo de poluentes, que participam dos processos físico-químicos de formação e remoção de reagentes fotoquímicos na atmosfera. Métodos. O estudo envolveu a obtenção e o tratamento de dados meteorológicos e de concentrações de poluentes fornecidos pela rede de monitoramento da qualidade do ar, bem como a realização de campanhas de amostragem passiva de ozônio (O ) e ativa de COVs, aldeídos e etanol na atmosfera da região. A amostragem de O VI 3 foi realizada com amostradores tipo Ogawa® e as concentrações foram determinadas por cromatografia iônica, com detecção por condutividade elétrica. Na amostragem de COVs foram utilizados tubos de aço contendo o adsorvente Tenax-GR, e a quantificação das amostras foi realizada por cromatografia gasosa e espectrometria de massas. A amostragem de aldeídos foi realizada com cartuchos de sílica gel revestido com 2,4 DNPH, e a quantificação realizada por cromatografia liquida de alta performance, com detector ultravioleta (UV/VIS). A amostragem de etanol foi realizada com cartuchos revestidos de florisil, e a quantificação realizada por flame ionization detector. O transporte de massas de ar foi analisado com base em backward trajectories, calculadas pelo modelo STILT. A interpretação dos dados foi realizada por estatística descritiva, boxplot, análise de correlação e análise multivariada (clusters). Resultados. A maioria dos episódios de ultrapassagem do PQAr de ozônio ocorreu no verão, entre 15h e 16h, com ventos predominantes de S/SE e velocidades superiores a 2,5m/s, típicos de períodos diurnos (brisa marítima). As espécies orgânicas precursoras de ozônio mais importantes foram: formaldeído, acetaldeído, tolueno, 1,2,3-trimetilbenzeno, m-xileno, etanol, oxileno, etilbenzeno, 1,3,5-trimetilbenzeno e benzeno. A retrotrajetória das massas de ar que chegam à Cubatão-Centro comprovou a influência de emissões exógenas. Os resultados obtidos na circulação de mesoescala, simulada pelo modelo BRAMS, concordam com os resultados obtidos por JAESCHKE (1997), onde apenas uma parcela da concentração média de poluentes de Cubatão-Centro era oriunda de fontes locais, sendo o restante decorrente do transporte de massas, com ocorrência de elevadas concentrações de poluentes com fluxo de direção norte-noedeste (brisa terrestre) e sul-sudeste (brisa marítima) / Objective. Demonstrate that critical episode occurrences of air pollution are influenced by external input of pollutants that participate in the processes of atmospheric photochemical reagent formation and removal. Methods. The study involved meteorological data collection and processing of pollutant concentration data gathered by the air quality monitoring network. Campaigns of passive sampling of O and active sampling of VOCs, aldehydes and ethanol in the atmosphere of the region were also performed. The O 3 sampling was conducted with the Ogawa ® type samplers and the concentrations were determined by ion chromatography with electrical conductivity detector. VOCs sampling was performed using steel tubes containing Tenax GR adsorbent, and quantification was done by gas chromatography and mass spectrometry. Aldehyde sampling was performed with silica gel cartridges coated with 2,4 DNPH and quantification done by High Performance Liquid Chromatography (HPLC) with ultraviolet detector (UV / VIS). Ethanol sampling was performed with florisil coated cartridges and quantification by flame ionization detector. The transport of air masses was analyzed based on Backward trajectories calculated by the model STILT. Interpretation of the data was performed using descriptive statistics, boxplots, correlation analysis and multivariate analysis (clusters). Results. Most episodes of Ozone exceeding Air Quality Standards occurred in the summer, between 15h and 16h, with prevailing winds from S / SE and with velocities greater than 2.5 ms -1 , typical of day periods (sea breeze). Major ozone precursor organic species are: formaldehyde, acetaldehyde, toluene, 1,2,3-trimethylbenzene, m-xylene, ethanol, xylene, ethylbenzene, 1,3,5trimethylbenzene and benzene. The retro trajectory of air masses arriving at Cubatão-Center proved the influence of exogenous emissions. Results in the mesoscale circulation given by model simulation by BRAMS, agree with the results obtained by JAESCHKE (1997), showing that only a portion of the average concentration of pollutants Cubatão-Centro was due to local sources, with the rest resulting from the transport of masses, with the occurrence of high concentrations of pollutants resulting when flow directions are from NW (land breeze) and SE (sea breeze).

