No description available.

<p>This thesis describes some new methods for analysis oforganic trace components from air and water by gaschromatography. The work is particularly focused on thedevelopment of new technologies for analyte enrichment, usingsorbent-based concepts. Short lengths of open tubular columnswere examined for their potential use as denuders.Polydimethylsiloxane-based stationary phases as well as anadsorbent-based column were evaluated in an equilibrium mode oftrapping. For the analytes selected, detection levels in theppb range were obtained (Paper I).</p><p>A new, fully automated set-up for analysis of organic tracecomponents in aqueous samples has been developed (Paper II).The work combines specific advantages of the solid phase microextraction (SPME) technology and stir bar sorptive extractionconcept. Ultra trace components, down to 0.1 ppt could bedetected. Finally a simple method for preparation a new type ofultra thick film open tubular trap is described (Paper III).The traps are characterized by an irregular coating, and it wasdemonstrated that the performance characteristics of thesetraps were practically as good as of traps with a smooth,regular coating. The technology can be utilized in many areas,e.g. environmental monitoring, process analysis and otherfields dealing with analysis of trace organic volatiles ingaseous samples.</p><p><b>Keywords:</b>Organic trace components, volatiles, denuders,sorbent trapping, thick film trapping, open tubular traps,SPME, automation, water analysis, gas analysis, environmentalanalysis.</p>

This thesis investigated the impact of aluminum (Al) substitution in ferrihydrite (FH) on both its chemical and physical properties. Al was coprecipitated with FH under controlled hydrolysis conditions to yield various % mol substitutions. Sulfate adsorption was measured across pHs to examine any changes in surface reactivity. The samples’ morphology, specific surface areas (SSAs), crystallinity, and phase transformation upon heating were evaluated and parameterized to allow conclusions on the role of Al on the physical properties. Sulfate sorption diminished across pHs for all Al saturation levels. X-ray Diffraction revealed goethite (GT) presence was negatively influenced by Al. The SSAs of samples increased non-linearly with increasing % mol Al, indicating a decreasing particle size with more Al content. Transmission Electron Microscopy micrographs showed the FH nanoparticles transformed to acicular/blocky laths of GT crystals and lenticular/platy hematite (HM) crystals with occasional grainy appearance at both room temperature and upon active heating. The phase transformation alongside the derived aspect ratios (length/width) of the GT crystals were retarded by the Al substitution.

A commercially available product, PURA PhosLock, was identified and evaluated for use as a sorbent to remove dissolved arsenic (As) from drinking water. Although marketed as a product to remove phosphate in aquaria, it is composed of iron oxide hydroxide (i.e., FeO(OH)), which is also known to adsorb dissolved As species from water. Arsenic was measured using standard methods and Graphite Furnace Atomic Absorption Spectroscopy. A first rough filtration test was performed to see if the PhosLock adsorbed As well. About 50 g of PhosLock was used to filter 10 L of tap water containing 100 ppb As. No detectable As was observed in the filtrate. A sorption study was then performed to determine the time required to reach equilibrium, which was attained after seven hours. A second set of sorption studies were performed using different As concentrations and the data was evaluated using the Langmuir adsorption model. The model predicted a maximum adsorption capacity of 457 to 636 mg/g. A final flowing water column breakthrough experiment was performed. Tap water spiked with 50 ppb was filtered through 0.5 grams of sorbent in a glass chromatography column. The results showed that seven liters of water were filtered before any As was detected. Over 10 L were filtered before the maximum contaminant level ( MCL) of 10 ppb was exceeded. The flow through study results showed that the PhosLock has an As adsorption capacity of 700 mg/g. This is consistent with the highest sorption capacity predicted by the Langmuir model. The results of this study show that PhosLock is a very effective and economical sorbent for the removal of As from drinking water.

No description available.

