Neste trabalho foi realizado um estudo estatístico do desempenho analítico das técnicas eletroquímicas Voltametria de pulso diferencial (VPD), Voltametria de onda quadrada (VOQ) e Voltametria de múltiplas ondas quadradas (VMOQ) para a redução do herbicida paraquat em ultramicroeletrodo de ouro (UME-Au) e sua análise e quantificação em águas puras e naturais. Os estudos da redução eletroquímica do paraquat foram realizados em eletrólito de suporte Na2SO4 0,1 mol L-1 em pH = 5,5. Os resultados mostraram a presença de dois picos de redução bem definidos , com o pico 1 em -0,64 V e o pico 2 em -0,94 V vs Ag/AgCl 3,0 mol L-1. Para as análises foi utilizado o pico 1 que é referente a uma reação em solução, onde a superfície eletródica serve apenas como intermediadora na transferência eletrônica. Utilizando-se os parâmetros experimentais e voltamétricos otimizados, curvas de trabalho foram construídas em eletrólito de suporte preparado com água ultrapurificada. Para a VPD, VOQ e VMOQ, os limites de detecção encontrados utilizando-se o método descrito em Miller & Miller e considerando-se o pico 1 foram: 55,35 ± 0,18 µg L-1 , 37,50 ± 0,32 µg L-1 e 21,42 ± 0,51 µg L-1, respectivamente. A metodologia foi aplicada em amostras de águas coletadas no Rio Mogi-Guaçu na cidade de São Carlos-SP. A variação da inclinação das curvas de trabalho obtida nas análises destas amostras foi praticamente insignificante em relação àquela obtida utilizando-se o eletrólito de suporte preparado com água ultrapurificada para as três técnicas utilizadas, mostrando pouca interferência da matéria orgânica presente nas amostras de águas naturais. Os menores valores de concentração mensuráveis de paraquat nas amostras de águas naturais foram inferiores ao valor máximo de resíduos permitido pela legislação brasileira para águas residuárias (100 µg L-1), mostrando a viabilidade na aplicação da metodologia proposta. Os cálculos dos limites de detecção e quantificação, a avaliação dos erros experimentais e os limites de confiança foram realizados a partir do procedimento estatístico descrito em Miller & Miller. Os valores de limites de detecção encontrados apresentam um significado físico e realístico para esta grandeza, já que foram determinados por interpolação nas curvas analíticas, construídas a partir da relação entre as concentrações do pesticida e os sinais obtidos. Estes mesmos limites foram calculados utilizando-se o método recomendado pela IUPAC e os valores encontrados foram 29,43 µg L-1 para VPD, 3,63 µg L-1 para VOQ e 0,37 µg L-1 para VMOQ. Estes resultados mostram diferenças de até 2 ordens de grandeza de uma técnica para outra, que se não forem bem avaliados podem levar o analista a conclusões equivocadas. / Statisctic studies of the analytical performance of Differential pulse voltammetry (DPV), Square wave voltammetry (SWV) and Multiple square wave voltammetry (MSWV) electrochemical techniques was performed for the electrochemical reduction of the paraquat herbicide on an gold ultramicroelectrode (Au-UME), aiming its analysis and quantification in pure and natural waters. The electrochemical reduction of paraquat was studied in 0.1 mol L-1 Na2SO4 support electrolyte in pH = 5.5 . The electrochemical responses showed two well-defined reduction peaks with potentials of -0.64 and -0.94 V vs Ag/AgCl 3.0 mol L-1 for peaks 1 and 2, respectively. The mathematical treatment was performed with data from peak 1, which is associated with a reversible solution reaction, where the electrode surface acts only as the electron transfer mediator. Working curves were obtained using the optimized experimental parameters in support electrolyte prepared with high purity water. To DPV, SWV and MSWV, the detection limits found for the peak currents associated to peak 1 were: 55.35 ± 0.18 µg L-1, 37.50 ± 0.32 µg L-1 and 21.42 ± 0.51 µg L-1, respectively. An analogous analytical procedure was applied in water samples collected in Mogi-Guaçu River, in São Carlos County, state of São Paulo. The variation in slope values, between curves obtained from pure water and those from river waters were practically depreciable for the three analytical methods, showing that the organic components and others contaminants present in natural waters caused only a minor interference in the measurements. The lower measurable values for paraquat in water samples were smaller than the allowed maximum of residue established by the Brazilian legislation for waste waters (100 µg L-1), indicating the developed methodology as convenient to such application. Calculations of detection and quantification limits, the evaluation of experimental errors and the limits of confidence were performed by the statistical procedure reported by Miller & Miller. The obtained detection limits values present a true physical significance, in a realistic order of magnitude, as they were determined by interpolation of the experimental analytical curves. The same analytical curves were submitted to the IUPAC methodology yielding the values of 29.43, 3.63 and 0.37 µg L-1 para DPV, SWV and MSWV, respectively, for pure water measurements. These results showed a difference up to two orders of magnitude from those obtained by the statistical methodology and may promote false conclusions, if not properly evaluated.