Sensors with very low power consumption are required so that they can last a long time without the need to replace the batteries very often. Low power sensors can save significant cost and time incurred in battery replacement, especially in establishments and organizations that span over several buildings, floors and rooms. In this thesis, we investigate the use of the low-power wireless protocol Z-wave for sensors solutions that can last for approximately 10 years. An algorithm was created and we concluded that 10 years on a 480 mAh battery is not possible and the expected years need to be lowered or we need to increase the battery capacity.

Thin Film CdS/CdTe Solar cells have been an attrative alternative to silicon solar cells because of their low cost. Numerical Modeliong using using various tools pertinent only to solar cells have been employed to study the device properties. In this work a powerful device simulation tool MEDICI is used to develop a quantitative device model. The model is modified to accommodate a glass layer and an AM1.5 spectrum is used as the simlation of light source. Analysis of the response of solar cell J-V parameters like voc and Jsc to changes in acceptor concentration, CdTe thickness and changes in the work function of the back contact under intrinsic conditions were done. Trap levels were then added in the midgap regionof the device and the earlier variations were comprehensively studied to establish the trap parameters. Further this model was extended to perform the C-V analysis of the device. Finally two cases were analysed having their energy band profile as the baseline to fix their corresponding J-V responses. The anamolous behaviour of the J-V curves namely the rollover and crossover effects were noted in detail.

Ce travail de thèse est issu d’une collaboration entre les laboratoires de recherche FEMTO-ST de l’université technologique de Belfort-Montbéliard et IRCELYON de l’université Claude Bernard à Villeurbanne. Les objectifs de cette étude portent sur la faisabilité d’élaborer par pulvérisation cathodique magnétron des films minces de cobaltite de lanthane nanostructurés. En effet, ces films présentent des propriétés catalytiques intéressantes pour l’oxydation des composés organiques volatiles comme le propène (C3H6) ou le monoxyde de carbone (CO) qui constituent la principale source de pollution de l’air. Il sera montré dans un premier temps que les cobaltites de lanthane de formule LaCoO3 ne sont pas efficaces pour ce type d’application. La composition chimique de ce matériau sera donc modifiée en y incorporant de l’argent de manière à faire varier les propriétés physico-chimiques des films et d’augmenter leurs performances catalytiques. La morphologie des films est directement impactée par l’introduction de Ag puisqu’elle évolue d’un système dense à un système « nanofilaire ». Une autre série de dépôts sera également élaborée et testée en catalyse constituée de cobaltites de lanthane dopées avec de l’argent mais aussi du cérium. On retiendra alors que les films de LaCoO3 + Ag sont plutôt efficaces et prometteurs puisqu’ils présentent des performances catalytiques se rapprochant de celles du platine (catalyseur de référence). Néanmoins, bien que les films aient toujours cette morphologie nanofilaire, les compositions chimiques des films élaborés à base de LaCoO3 + Ag + Ce doivent être optimisées afin d’augmenter leurs activités catalytiques. / This work was made in the frame of a scientific research relationships between the laboratory FEMTO-ST of the Technological University of Belfort-Montbéliard and the laboratory IRCELYON of the Claude Bernard University of Villeurbanne. This study aims at characterizing the feasibility of nanostructured lanthanum cobaltite thin films via magnetron sputtering. Indeed, it is well known these materials have interesting catalytic properties regarding the oxidation of volatile organic compounds such as propene (C3H6) or carbon monoxide (CO), the latter being the main source of air pollution. First, it has been shown that lanthanum cobaltites of formula LaCoO3 are not efficient for this type of application. The chemical composition of this material was then modified by incorporating silver so as to vary the physicochemical properties of the films and increase their catalytic performance. In consequence, the morphology of the films was directly impacted by the introduction of Ag since it evolved from a dense system to a "nanowire" system. Another series of deposits based on cobaltite modified by both silver and cerium additions have been also developed and tested during catalytic tests. It should be noted that the Ag containing thin films of LaCoO3 are rather efficient and then promising since they have catalytic performances close to those of platinum (the reference catalyst). Concerning the Ag and Ce containing perovskite films, although they still have this peculiar nanowired morphology, their chemical compositions have to be optimized in order to increase their catalytic activities.

