Reflexo de um modo de vida que exige locomoção rápida e com um mínimo de conforto, atualmente, nas grandes metrópoles, há um grande número de veículos em circulação que emitem gases poluentes (hidrocarbonetos, CO e óxidos de nitrogênio - NOx). Para minimizar a emissão desses gases, os carros atuais são dotados de conversores catalíticos, formados pelos metais do grupo da platina, com a finalidade de converter gases nocivos em gases menos agressivos ao ambiente e ao homem. Porém, esses elementos constituintes dos conversores catalíticos podem ser expelidos para o ambiente, na forma de materiais particulados em suspensão, por volatilização ou junto com os gases da combustão. Desta forma, esses elementos podem acumular-se nos mais diversos ambientes. A utilização de amostras biológicas, tal como sangue, na investigação e no controle à exposição de elementos nos seres humanos vem sendo praticada há muito tempo. Estudos com materiais biológicos apontam que as concentrações de metais do grupo da Platina estão na ordem de ng/kg. Tais níveis de concentração representam um grande desafio para a Química Analítica, pois são muito baixos para que se tenham resultados com boa precisão e exatidão nas análises, mesmo utilizando técnicas muito sensíveis. Como alternativa para contornar os problemas, nas determinações destas baixas concentrações, etapas prévias de pré-concentração, com posterior determinação, vem sendo propostas com sucesso. Nessa pesquisa, para a pré-concentração dos analito, extração em ponto nuvem foi empregada com determinação por espectrometria de absorção atômica por forno de grafite. O procedimento da extração em ponto nuvem consiste em derivatizar os analitos em espécies hidrofóbicas por meio de um agente complexante, e extrair por micelas formadas a partir de um surfactante não iônico, induzidas por mudança de temperatura. Essa extração se baseia no fenômeno que ocorre com a formação de agregados micelares, quais apresentam caráter hidrofóbico. Foram estudados diferentes ligantes, e o melhor resultado para a extração foi obtido empregando-se o APDC (pirrolidina ditiocarbamato de amônio). Os parâmetros da extração em ponto nuvem otimizados para o melhor ligante foram: pH=7; 3,0x10-2 mol L-1 de APDC; 0,5 % m v-1 de Triton X-114; 60ºC durante 10 min de banho, 10 min de centrifugação e 50 mg L-1 Cu(II) como modificador químico. O método apresentou fator de enriquecimento de 24 vezes, mas o LOD (0,24 µg L-1) ficou muito acima dos valores apresentados em amostras de indivíduos expostos e não expostos. Adições de 1, 5 e 10 µg L-1 foram realizadas para avaliar a exatidão do método e apresentaram recuperações média de 91%. / Reflecting a way of life that requires fast displacement with a minimum of comfort, currently in big cities, there are a large number of vehicles that produce a large amount of waste gases (hydrocarbons, CO and nitrogen oxides - NOx) to atmosphere. To minimize the emission of these gases, current cars are equipped with catalytic converter, made of platinum group metals, which has the purpose of converting the noxious gases into less harmful gases to environment and man. However, these constituents of the catalytic converter can be expelled to the environment in form of particulates in suspension, or by volatilization along with the combustion gases. Thus, these elements can accumulate. Biological samples such as blood, urine, hair, nail, have been used for a long time in studies and control of human exposition to elements. Studies of biological materials indicate that the concentrations of platinum group metals are the order of ng/kg. Such concentration levels means a huge challenge for analytical chemistry, as they are too low to provide the necessary results with good precision and accuracy in the analysis, even using very sensitive techniques. As an alternative to overcome the problems in the provisions of these low concentrations, preconcentration methods, with subsequent determination has been proposed successfully. Cloud point extraction (CPE) was proposed in this work for pre-concentration of the analytes. CPE procedure consists in derivatizing the analytes into hydrophobic species by a complexing agent and extracts them trapped inside micelles formed from a nonionic surfactant, induced by temperature change. The cloud point extraction is based on the phenomenon that occurs with the formation of these hydrophobics aggregates by those micelles. Dithizone, DBTC, DMG, DDTC and APDC ligands were studied. The optimized parameters of cloud point extraction were: pH=7; 3,0x10-2 mol L-1 APDC; 0,5% m v-1 Triton X-114; 60 ºC while 10 min of termal bath and 10 min of centrifugation time. A Cu (II) 50 mg L-1 solution was used as a chemical modifier. The method was evaluated after optimized cloud point extraction\'s parameters conditions. It showed enrichment factor of 24-fold, but the limit of detection (0.24 µg L-1) was higher than the values expected to samples of exposed and non exposed individuals. A recovery test was done and a satisfactory recovery result was provided, up to 91%.