Aluminized steel pipes are expected to have a long service life, e.g. 75 years. Spiral ribbed aluminized pipes (SRAP) have been widely specified and used by the Florida Department of Transportation (FDOT) for drainage of runoff water. Confidence in the long term durability of SRAP has been challenged by recent unexpected early corrosion failures in various Florida locations. SRAP premature corrosion incidents have occurred in two modalities. Mode A has taken place in near-neutral soil environments and has often been associated with either gross manufacturing defects (i.e. helical cuts) or corrosion concentration at or near the ribs. Mode B took place in pipes in contact with limestone backfill and corrosion damage was in the form of perforations, not preferentially located at the ribs, and not necessarily associated with other deficiencies. These failures motivated this research. The objectives of this work are to establish to what extent the Mode A corrosion incidents can be ascribed to manufacturing defects, that can be rectified by appropriate quality control, as opposed to an intrinsic vulnerability to corrosion of regularly produced SRAP due to ordinary forming strains and to determine the mechanism responsible for Mode B corrosion including the role that limestone backfill played in that deterioration. To achieve those objectives, laboratory experiments were conducted to replicate the conditions for Mode A and Mode B. Overall, the findings of this and previous work suggest that much of the corrosion damage observed in the Mode A incidents were promoted more by manufacturing deficiencies and less by any possible inherent susceptibility of corrosion at the ribs of SRAP that was produced following appropriate quality control. Experiments to explore the causes of Mode B corrosion showed that high pH values, sufficient to cause dissolution of the passive film on aluminum, can develop under exposure of limestone to flowing natural water. The findings substantiate, for the first time, an important vulnerability of aluminized steel in limestone soils and provide an explanation for the rapid onset deterioration observed at the field under Mode B. The findings also provide strong evidence in support of service guidelines to disallow the use of limestone bedding for aluminized steel pipe, including SRAP.

Throughout this body of work, three classes of sorbent materials were created and optimized, each designed to selectively capture organics or desired metals from natural water sources. These target species included toxic heavy metals, uranium, rare earths, and simple organics, such as benzene. Each class of sorbent materials is functionalized nanostructured silicas, created by the development of several functionalization methods: utilizing thiol-ene click chemistry, aromatic interactions, and the formation of inclusion complexes. Thiol-ene click surface modification gave rise to sorbent materials with impressive affinities for both soft metals, such as gold, and harder metals, such as uranium and rare earth elements. Applications of these materials for aqueous mining of uranium and rare earth elements from various natural water sources are presented. Two classes of materials based on supramolecular functionalization methods were prepared. In the first class, aromatic interactions allowed for surface functionalization with thiol containing aryl ligands. These materials proved to have an excellent affinity for heavy metals from natural waters, and hold promise for regenerable nanostructured silica sorbents. The second class of materials utilizes the ability of β-cyclodextins to form inclusion complexes with small molecule organics, such as benzene. The formation of inclusion complexes drove both surface functionalization and the capture of small molecule organics from aqueous solutions. This work serves to inspire the development of novel functionalized nanostructured sorbents for trace collection of toxic organics from aqueous streams. These supramolecular methods for surface medication can be expanded to nanomaterials at large. This dissertation includes both previously published/unpublished and co-authored material. / 10000-01-01