Sample preparation has a critical role as a first step in analytical processes, especially in bioanalysis and environmental analysis. A good sample preparation technique should be robust and stable, regardless of the sample matrix. The aim of this thesis is to design and synthesize molecularly imprinted polymers that can be used in various sample preparation techniques, such as on-line MEPS, on-line SPE and on-line monolithic pre-columns used for the extraction of drugs, hormones, and cancer biomarkers from human plasma and urine samples. Additional aim was to provide full automation, on-line coupling, short sample preparation time and high-throughput. In this thesis MIP in MEPS was used on-line with liquid chromatography-tandem mass spectrometry (LC/MS/MS) for the determination of sarcosine in human urine and plasma samples. The method was fully automated and the packed sorbent could be used for about hundred extractions. In additional work a coated needle with MIP-Sol-Gel as thin layer was prepared and used for the microextraction of bilirubin from human plasma and urine. Small sample volumes could be handled and the validation of the method showed that the method was robust and selective. In a further work MIP-SPE on-line with HPLC was used for the extraction and determination of dextromethorphan in human plasma samples. MIP-SPE showed a good selectivity and high recovery (87% - 92%). On-line MIP monolithic pre-column was prepared and used in a coupled system for the extraction of tramadol in human plasma and urine samples. The MIP monolithic pre-column showed good selectivity and high extraction recovery was obtained (91-96%). The extraction and analysis of human insulin in plasma and pharmaceutical formulation solutions were carried out using MIP-SPE on-line with HPLC. The validation of the method showed that the method was accurate and robust. / <p>At the time of the doctoral defense, the following paper was unpublished and had a status as follows: Paper 5: Submitted.</p>

Orientador: Carla Beatriz Grespan Bottoli / Dissertação (mestrado) - Universidade Estadual de Campinas, Instituto de Quimica / Made available in DSpace on 2018-08-11T10:14:09Z (GMT). No. of bitstreams: 1 Gorzalka_ThaisProenca_M.pdf: 829922 bytes, checksum: f9029b9c9c8227216344c808efc2ffdd (MD5) Previous issue date: 2008 / Resumo: Este trabalho teve como objetivo desenvolver um material baseado em polibutadieno (PBD) e sílica e avaliar seu desempenho como fase estacionária em cromatografia líquida de alta eficiência no modo fase reversa (CLAE-FR) e como sorvente para extração em fase sólida (SPE). O preparo do material consistiu na deposição do PBD na superfície da sílica seguida de imobilização por tratamento térmico na presença de peróxido de dicumila (PDC). Para a aplicação como fase estacionária, algumas variáveis de preparo foram otimizadas, como a pressão de enchimento das colunas cromatográficas (5000 psi), porcentagem de carga de polibutadieno (10 % m/m), porcentagem de peróxido de dicumila (2,5 % m/m PDC/PBD), tempo, temperatura e atmosfera de tratamento térmico (1 h a 120 °C seguida de 4 h a 160 °C, atmosfera oxidante). A fase estacionária preparada nas condições otimizadas proporcionou colunas com eficiência de 81 000 pratos por metro para o acenafteno. Valores típicos de colunas quimicamente ligadas são de 100 000 pratos por metro. No teste de estabilidade, realizado sob condições drásticas, a fase estacionária preparada na presença de peróxido de dicumila se mostrou mais estável que a fase estacionária preparada na ausência do peróxido. Também foi observado que o PBD se altera no frasco de estocagem independente dos cuidados tomados para evitar o contato com o ar durante seu manuseio. Esta alteração resultou em redução da eficiência das colunas, dificuldade de reprodutibilidade no preparo das fases e uma maior atividade silanofílica ao longo do tempo. Para a aplicação do material como sorvente para extração em fase sólida os cartuchos foram avaliados na extração de agrotóxicos em uma amostra de vinho. Pôde-se concluir que o sorvente baseado em polibutadieno é um material promissor, sendo comparável aos cartuchos C18 disponíveis comercialmente, apresentando boas eficiências de extração (95 - 119 %) / Abstract: This study aimed to develop a material based on polybutadiene (PBD) and silica and to evaluate its performance as a stationary phase in Reversed-Phase High Performance Liquid Chromatography (RP-HPLC) and as sorbent for Solid-Phase Extraction (SPE). The preparation of the material consisted of the deposition of PBD onto the surface of porous silica, followed by immobilization by thermal treatment in the presence of dicumyl peroxide (DCP). For application as a stationary phase some variables were optimized, such as packing pressure (5000 psi), polybutadiene load (10 % m/m), dicumyl peroxide load (2.5% m/m DCP/PBD), temperature, time and atmosphere of thermal treatment (1 h at 120 °C followed by 4 h at 160 °C, in an oxidizing atmosphere). The stationary phase prepared under these conditions yielded a column with efficiency of 81 000 plates per meter for acenaphthene. Tipical values for chemical-bonded stationary phases are about 100 000 plates per meter. A chemical stability test, carried out under drastic conditions, showed that the stationary phase prepared in presence of dicumyl peroxide was more stable than a stationary phase prepared in the absence of peroxide. It was also observed that PBD is altered during storage, independent of the care taken to avoid contact with air during its handling. This change resulted in reduced efficiency of the columns, difficulty in reproducing preparations and higher silanophilic activity over the time. For application of the material as a sorbent in solid-phase extraction, the prepared cartridges were evaluated for extraction of pesticides from a sample of wine. It can be conclude that a sorbent based on polybutadiene is a promising material, and is comparable to a commercially available C18 cartridge showing good efficiencies of extraction (95 - 119 %) / Mestrado / Quimica Analitica / Mestre em Química