O trabalho tem como objetivo avaliar a exposição ao mercúrio de crianças residentes em área de garimpo e em área de controle, sem garimpo. Para isso foi realizado um estudo transversal com crianças residentes nos municípios de Chapada de Natividade e Porto Nacional, no Estado de Tocantins onde foi realizada a coleta de cabelo para análise laboratorial dos teores de mercúrio, comparando com relação aos municípios, gênero, consumo mensal de peixe, profissão dos pais e presença de amálgama em restaurações dentárias. As amostras de cabelo foram analisadas pelos métodos de análise por ativação com nêutrons e também por meio do equipamento DMA (Direct Mercury Analyser) sendo esse último em parceria com a CETESB. Não foram encontradas evidências de doenças causadas pelo mercúrio nas crianças estudadas. A concentração média de mercúrio nas crianças de Chapada de Natividade foi significativamente maior que as de Porto Nacional. Não houve relação significante entre concentrações de mercúrio e o gênero, consumo mensal de peixe, profissão dos pais e presença de amálgama em restaurações dentárias. Análises de amostras de peixes mais consumidos na região exposta ao garimpo apontam concentrações de mercúrio abaixo dos valores recomendados, necessitando de estudo mais aprofundado. Os resultados sugerem que as crianças habitantes em região exposta ao garimpo sofrem maior exposição ambiental ao mercúrio, independente de seus hábitos alimentares ou gênero. / The objective of the work is to evaluate the mercury exposure of children living in the artisanal gold mining area and in a control area, without mining. A cross-sectional study was conducted with children living in the municipalities of Chapada de Natividade and Porto Nacional, in the State of Tocantins, where hair samples were collected for laboratorial analysis of mercury concentrations, comparing between municipalities, gender, monthly fish consumption, profession of parents and the presence of amalgam in dental restorations. The hair samples were analyzed by the methods of neutron activation analysis and also by means of the DMA (Direct Mercury Analyzer) equipment, in the last case being a partnership with CETESB. There was no evidence of mercury-related diseases in the studied children. The mean concentration of mercury in children in Chapada de Natividade was significantly higher than in Porto Nacional. Children exposed to artisanal gold mining areas have higher concentrations of mercury than children living in non-artisanal gold mining areas. There was no significant relationship between mercury concentrations and gender, monthly fish consumption, parental profession and amalgam presence in dental restorations. Analyzes of samples of fish most consumed in the region exposed to the artisanal gold mining area indicate concentrations of mercury below the recommended values, needing further study. The results suggest that the children living in an area exposed to artisanal gold mining experience greater environmental exposure to mercury, regardless of their eating habits or gender.