Made available in DSpace on 2014-06-11T19:31:36Z (GMT). No. of bitstreams: 0 Previous issue date: 2004-04-22Bitstream added on 2014-06-13T19:41:57Z : No. of bitstreams: 1 bassan_cfd_dr_botfca.pdf: 763512 bytes, checksum: d8464f6ac6e486c2b19bc8c3b3b6f5aa (MD5) / Universidade Estadual Paulista (UNESP) / Certain cultures present especification in the assimilation of some ions, that are or not in available ways in the soil. The minerals have fundamental paper in the presence of those elements that, a lot of times, they are together originating from of the processes of meteorization of the rocks with the decomposition of the organic matter. This work had for objective to study the extraction and/or solubilization of some present chemical elements in the studied minerals and in a red latosoil, for the action of some organic acids produced starting from the decomposition of the matter ligno-cellulousic, through the microbial action, hoping to contribute in some way in the understanding of the mechanisms of fertility of the soil and, consequently, in the mineral nutrition of plants. The used minerals were: manganite [MnO(OH)], hematite (Fe2O3), pirolusite (MnO2), caolinite [Al2Si2O5(OH)4], goethite (HFeO2), bentonite [Na3(Al,Mg)2 2(Si4O10)(OH)2.H2O] e magnetite(Fe3O4), that commonly happen in areas humid intertropicals and a red latosoil, of sandy texture that, it represents more that 20% of the area of the State of Saint Paulo. The minerals and LV were triturated and drizzled in 0,05mm mesh, separately. After having examined with relationship your structure for Difratometric of Ray-X (XRD), 1g of those minerals and LV were conditioned, separately, in glass flasks. Some samples were only treated with distilled water and other with solution 0,02 mol.L-1 of the following acids: acetic, butyric, citric, carbolic, lactic, malic, oxalic, propionic and tannic, separately, for 53 days, with weekly agitations and conditions aerobics. After the digestion of the samples, they were certain the litio concentrations, sodium, potassium, magnesium, calcium, barium, vanadium, cromium, molibdenium, manganese, iron, cobalt, nickel, copper, zinc, cadmium, mercury, boron, aluminum, silicio, tin, lead, match... (Complete abstract click electronic access below)

Submitted by ELISSANDRO SOARES EMÍDIO null (elissandro_se@yahoo.com.br) on 2016-05-12T21:01:18Z No. of bitstreams: 1 Tese Elissandro Soares Emidio_IQ UNESP.pdf: 4935815 bytes, checksum: 2ed4a096c784661153f0589f1feaccf4 (MD5) / Approved for entry into archive by Felipe Augusto Arakaki (arakaki@reitoria.unesp.br) on 2016-05-16T13:18:46Z (GMT) No. of bitstreams: 1 emidio_es_dr_araiq_par.pdf: 512252 bytes, checksum: abe4aee98ccd84a2227db13788c6221b (MD5) / Made available in DSpace on 2016-05-16T13:18:46Z (GMT). No. of bitstreams: 1 emidio_es_dr_araiq_par.pdf: 512252 bytes, checksum: abe4aee98ccd84a2227db13788c6221b (MD5) Previous issue date: 2016-04-11 / Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq) / Micotoxinas estrogênicas (EM) são estrógenos produzidos como metabólitos secundários de fungos. Entre as EM estão a zearalenona (ZEN) e seus metabólitos produzidos principalmente pelo fungo do gênero Fusarium que cresce em várias culturas agrícolas. A influência da exposição às EM na saúde de mamíferos /humanos, por meio dos alimentos, tem sido extensivamente estudada. Em contraste, estudos