This diploma thesis deals with the preparation of solid hydrophilic sponges made of acetalized PVAl. The sponges were produced by foaming by gaseous reaction by-product. The experimental work also includes the study of active compound immobilization into the sponge (finely ground lignite as a heavy metal sorbent).

This thesis describes some new methods for analysis oforganic trace components from air and water by gaschromatography. The work is particularly focused on thedevelopment of new technologies for analyte enrichment, usingsorbent-based concepts. Short lengths of open tubular columnswere examined for their potential use as denuders.Polydimethylsiloxane-based stationary phases as well as anadsorbent-based column were evaluated in an equilibrium mode oftrapping. For the analytes selected, detection levels in theppb range were obtained (Paper I). A new, fully automated set-up for analysis of organic tracecomponents in aqueous samples has been developed (Paper II).The work combines specific advantages of the solid phase microextraction (SPME) technology and stir bar sorptive extractionconcept. Ultra trace components, down to 0.1 ppt could bedetected. Finally a simple method for preparation a new type ofultra thick film open tubular trap is described (Paper III).The traps are characterized by an irregular coating, and it wasdemonstrated that the performance characteristics of thesetraps were practically as good as of traps with a smooth,regular coating. The technology can be utilized in many areas,e.g. environmental monitoring, process analysis and otherfields dealing with analysis of trace organic volatiles ingaseous samples. <b>Keywords:</b>Organic trace components, volatiles, denuders,sorbent trapping, thick film trapping, open tubular traps,SPME, automation, water analysis, gas analysis, environmentalanalysis. / NR 20140805

Replacing the lost Phosphates from different ecosystems is not a question it’s an onus. This none replaceable and renewable resource is one of the vital nutrients where without it, cells, crops and human beings cannot function and live. Though available in environment, its natural cycle is disturbed as its need especially in agriculture sector increases significantly. Phosphorus recovery from waste water sorbents is one of the innovative and promising concepts. The core goal of this paper is to evaluate the phosphorus desorbing capacity of two reactive materials (waste water sorbents) using chemical extracts. The experimental work emphasized on investigation four extracts, HNO3, NaHCO3, P-AL and H2O on phosphate desorption capacity of two inorganic reactive materials namely Polonite® and Sorbulite® which are widely known for their high P-sorption capacity. The kinetics and desorption were examined in batch experiments and consequently the plant availability were investigated using Flow Injection Analyzing (FIA) spectroscopy (wet chemistry) method. The maximum average orthophosphate desorption at 100 rpp for 48 hrs was interpreted to be 33.12 mg g−1and 3.11 mg g−1 from Sorbulite® and Polonite® respectively using 4M HNO3 extract. The orthophosphate desorption characteristic using the above extracts tended to decrease in the following order HNO3 ≤ P-AL ≤ NaHCO3 ≤ H2O. Polonite® shows a higher recovery potential, where almost 6 times higher ammonium lactate (AL)-extractable P was observed when compared with Sorbulite®. Batch experiment was proved to be a tool for investigating and evaluating Phosphorus desorption capacity of mineral-based filter materials.