Kin-Fai Ho. / Thesis (M.Phil.)--Chinese University of Hong Kong, 1999. / Includes bibliographical references (leaves [61-66]). / Abstracts in English and Chinese. / Contents / ACKNOWLEDGMENT / ABSTRACT / Chapter CHAPTER 1 --- INTRODUCTION / Chapter 1.1 --- Air Pollution in Hong Kong / Chapter 1.2 --- Brief introduction of Particulate Matter / Chapter 1.2.1 --- Total suspended particulates / Chapter 1.2.2 --- Respirable suspended particulates / Chapter 1.2.3 --- PM2.5 / Chapter 1.3 --- Lead in Air Particulate and its Harmful Effects on Human / Chapter 1.4 --- Air Sampling / Chapter 1.5 --- Sample Treatment / Chapter 1.5.1 --- Acid digestion method / Chapter 1.5.2 --- Slurry sampling method / Chapter 1.5.3 --- Comparison between acid digestion and slurry sampling method / Chapter 1.5.4 --- Chemical modification / Chapter CHAPTER 2 --- EXPERIMENTAL / Chapter 2.1 --- Apparatus / Chapter 2.2 --- Instrumental analysis / Chapter 2.2.1 --- Electrothermal atomic absorption spectrometry / Chapter 2.2.2 --- Background correction by the Zeeman effect / Chapter 2.3 --- Reagents / Chapter 2.4 --- Procedure / Chapter 2.4.1 --- Collection of air sample / Chapter 2.4.2 --- Treatment of sample collected on filter / Chapter 2.4.2.1 --- Digestion Procedure / Chapter 2.4.2.2 --- Procedure for Slurry Preparation / Chapter 2.4.3 --- Temperature program employed / Chapter 2.4.4 --- Sample introduction / Chapter 2.4.5 --- Determination of Lead in PM 2.5 by Acid Digestion Method / Chapter 2.4.6 --- Determination of Lead in PM 2.5 by Developed Method / Chapter 2.4.7 --- Study of particle size and suspension behavior of PM 2.5 in solvent / Chapter CHAPTER 3 --- RESULTS AND DISCUSSION / Chapter 3.1 --- Choice of filter for air sampling / Chapter 3.2 --- Choice of Solvents for Suspension of Air Particulates / Chapter 3.3 --- Ultrasonic agitation / Chapter 3.4 --- Effect of the sonication time / Chapter 3.5 --- Particle size and Effect of stabilization agents / Chapter 3.6 --- Effect of acid predigestion of the slurry sample / Chapter 3.7 --- Chemical Modification / Chapter 3.7.1 --- Use palladium as chemical modifier / Chapter 3.7.2 --- Amount of chemical modifier / Chapter 3.7.3 --- Effect of nitric acid / Chapter 3.8 --- Optimization of the graphite furnace temperature / Chapter 3.9 --- Effect of using platform / Chapter 3.10 --- Sample injection volume / Chapter 3.11 --- Recovery study of Lead in PM2.5 / Chapter 3.12 --- The limit of detection and precision of the developed method / Chapter CHAPTER 4 --- CONCLUSION / APPENDIX / REFERENCES

O trabalho tem como objetivo avaliar a exposição ao mercúrio de crianças residentes em área de garimpo e em área de controle, sem garimpo. Para isso foi realizado um estudo transversal com crianças residentes nos municípios de Chapada de Natividade e Porto Nacional, no Estado de Tocantins onde foi realizada a coleta de cabelo para análise laboratorial dos teores de mercúrio, comparando com relação aos municípios, gênero, consumo mensal de peixe, profissão dos pais e presença de amálgama em restaurações dentárias. As amostras de cabelo foram analisadas pelos métodos de análise por ativação com nêutrons e também por meio do equipamento DMA (Direct Mercury Analyser) sendo esse último em parceria com a CETESB. Não foram encontradas evidências de doenças causadas pelo mercúrio nas crianças estudadas. A concentração média de mercúrio nas crianças de Chapada de Natividade foi significativamente maior que as de Porto Nacional. Não houve relação significante entre concentrações de mercúrio e o gênero, consumo mensal de peixe, profissão dos pais e presença de amálgama em restaurações dentárias. Análises de amostras de peixes mais consumidos na região exposta ao garimpo apontam concentrações de mercúrio abaixo dos valores recomendados, necessitando de estudo mais aprofundado. Os