Chlorophenols in tap water from wells and surface sources in Rio de Janeiro, Brazil: method validation and analysis

Two analytical methods were validated for determination of trichlorophenols, tetrachlorophenols and pentachlorophenol in drinking water. Limits of quantification were at least ten times lower than maximum permissible levels set by the Brazilian legislation, which are 200 ng mL-1 for 2,4,6-trichlorophenol and 9 ng mL-1 for pentachlorophenol. Chlorophenol levels were determined in tap water collected in the Municipality of Rio de Janeiro. 2,4,6-Trichlorophenol residues were detected in 36% of the samples, varying from 0.008 to 0.238 ng mL-1. All other analytes were below the limit of quantification. The validated methods showed to be suitable for application in routine quality control.

Occurrence of agrochemicals in surface waters of shallow soils and steep slopes cropped to tobacco

Tobacco cultivation in shallow soils and steep landscape under intense use of agrochemicals contributes to environment degradation. In this study, we assessed the concentration of agrochemicals in draw wells used for human consumption and a creek in a small catchment predominantly cropped to tobacco. Chlorpyrifos, flumetralin, and iprodione were determined by gas chromatography with electron capture detection, while imidalcloprid, atrazine, simazine, and clomazone were quantified by high-performance liquid chromatography with UV detection. Considering all sampling sites, all agrochemicals were detected at least once, except for flumetralin. The occurrence of agrochemicals in tobacco crops is a consequence of their fast transfer to surface water.

GLOBAL AND LOCAL REACTIVITY DESCRIPTORS FOR PICLORAM HERBICIDE: A THEORETICAL QUANTUM STUDY

In this work, we studied the reactivity of picloram in the aqueous phase at the B3LYP/6-311++G(2d,2p) and MP2/6-311++G(2d,2p) levels of theory through global and local reactivity descriptors. The results obtained at the MP2 level indicate that the cationic form of picloram exhibits the highest hardness while the anionic form is the most nucleophilic. From the Fukui function values, the most reactive site for electrophilic and free radical attacks are on the nitrogen in the pyridine ring. The more reactive sites for nucleophilic attacks are located on the nitrogen atom of the amide group and on the carbon atoms located at positions 2 and 3 in the pyridine ring.

METHANE DRY REFORMING OVER Ni SUPPORTED ON PINE SAWDUST ACTIVATED CARBON: EFFECTS OF SUPPORT SURFACE PROPERTIES AND METAL LOADING

The influence of metal loading and support surface functional groups (SFG) on methane dry reforming (MDR) over Ni catalysts supported on pine-sawdust derived activated carbon were studied. Using pine sawdust as the catalyst support precursor, the smallest variety and lowest concentration of SFG led to best Ni dispersion and highest catalytic activity, which increased with Ni loading up to 3 Ni atoms nm-2. At higher Ni loading, the formation of large metal aggregates was observed, consistent with a lower "apparen" surface area and a decrease in catalytic activity. The H2/CO ratio rose with increasing reaction temperature, indicating that increasingly important side reactions were taking place in addition to MDR.

SIMULTANEOUS DETERMINATION OF PROTOCATECHUIC ALDEHYDE AND PROTOCATECHUIC ACID USING THE LOCALIZED SURFACE PLASMON RESONANCE PEAK OF SILVER NANOPARTICLES AND CHEMOMETRIC METHODS

A simple and sensitive spectrophotometric method is proposed for the simultaneous determination of protocatechuic acid and protocatechuic aldehyde. The method is based on the difference in the kinetic rates of the reactions of analytes with [Ag(NH3)2]+ in the presence of polyvinylpyrrolidone to produce silver nanoparticles. The data obtained were processed by chemometric methods using principal component analysis artificial neural network and partial least squares. Excellent linearity was obtained in the concentration ranges of 1.23-58.56 µg mL-1 and 0.08-30.39 µg mL-1 for PAC and PAH, respectively. The limits of detection for PAC and PAH were 0.039 and 0.025 µg mL-1, respectively.

Surface Modification of Ceramics

Ceramics are widely used in industrial applications due to their advantageous thermal and mechanical stability. Corrosion of ceramics is a great problem resulting in significant costs. Coating is one method of reducing adversities of corrosion. There are several different thin film deposition processes available such as sol-gel, Physical and Chemical Vapour Deposition (PVD and CVD). One of the CVD processes, called Atomic Layer Deposition (ALD) stands out for its excellent controllability, accuracy and wide process capability. The most commonly mentioned disadvantage of this method is its slowness which is partly compensated by its capability of processing large areas at once. Several factors affect the ALD process. Such factors include temperature, the grade of precursors, pulse-purge times and flux of precursors as well as the substrate used. Wrongly chosen process factors may cause loss of self-limiting growth and thus, non-uniformities in the deposited film. Porous substrates require longer pulse times than flat surfaces. The goal of this thesis was to examine the effects of ALD films on surface properties of a porous ceramic material. The analyses applied were for permeability, bubble point pressure and isoelectric point. In addition, effects of the films on corrosion resistance of the substrate in aqueous environment were investigated. After being exposured to different corrosive media the ceramics and liquid samples collected were analysed both mechanically and chemically. Visual and contentual differences between the exposed and coated ceramics versus the untreated and uncoated ones were analysed by scanning electron microscope. Two ALD film materials, dialuminium trioxide and titanium dioxide were deposited on the ceramic substrate using different pulse times. The results of both film materials indicated that surface properties of the ceramic material can be modified to some extent by the ALD method. The effect of the titanium oxide film on the corrosion resistance of the ceramic samples was observed to be fairly small regardless of the pulse time.