Thin-film solar cells on glass substrates are likely to have a bright future due to the potentially low costs and the short energy payback times. Polycrystalline silicon (poly-Si, grain size &gt 1 pm) has the advantage of being non-toxic, abundant, and long-term stable. Glass as a substrate, however, limits the processing temperatures to ~600??C for longer process steps. Films with large grain size can be achieved by solid phase crystallisation (SPC), and especially by solid phase epitaxy (SPE) on seed layers, using amorphous silicon deposited at low temperatures as a precursor film. With SPC and SPE, the amorphous silicon film is typically crystallised at ~600??C over hours. During this anneal at atmospheric pressure -depending on the properties of the amorphous silicon film- ambient gas can percolate the film and can negatively affect the crystallisation. In this work, a high-vacuum anneal chamber was designed and built to allow the in-situ crystallisation of amorphous silicon films deposited on glass in a PECVD cluster tool. An important aspect of the design was the comfortable and safe operation of the vacuum anneal chamber to enable unattended operation. This was realised by means of a state-of-the-art, programmable temperature controller and a control circuit design that incorporates various safety interlocks. The chamber interior was optimised such that a temperature uniformity of 2-3K across the sample area was achieved. The chamber was calibrated and tested, and SPC and SPE samples were successfully crystallised. In initial SPC crystallisation experiments with solar cell structures, after post-deposition treatments, a 1 -sun open-circuit voltage of 465 mV was obtained, similar to furnace-annealed samples. In initial experiments with SPE solar cell structures, difficulties regarding the characterisation of the unmetallised solar cells with the quasi-steady-state open-circuit voltage method (QSSVOC) were encountered after post-deposition hydrogen treatment. A possible explanation for these difficulties is the contact formation with the metal probes. Furthermore, limiting factors of the QSSVOC method for the characterisation of unmetallised cells with high contact resistance values were investigated and, additionally, the accuracyof the QSSVOC setup was improved in the low light intensity range.

In this thesis the sink-effect in indoor materials wasstudied using mathematical modelling and experimental studies.The sink-effect is a concept which is commonly used tocharacterise the ability of different indoor materials to sorbcontaminants present in the indoor air. The sorption process ismore or less reversible, i.e. molecules sorbed in materials athigh contaminant concentrations may again be desorbed at lowerconcentrations. Knowledge of the sorption capacity of materialsand the rate at which sorption and desorption takes place is offundamental importance for mathematical simulation of indoorair quality. The aim of this work is to contribute withknowledge about how the sink-effect can be described inmathematical terms and how the interaction parametersdescribing the sorption capacity and sorption/desorptionkinetics can be determined. The work has been of amethodological nature. The procedure has been to set upphysically sound mathematical models of varying complexity andto develop small-scale chamber experiments. Two differentdynamic chamber methods have been used. One is based on amodified standard FLEC-chamber while the other uses a chamberwith two compartments, one on each side of the material. The"twin-compartment" method was designed due to the observationthat the contaminant readily permeated straight through theselected materials, which resulted in uncontrolled radiallosses in the FLEC-chamber. In order to be useful forcomparison between experiments and calculations and parameterfitting, the boundary conditions in the chambers must beprecisely known and controlled. This matter has shown to be themost crucial and difficult problem in the research. A varietyof mathematical models for the sink-effect have been proposed.In some models advanced fluid simulations were used in order totest the influence ofill-defined flow boundary conditions. Theaim of the modelling is to find a formulation with a minimum ofinteraction parameters, which is generally useful, i.e. both insmall-scale laboratory environments and in full-scale like anoffice room. Estimated model parameters are shown to be able toyield a reasonably good fit to experimental data for thesorption process but a less satisfactory fit for the desorptionprocess. <b>Keywords:</b>sink-effect, sorption, adsorption, diffusion,indoor air quality, volatile organic compounds, VOC,contaminants, building materials