resultados sugerem que as crianças habitantes em região exposta ao garimpo sofrem maior exposição ambiental ao mercúrio, independente de seus hábitos alimentares ou gênero. / The objective of the work is to evaluate the mercury exposure of children living in the artisanal gold mining area and in a control area, without mining. A cross-sectional study was conducted with children living in the municipalities of Chapada de Natividade and Porto Nacional, in the State of Tocantins, where hair samples were collected for laboratorial analysis of mercury concentrations, comparing between municipalities, gender, monthly fish consumption, profession of parents and the presence of amalgam in dental restorations. The hair samples were analyzed by the methods of neutron activation analysis and also by means of the DMA (Direct Mercury Analyzer) equipment, in the last case being a partnership with CETESB. There was no evidence of mercury-related diseases in the studied children. The mean concentration of mercury in children in Chapada de Natividade was significantly higher than in Porto Nacional. Children exposed to artisanal gold mining areas have higher concentrations of mercury than children living in non-artisanal gold mining areas. There was no significant relationship between mercury concentrations and gender, monthly fish consumption, parental profession and amalgam presence in dental restorations. Analyzes of samples of fish most consumed in the region exposed to the artisanal gold mining area indicate concentrations of mercury below the recommended values, needing further study. The results suggest that the children living in an area exposed to artisanal gold mining experience greater environmental exposure to mercury, regardless of their eating habits or gender.

Flame Atomic Absorption Spectrometry (FAAS) still keeps its importance despite the relatively low sensitivity / because it is a simple and economical technique for determination of metals. In recent years atom traps have been developed to increase the sensitivity of FAAS. Although the detection limit of FAAS is only at the level of mg/L, with the use of atom traps it can reach to ng/mL. Slotted quartz tube (SQT) is one of these atom traps, it is applied for determination of volatile elements / it is economical, commercially available and easy to use. In this study, a sensitive analytical method has been developed for the determination of lead with the help of SQT. Regarding the angle between the two slots of SQT, 120&deg / and 180&deg / configurations were used and the results were compared. There were three modes of SQT used. The first application was for providing longer residence time of analyte atoms in the measurement zone / 3 fold sensitivity enhancement was observed. The second mode was the usage of SQT for preconcentration of lead atoms. In the presence of a lean air-acetylene flame, analyte atoms were trapped in the inner surface of SQT for a few minutes. Then, by the help of a small volume (10-50 &amp / #956 / L) of Methyl isobutyl ketone (MIBK), analyte atoms were revolatilized and a rapid atomization took place. Using this mode, a sensitivity enhancement of 574 was obtained at a rather low (3.9 mL/min) suction rate / 1320 fold improvement was reached at higher sample suction rate (7.4 mL/min) for 5.0 min collection. The last mode involves coating of the inner surface of SQT with several kinds of transition metals. The best sensitivity enhancement, 1650 fold, was obtained by the Ta coated SQT. In addition, effects of some elements and anions on Pb signal in Tacoated-SQT-AT-FAAS were examined. Final step consists of surface analysis / chemical nature of Pb trapped on quartz and Ta surface, and the chemical nature of Ta on quartz surface were investigated by X-ray Photoelectron Spectroscopy (XPS) and Raman Spectroscopy.