que focam nas EM em águas superficiais e seus possíveis impactos no ambiente aquático são negligenciados. O presente trabalho apresenta os desenvolvimentos mais recentes no que concerne às micotoxinas estrogênicas, em relação às metodologias analíticas utilizadas na sua determinação e avaliação do comportamento em águas superficiais. As atividades desenvolvidas foram divididas em duas etapas: (1) Estudo analítico - desenvolvimento de um método analítico verde para a determinação das micotoxinas estrogênicas empregando a microextração líquido-líquido dispersiva (DLLME) utilizando bromosolventes e líquido iônico (IL) por cromatografia líquida de alta eficiência (HPLC) com detecção por fluorescência (FLD) ou espectrometria de massas (MS); (2) Estudo ambiental - avaliação da presença dos analitos na microbacia hidrográfica do Córrego Rico com avaliação espaço-temporal e a persistência da micotoxina zearalenona em ambientes aquáticos sob irradiação solar simulada. Vários parâmetros importantes que influenciam a eficiência de extração para DLLME foram otimizados. Em condições ótimas, a recuperação de extração para ZEN e seus metabólitos para DLLME e IL-DLLME variaram de 81 a 118 % e 76 a 81 %, respectivamente; Os desvios padrão relativos (RSD) para a precisão intra-dia e inter-dia foram menores do que 13%, em DLLME, e inferior a 5,7 % (intra-dia) para IL-DLLME. Os limites de detecção do método (LOD) e quantificação (LOQ) foram de 4-20 ng L-1 e de 8-40 ng L-1 para DLLME e 0,2 ng L-1 e 0,5 ng L-1 para IL-DLLME, respectivamente. A determinação das micotoxinas estrogênicas nas amostras de água da microbacia hidrográfica do Córrego Rico alcançaram níveis de até 59,3 ng L-1 com concentração equivalente em estradiol calculada (cEEQ) entre <0,06 e 1,42 ng L-1. Essas concentrações estão relacionadas a efeitos adversos no crescimento e reprodução de algumas espécies de peixes. No estudo de fototransformação a ZEN foi degradada rapidamente em águas naturais, com meia-vida (t1/2) de 28,3 min (água estuarina) e 135,9 min (água de rio). Os resultados indicaram que, após 1 h do tempo de irradiação, o percentual de degradação da ZEN foi de 69,4% (água do rio) e 90,8% (água estuarina). Do ponto de vista ambiental, a rápida degradação observada não deve ser interpretada “a priori”, como indicativo de baixo risco ambiental do aporte de ZEN, devendo ser investigados o comportamento ambiental e toxicológico dos seus produtos de degradação, além do que há que se considerar a constante introdução, nas águas superficiais, de microcontaminantes associados ao esgoto sanitário, como a ZEN. / Estrogenic mycotoxins (EM) are estrogens produced as secondary metabolites of fungi. The well known EM are zearalenone (ZEN) and its metabolites primarily produced by the mold Fusarium growing on a variety of crops. The influence of exposure to EM on human/mammalian health via food has been extensively studied. In contrast, studies focus on EM in surface waters and their possible impacts in aquatic environment are negligible. The current work presents the most recent developments concerning estrogenic mycotoxins, in regard to the analytic methodologies utilized in their determination and the behavior assessment in surface waters. The study was developed in two steps: (1) analytical study - Green analytical method development for determination of estrogenic mycotoxin employing microextraction liquid-liquid dispersive (DLLME) using bromosolvent and ionic liquid (IL) followed by high-performance liquid chromatography (HPLC) with fluorescence detection (FLD) or mass spectrometry (MS); (2) Environmental study - evaluation of the presence of analytes in Rico stream watershed with spatial-temporal distribution and the persistence of zearalenone mycotoxin in aquatic