The Li+, Na+ and K+ ion exchange reaction process on the surface of mixed oxide SiO2/TiO2/Sb2O5 surface prepared by the sol-gel processing method

The porous mixed oxide SiO2/TiO2/Sb2O5 obtained by the sol-gel processing method presented a good ion exchange property and a high exchange capacity towards the Li+, Na+ and K+ ions. In the H+/M+ ion exchange process, the H+ / Na+ could be described as presenting an ideal character. The ion exchange equilibria of Li+ and K+ were quantitatively described with the help of the model of fixed tetradentate centers. The results of simulation evidence that for the H+ / Li+ exchange the usual situation takes place: the affinity of the material to the Li+ ions is decreased with increasing the degree of ion exchange. On the contrary, for K+ the effects of positive cooperativity, that facilitate the H+ / K+ exchange, were revealed.

A water soluble 3-n-propyl-1-azonia-4-azabicyclo[2.2.2]octanechloride silsesquioxane grafted onto Al/SiO2 surface: chromium adsorption study

The water soluble material, 3-n-propyl-1-azonia-4-azabicyclo[2.2.2]octanechloride silsesquioxane (dabcosil silsesquioxane) was obtained. The dabcosil silsesquioxane was grafted onto a silica surface, previously modified with aluminum oxide. The resulting solid, dabcosil-Al/SiO2, presents 0.15 mmol of dabco groups per gram of material. The product of the grafting reaction was analyzed by infrared spectroscopy and N2 adsorption-desorption isotherms. The dabcosil-Al/SiO2 material was used as sorbent for chromium (VI) adsorption in aqueous solution.

Immersion enthalpy variation of surface-modified mineral activated carbon in lead (II) aqueous solution adsorption: the relation between immersion enthalpy and adsorption capacity

An activated carbon was obtained by chemical activation with phosphoric acid, CM, from a mineral carbon. Afterwards, the carbon was modified with 2 and 5 molL-1, CMox2 and CMox5 nitric acid solutions to increase the surface acid group contents. Immersion enthalpy at pH 4 values and Pb2+ adsorption isotherms were determined by immersing activated carbons in aqueous solution. The surface area values of the adsorbents and total pore volume were approximately 560 m².g-1 and 0.36 cm³g-1, respectively. As regards chemical characteristics, activated carbons had higher acid sites content, 0.92-2.42 meq g-1, than basic sites, 0.63-0.12 meq g-1. pH values were between 7.4 and 4.5 at the point of zero charge, pH PZC. The adsorbed quantity of Pb2+ and the immersion enthalpy in solution of different pH values for CM activated carbon showed that the values are the highest for pH 4, 15.7 mgg-1 and 27.6 Jg-1 respectively. Pb2+ adsorption isotherms and immersion enthalpy were determined for modified activated carbons and the highest values were obtained for the activated carbon that showed the highest content of total acid sites on the surface.

Adsorption of hidrogen peroxide on the surface of silica - titania mixed oxide obtained by the sol-gel processing method

This work describes the sol-gel mixed oxide SiO2/TiO2 property, ST, as prepared, and submitted to heat treatment a 773 K, STC. SEM and EDS images show, within magnification used, a uniform distribution of the TiO2 particles in SiO2/TiO2 matrix. Both, ST and STC adsorb hydrogen peroxide on the surface and through EPR and UV-Vis diffuse reflectance spectra, it was possible to conclude that the species on the surface is the peroxide molecule attached to the Lewis acid site of titanium particle surface, alphaTi(H2O2)+. As the material is very porous, presumably the hydrogen peroxide molecule is confined in the matrix pores on the surface, a reason why the adsorbed species presents an exceptional long lived stability.

Lanthanum based high surface area perovskite-type oxide and application in CO and propane combustion

The perovskite-type oxides using transition metals present a promising potential as catalysts in total oxidation reaction. The present work investigates the effect of synthesis by oxidant co-precipitation on the catalytic activity of perovskite-type oxides LaBO3 (B= Co, Ni, Mn) in total oxidation of propane and CO. The perovskite-type oxides were characterized by means of X-ray diffraction, nitrogen adsorption (BET method), thermo gravimetric and differential thermal analysis (ATG-DTA) and X-ray photoelectron spectroscopy (XPS). Through a method involving the oxidant co-precipitation it's possible to obtain catalysts with different BET surface areas, of 33-44 m²/g, according the salts of metal used. The characterization results proved that catalysts have a perovskite phase as well as lanthanum oxide, except LaMnO3, that presents a cationic vacancies and generation for known oxygen excess. The results of catalytic test showed that all oxides have a specific catalytic activity for total oxidation of CO and propane even though the temperatures for total conversion change for each transition metal and substance to be oxidized.