In recent years speciation analysis is becoming more important as it is known that each chemical form of an element behaves differently in biological and environmental media. Since abundance of tellurium in earth crust is extremely low, very sensitive and accurate methods are needed to determine the concentration of tellurium. Hydride generation atomic absorption is a sensitive, fast and economical technique applied for the determination of tellurium. Speciation of tellurium can be achieved by making use of different kinetic behaviors of Te(IV) and Te(VI) upon its reaction with sodiumborohydride. A continuous flow hydride generation system was developed and parameters that affect the analytical signal were optimized. Sample solutions were prepared in 4.0 mol/L HCl / as reductant 0.5 % (w/v) sodiumborohydride in 0.5 % (w/v) NaOH was used. Quantitative reduction of Te(VI) was achieved through application of a microwave assisted prereduction of Te(VI) in 6.0 mol/L HCl solution. Sensitivity of the system was further enhanced by in-situ trapping of the formed H2Te species in a previously heated graphite furnace whose surface was modified using Pd or Ru. Overall efficiency of pyrolytic coated graphite surface was found to be 15% when hydrides are trapped for 60 seconds at 300 oC. LOD and LOQ values were calculated as 86 pg/mL and 287 pg/mL according to peak height values. Efficiency was increased by 46% and 36% when Pd and Ru modifiers were used, respectively. With Ru modified graphite tube 173 fold enhancement was obtained over 180 seconds trapping period with respect to direct ETAAS. LOD values were 6.4 and 2.2 pg/mL for Pd and Ru treated systems, respectively, for 180 s collection of 9.6 mL sample solution.

ABSTRACT DETERMINATION OF CADMIUM USING SLOTTED QUARTZ TUBE ATOM TRAP ATOMIC ABSORPTION SPECTROMETRY AND METAL COATINGS &Ouml / zcan Gurbetoglu, G. Pelin M.S., Department of Chemistry Supervisor: Prof. Dr. O. Yavuz Ataman July 2010, 76 pages Flame atomic absorption spectroscopy (FAAS) is a common technique for detecting metals and metalloids in environmental, biological and metallurgical samples. Although it is a rather old technique, it is still very reliable, simple to use and inexpensive. The technique can be used to determine the concentration of over 70 different metals in a solution. However, it has detection limits at mg/L levels. Some atom trapping methods have been developed to reach the detection limits of ng/mL levels. Slotted quartz tube (SQT) is one of these atom trapping methods. It is an important technique, since it is easy to use, applicable in all laboratories, commercially available and economical. This thesis consists of development of a sensitive method for cadmium with the help of SQT atom trap. In this study, it was used for two different purposes. One was for keeping the analyte atoms more in the light path / in other words, for increasing the residence times of analyte atoms in the measurement zone. This first application was provided a 2.9 times enhancement with respect to conventional FAAS. Second application was for trapping the analyte on the surface of the SQT, in other words, for performing on-line preconcentration of cadmium in SQT. In the presence of a lean flame, analyte samples were trapped and collected for a few minutes at a low suction rate. After finishing the collection period, analyte atoms were revolatilized with the help of a small volume of (10-50 &micro / L) methyl isobutyl ketone (MIBK) and a rapid atomization occurred. This introduction also altered the flame composition momentarily and analyte atoms were released from the surface of the SQT. Application of this method enhanced the sensitivity 2065 times with respect to conventional FAAS. Another approach to this type of atom trapping has been investigated also in this study, which was coating of SQT with some metals having low volatility. Therefore, some transition metals were coated to the surface of SQT and among them zirconium was selected as the best coating material as having the most sensitivity enhancement factor. That is why, rest of the study was performed with the Zr coated SQT. The enhancement was 3368 as compared with FAAS. Cd determination with this method provides LOD value of 8 pg/mL and Co value of 19 pg/mL. In order to see the effect of some other type of elements or ions on determination of cadmium, interference study was done.