Printed Circuit Board (PCB) industry is one of the two major Integrated Circuit (IC) part manufacturing industries in Taiwan, but it derives many environmental problems because large amount of chemicals and special materials are used in its process, especially copper sludge generated from wastewater treatment. Although the heavy metal sludge can be treated by solidification, heavy metals contained in the sludge may still be leached out due to longtime exposure to acid rain. Therefore, there are urgent needs of research and development of technologies regarding how to reduce both quantity and volume of the hazardous heavy metal sludge and how to recycle the valuable heavy metals. Acid leaching method, chemical exchange method and ferrite process are applied to study how to recycle and stabilize copper sludge of PCB industry. The ultimate goal is to achieve cleaning production and sustainable development by transforming the hazardous waste into valuable byproducts, reducing the amount of the waste and lowering the treatment costs. Experimental results show that a method is successfully developed to recycle copper from the sludge generated by PCB industry by using the combination of acid leaching, chemical exchange and ferrite process. Via this method, not only is pure copper powder recycled, but highly valuable nano-scaled catalyst-CuFe2O4 is also produced. Hence, the problem that copper sludge has nowhere to go is solved, as well as the high cost of catalyst in catalytic incineration is reduced to nearly zero. The achievements of this study are summarized as follow: (1) Characteristic analysis of industrial sludge Water content and pH of the sludge is 60% and 7.05, respectively. The drop in quantity of ignition is 23%. The screening test results show that particle size of the sludge varies from 0.4 £gm to 200 £gm, with D50 of 25.0 £gm. Cu, Pb, Cd, Zn, Ni and Cr are found in the sludge, and the biggest part of heavy metals is Cu, with a concentration of 158,000 mg/kg (dry basis), whereas the other heavy metals are all below 105 mg/kg (dry basis). (2) Study of recycling of pure copper powder The optimal operational condition of acid leaching method is that concentration of sulfuric acid is 2.0 N, temperature is 50¢J and treatment time is 60 minutes. Under this operational condition, more than 99% of heavy metals can be extracted to liquid phase and the sediment of treated sludge meet Toxicity Characteristic Leaching Procedure (TCLP) standards and therefore is considered as general industrial waste. The optimal operational condition of chemical exchange method is that molar ratio of Fe/Cu is 5.0, pH is 2.0 and treatment temperature is 50¢J. Under this operational condition, more than 95.0% of Cu can be recovered. The optimal operational condition of ferrite process is that Fe/Cu=10.0, pH=9.0, treatment temperature=80¢J, aeration rate=3 L/min/per liter waste liquid and reaction time = 30 min. Under this operational condition, TCLP concentrations of all heavy metals of both supernatant and sludge are well below regulatory standards, which proves that ferrite process is very effective. (3) Resourcing of spinel sludge In the potential of catalytic incineration of volatile organic compounds test, the sludge generated from ferrite process is used to catalyze the isopropyl alcohol (IPA). The catalyst is replaced by the same volume of glass wool on a reactive bed as a blank. Experimental result shows that the conversion of IPA is only 10% at 200¢J and 75% at 500¢J in the absence of catalyst under the conditions that IPA inlet concentration=1,700 ppm, space velocity=24,000 hr-1, O2 concentration=21%, and relative humidity=19%, which indicates that the destruction of IPA is associated with the consumption of much energy when no catalyst was used. But when ferrite catalyst is applied, IPA is decomposed completely at 200¢J, showing that the sludge has great potential of catalyst. (4) Synthesizing five VOCs catalyzing ferrite catalysts via ferrite process As to the synthesis of five ferrite catalysts in the laboratory, IPA conversion rate is higher than 58% at 200¢J. The sequence of IPA conversion from good to bad is Cu-ferrite catalyst > Mn-ferrite catalyst > Ni-ferrite catalyst > Zn-ferrite catalyst > Cr-ferrite catalyst, where Cu/Fe is most efficiency, with IPA conversion rate of 75% at 150¢J and 100% at 200¢J.

Chlorinated solvent are volatile organic substances that can be harmful for humans and for the environment. Examples of common chlorinated solvents are perchloroethene, PCE, and trichloroethene, TCE. Chlorinated solvents appear as contaminants in soils primarily where they have been used as washing fluids in dry-cleaning facilities or as degreasers in metal industries. Chlorinated solvents are DNAPLs (dense non-aqueous phase liquids), which means that they are not easily dissolved in water and that they sink to the bottom of the aquifer. Adsorption to soils is low so chlorinated solvents are mobile in soils. Chlorinated solvents can be harmful at low concentrations. Complete degradation can only occur under specific conditions. Because of the properties of these substances, investigation and analysis methodology are extra important for determining transport and risks in a contaminated area. In this work, investigation and analysis methods for chlorinated solvents are described. Planning, fieldwork, modeling and risk analysis are described. Projects concerning chlorinated solvents completed by Golder Associates AB have been compiled and analysed. Based on the compilation, conclusions have been drawn and statistics have been calculated. Investigations of the relation between concentrations in different media have been made as well as investigations of the relation between degradation products at different distances from the source and at different times after release. The data from the environmental investigations have been compared with theoretical literature values and modelling results. The results show that there is a large natural variation in the data and that the differences between different areas are quite large. The results confirm the theory that the percentage of degradation products increases with distance from the source and with time from release. In addition, solvents with a higher degree of chlorination seams to appear to a greater extent in the soil and the more volatile substances seams to appear to a greater extent in the soil air. / Klorerade lösningsmedel är flyktiga klorerade organiska ämnen som kan vara skadliga för människor och miljön. Exempel på vanliga klorerade lösningsmedel är perkloreten, PCE och trikloreten, TCE. Klorerade lösningsmedel förekommer som markföroreningar främst efter användning som tvättvätska i kemtvättar och som avfettningsmedel i metallindustrin. Klorerade lösningsmedel är DNAPLs (dense non-aqueous phase liquids), det innebär att de är svårlösliga i vatten och att de sjunker och lägger sig på botten av akviferen. Fastläggningen i jorden är liten hos klorerade lösningsmedel som därmed är rörliga i marken. De är farliga redan vid små koncentrationer och fullständig nedbrytning sker endast under vissa förutsättningar. Ämnenas egenskaper gör att undersöknings- och analysmetodiken är viktig för att riktigt kunna bestämma deras utbredning och risk på ett förorenat område. I detta arbete beskrivs undersöknings- och analysmetodiken för områden förorenade med klorerade lösningsmedel. Upplägg, fältarbete, modellering och riskbedömning beskrivs. Projekt som handlar om klorerade lösningsmedel utförda av Golder Associates AB har sammanställts. Sammanställningen har analyserats och utifrån den har olika slutsatser dragits och statistik beräknats. Bland annat har samband mellan halter i olika medier samt samband mellan halter av nedbrytningsprodukter på olika avstånd från källan respektive efter olika lång tid från läckage har undersökts. Data från miljöundersökningarna har även jämförts med teoretiska litteraturvärden samt modelleringsresultat. Resultatet visar att den naturliga spridningen av data är stor samt att resultaten skiljer sig åt mellan olika områden. Resultaten bekräftar teorierna att halten nedbrytningsprodukter ökar med avståndet från källan och med tiden samt att ämnen med högre kloreringsgrad finns i större utsträckning i jorden och att flyktigare ämnen finns i större utsträckning i porluften.