Comparison of Local Feature Detectors and Descriptors for Visual Object Categorization

Local features are used in many computer vision tasks including visual object categorization, content-based image retrieval and object recognition to mention a few. Local features are points, blobs or regions in images that are extracted using a local feature detector. To make use of extracted local features the localized interest points are described using a local feature descriptor. A descriptor histogram vector is a compact representation of an image and can be used for searching and matching images in databases. In this thesis the performance of local feature detectors and descriptors is evaluated for object class detection task. Features are extracted from image samples belonging to several object classes. Matching features are then searched using random image pairs of a same class. The goal of this thesis is to find out what are the best detector and descriptor methods for such task in terms of detector repeatability and descriptor matching rate.

Influence of plasma modification on surface properties and offset printability of coated paper

The properties of the paper surface play a crucial role in ensuring suitable quality and runnability in various converting and finishing operations, such as printing. Plasma surface modification makes it possible to modify the surface chemistry of paper without altering the bulk material properties. This also makes it possible to investigate the role of the surface chemistry alone on printability without influencing the porous structure of the pigment-coated paper. Since the porous structure of a pigment coating controls both ink setting and optical properties, surface chemical changes created by a plasma modification have a potential to decouple these two effects and to permit a better optimization of them both. The aim of this work was to understand the effects of plasma surface modification on paper properties, and how it influences printability in the sheet-fed offset process. The objective was to broaden the fundamental understanding of the role of surface chemistry on offset printing. The effects of changing the hydrophilicity/ hydrophobicity and the surface chemical composition by plasma activation and plasma coatings on the properties of coated paper and on ink-paper interactions as well as on sheet-fed offset print quality were investigated. In addition, the durability of the plasma surface modification was studied. Nowadays, a typical sheet-fed offset press also contains units for surface finishing, for example UVvarnishing. The role of the surface chemistry on the UV-varnish absorption into highly permeable and porous pigment-coated paper was also investigated. With plasma activation it was possible to increase the surface energy and hydrophilicity of paper. Both polar and dispersion interactions were found to increase, although the change was greater in the polar interactions due to induced oxygen molecular groups. The results indicated that plasma activation takes place particularly in high molecular weight components such as the dispersion chemicals used to stabilize the pigment and latex particles. Surface composition, such as pigment and binder type, was found to influence the response to the plasma activation. The general trend was that pilot-scale treatment modified the surface chemistry without altering the physical coating structure, whereas excessive laboratory-scale treatment increased the surface roughness and reduced the surface strength, which led to micro-picking in printing. It was shown that pilot-scale plasma activation in combination with appropriate ink oils makes it possible to adjust the ink-setting rate. The ink-setting rate decreased with linseed-oil-based inks, probably due to increased acid-base interactions between the polar groups in the oil and the plasma-treated paper surface. With mineral-oil-based inks, the ink setting accelerated due to plasma activation. Hydrophobic plasma coatings were able to reduce or even prevent the absorption of dampening water into pigmentcoated paper, even when the dampening water was applied under the influence of nip pressure. A uniform hydrophobic plasma coating with sufficient chemical affinity with ink gave an improved print quality in terms of higher print density and lower print mottle. It was also shown that a fluorocarbon plasma coating reduced the free wetting of the UV-varnish into the highly permeable and porous pigment coating. However, when the UV-varnish was applied under the influence of nip pressure, which leads to forced wetting, the role of the surface chemical composition seems to be much less. A decay in surface energy and wettability occurred during the first weeks of storage after plasma activation, after which it leveled off. However, the oxygen/carbon elemental ratio did not decrease as a function of time, indicating that ageing could be caused by a re-orientation of polar groups or by a contamination of the surface. The plasma coatings appeared to be more stable when the hydrophobicity was higher, probably due to fewer interactions with oxygen and water vapor in the air.

Influence of topography and surface chemistry on the wetting properties of TiO2-based ceramic coatings

Vätning av fasta ytor är ett viktigt fenomen i såväl naturen som i en lång rad av industriella tillämpningar. Det är allmänt känt att vätningen av en fast yta styrs av ytans kemi samt struktur. Målsättningen med avhandlingen var att studera hur kemisk heterogenitet och ytråhet på nanometernivå påverkar vätningsegenskaperna hos en fast yta. Ytorna som studerades var titandioxid-baserade kerama ytor som framställdes med hjälp av en sol-gel process. Vätningstudierna utfördes genom kontaktvinkelmätningar, vilket innebär att man mäter vinkeln som vätska/luft-gränsskiktet hos en vätskedroppe bildar mot en fast yta. Ytråheten hos materialen studerades främst genom atomkraftsmikroskopi (AFM). I AFM detekteras ytans struktur av en mycket skarp nål som skannar ytan. Resultaten i avhandlingen kunde framgångsrikt modelleras med existerande teorier för vätning av heterogena ytor.