Flame Atomic Absorption Spectroscopy (FAAS) has lover sensitivity than similar analytical methods, however it has an important place for analysis due to its easy application and economic practicability especially in metal determinations. In order to increase the sensitivity of FAAS from mg/L level to ng/L level, various atom trap systems have been used. One of these atom traps, Slotted Quartz Tube (SQT), which is easy, economical and useful for volatile element determination, is used in this study as a sensitive analytical method for determination of tellurium. In the study, determination of Te by SQT is handled in three different modules. First, only with SQT itself, longer residence time for Te atoms in the measurement zone is provided and consequently 3.2 fold sensitivity enhancement is obtained both for Te (VI) and Te (IV). In the second module, SQT is used for concentration of tellurium species in a lean flame by sending the analyte into SQT for a definite time and trapping them on the inner surface of the SQT. After trapping the analyte, in order to determine the Te concentration, a small volume (10-50 &micro / L) of organic solvent such as methyl ethyl ketone (MEK) is introduced to the flame for revolatilization and a rapid atomization of Te on the surface is provided. In this trapping method, for 5 minutes collection with a 6 mL/min suction rate, 143 fold enhancement for Te (VI) and 142 fold enhancement for Te (IV) were obtained. In the third module, different from the second one, the inner surface of the SQT is coated with different metals for increasing the amount of Te trapped on the surface and the best enhancement for tellurium is obtained with Tantalum-coated SQT with 252 fold enhancement for Te (VI) and 246 fold enhancements for Te (IV). All improvements are calculated according to the signals obtained in FAAS method. Separate calibration plots were used for Te (IV) and Te (VI).

Silver is a precious metal having antibacterial property and widely used in industry mostly for water purification and medicinal products. Therefore, the determination of trace levels of silver is important for industrial applications. Flame atomic absorption spectrometry (FAAS) is a popular technique for the determination of relatively low concentration levels. This mature technique owes its widespread application to its simplicity and low cost. However, for some occasions, FAAS technique suffers from its low sensitivity because of low nebulization efficiency and relatively short residence time of analyte atoms in the measurement zone. In order to overcome this sensitivity problem, atom traps have been developed in recent years. Slotted quartz tube (SQT) is an accessory designed to use as an atom trap in conventional flame atomic absorption burner head. This thesis study involves the development of a sensitive, simple and economical technique with the help of the SQT for the determination silver. Firstly, the technique known as SQT-FAAS was used to increase the residence time of analyte atoms in the measurement zone. In this case, limit of detection (LOD) and characteristic concentration (C0) values were found to be 19 ng/mL and 35 ng/mL, respectively. Enhancement in sensitivity with respect to FAAS was found to be 2.31 fold using SQT-FAAS. Regarding the angle between the two slots of the SQT, 180&deg / configuration was used. Secondly, in order to improve sensitivity further, the SQT was used as an atom trap (AT) where the analyte is accumulated in its inner wall prior to re-atomization. The signal is formed after reatomization of analyte atoms on the trap surface by introduction of organic solvent. For this purpose, uncoated SQT was used as a trap medium. However, there was a memory effect. Therefore, the SQT inner surface was coated with different coating elements and theoptimum conditions were found by using W-coated SQT-AT-FAAS technique. In the presence of a lean air-acetylene flame, analyte atoms were trapped in the inner surface of the SQT for 5.0 min and then revolatilized with the introduction of 25 &mu / L isobutyl methyl ketone (IBMK) / afterwards, a transient signal was obtained. These optimized parameters were used for uncoated SQT, W-coated SQT and Zr-coated SQT atom trap techniques. Sample suction rate was 6.25 mL/min in all techniques. Sensitivity was increased 54 fold using uncoated SQT-AT-FAAS technique with respect to simple FAAS technique. When W-coated SQT-AT-FAAS technique was applied, 135 fold sensitivity enhancement was obtained with respect to FAAS technique. The best sensitivity enhancement, 270 fold, was obtained using Zr-coated SQT-AT-FAAS technique. In addition, the Ag signals were more reproducible (%RSD, 1.21) when Zr was used as a coating element. After the sensitive technique was developed, interference effects of some transition and noble metals and hydride forming elements on Ag signals were investigated. Finally, surface studies were done to determine the chemical state of Ag during trapping period by using X-ray Photoelectron Spectroscopy (XPS). It was observed that the Ag analyte is retained on the SQT surface in its oxide form.

published_or_final_version / Chemistry / Master / Master of Philosophy