In this study, atmospheric levels and sources of VOCs at Aliaga industrial area was investigated. For this, VOC concentrations were measured at two monitoring stations through winter and summer campaigns in 2005 and 2006. Sampling stations were located in downtown Aliaga and downwind of industrial facilities, approximately 500 m to the south east of Horozgedigi village. After the summer sampling, another temporary station was installed in between PETKIM and T&Uuml / PRAS, named as T&Uuml / PRAS Station to generate T&Uuml / PRAS and PETKIM profiles. More than 50 species were measured in all stations. In all stations, toluene has the highest contribution to total VOC concentration. Toluene is followed by m,p-xylene and benzene. While higher concentrations of traffic related VOCs were measured at Aliaga station, VOCs from industrial solvents and industrial processes were higher at Horozgedigi station. The concentration levels in Aliaga and Horozgedigi are found to be comparable to the other industrial regions reported in the literature. Investigation of episodes, diurnal variations of VOCs and meteorological parameters showed that PETKIM and T&Uuml / PRAS emissions affect the concentrations levels at Horozgedigi and Aliaga stations. Source profiles of PETKIM and T&Uuml / PRAS are determined by using the T&Uuml / PRAS station data set. 2-methyl-hexane, benzene and 2,2,3-tri-methyl-butane+2,3-di-methyl-pentane are found to be good markers of PETKIM emissions. Ten different VOC sources were identified in the region. These were gasoline exhaust, diesel exhaust, natural gas use, gasoline evaporation, industrial emissions-1, natural gas construction, non-industrial solvent use, industrial emissions-2, PETKIM emissions, and mixed emissions from PETKIM and shipbreaking facilities.

There has always been a desire to develop industrial processes that minimize the resources they use, and the wastes they generate. The problem is when new guidelines are forced upon long established processes, such as solvent based coating operations. This means instead of integrating an emission reduction technology into the original design of the process, it is added on after the fact. This significantly increases the costs associated with treating emissions. In this work the ultimate goal is the design of an “add-on” abatement system to treat emissions from solvent based coating processes with high destruction efficiency, and lower costs than systems in current use. Since emissions from processes that utilize solvent based coatings are primarily comprised of volatile organic compounds (VOCs), the treatment of these compounds will be the focus. VOCs themselves contain a significant amount of energy. If these compounds could be destroyed by simultaneously extracting the energy they release, operational costs could be substantially reduced. This thesis examines the use of model-based design to develop and optimize a VOC abatement technology that uses a Solid Oxide Fuel Cell (SOFC) for energy recovery. The model was built using existing HYSYS unit operation models, and was able to provide a detailed thermodynamic and parametric analysis of this technology. The model was validated by comparison to published literature results and through the use of several Design of Experiment factorial analyses. The model itself illustrated that this type of system could achieve 95% destruction efficiency with performance that was superior to that of Thermal Oxidation, Biological Oxidation, or Adsorption VOC abatement technologies. This was based upon design criteria that included ten year lifecycle costs and operational flexibility, as well as the constraint of meeting (or exceeding) current regulatory thresholds.