environments by simulated sunlight. Several important parameters influencing the extraction efficiency of DLLME were optimized. Under optimal conditions, extraction recovery for ZEN and its metabolites by DLLME and IL-DLLME were within the range of 81-118 % e 76-81 % respectively; the relative standard deviations (RSDs) for intra-day and inter-day precision were lower than 13% by DLLME, and lower than 5.7 % (intra-day) by ILDLLME. The method limits of detection (LOD) and quantification (LOQ) were from 4– 20 ng L−1 and 8–40 ng L−1, for DLLME and from 0.2 ng L−1 and 0.5 ng L−1 for ILDLLME, respectively. Determination of estrogenic mycotoxins in water samples from Rico Stream watershed reached levels of up to 59.3 ng L-1 and their corresponding calculated estrogenic equivalents (cEEQ) values were <0.06 and 1.42 ng L-1. These concentrations are related to adverse effects on growth and reproduction of some fish species. In phototransformation study ZEN degraded quickly in natural waters, with half-lives (t1/2) of 28.3 min (estuarine water) and 135.9 min (river water). The results indicated that after 1 h irradiation time, the degradation percentage of ZEN were 69.4% (river water) and 90.8% (estuarine water). From an environmental point of view, the rapid degradation observed, under laboratory conditions, should not be interpreted "a priori" as indicative of low environmental risk for ZEN, should be investigated environmental behavior and toxicology of degradation products, beyond it is necessary to considering the constant introduction into surface water of microcontaminants associated with sewage, such as this mycotoxin. / CNPq: 140990/2012-7

Conselho Nacional de Desenvolvimento CientÃfico e TecnolÃgico / No presente trabalho apresentou-se o emprego de sensores e de biossensores eletroquÃmicos para a determinaÃÃo dos pesticidas endossulfam (EDS), tiabendazol (TBZ) e cloridrato de formetanato (FMT) em amostras de cana-de-aÃÃcar, tomate, manga, uva e Ãguas naturais. AlÃm disso, informaÃÃes acerca do mecanismo redox dos pesticidas EDS, TBZ e FMT tambÃm foram apresentadas. Os sensores consistiram em eletrodos de gota pendente de mercÃrio (HMDE, do inglÃs Hanging Mercury Drop Electrode), de diamante dopado com boro (EDDB) e de carbono vÃtreo modificado com nanotubos de carbono de paredes mÃltiplas funcionalizados e ftalocianina de cobalto (CV/NTCPMF-FcCo-Naf.0,5%). Para os biossensores, a enzima Lacase (Lac) foi imobilizada pelo mÃtodo de ligaÃÃes cruzadas sobre ouro previamente modificado com nanopartÃculas de ouro (Au/NpAu/Lac-Glu.2%) e sobre eletrodo modificado com NTCPMF-FcCo (CV/NTCPMF-FcCo-Naf.0,5%/Lac-Glu.2%). A reduÃÃo do EDS foi regida por processo quase-reversÃvel. TBZ sofreu oxidaÃÃo irreversÃvel sobre EDDB e CV/NTCPMF-FcCo-Naf.0,5%. FMT sobre EDDB apresentou oxidaÃÃo irreversÃvel do tipo quÃmico-eletroquÃmico. No entanto, mecanismo eletroquÃmico-quÃmico-eletroquÃmico foi observado para FMT sobre CV/NTCPMF-FcCo-Naf.0,5%, totalizando quatro processos de oxidaÃÃo (um irreversÃvel, dois quase-reversÃveis e um reversÃvel). Os valores dos limites de detecÃÃo (LD) e de quantificaÃÃo (LQ) calculados foram: LD = 0,121 mg kgâ1 e LQ = 0,406 mg kgâ1 (EDS sobre HMDE), LD = 0,074 mg kgâ1 e LQ = 0,247 mg kgâ1 (EDS sobre CV/NTCPMF-FcCo-Naf.0,5%/Lac-Glu.2%), LD = 0,052 mg kgâ1 e LQ = 0,177 mg kgâ1 (TBZ sobre EDDB), LD = 0,019 mg kgâ1 e LQ = 0,064 mg kgâ1 (TBZ sobre CV/NTCPMF-FcCo-Naf.0,5%), LD = 0,094 mg kgâ1 e LQ = 0,311 mg kgâ1 (TBZ sobre CV/NTCPMF-FcCo-Naf.0,5%/Lac-Glu.2%), LD = 0,094 mg kgâ1 e LQ = 0,314 mg kgâ1 (FMT sobre EDDB), LD = 0,025 mg kgâ1 e LQ = 0,083 mg kgâ1 (FMT sobre CV/NTCPMF-FcCo-Naf.0,5%), LD = 0,088 mg kgâ1 e LQ = 0,299 mg kgâ1 (FMT sobre Au/NpAu/Lac-Glu.2%). Estes valores estÃo de acordo com os limites mÃximos de resÃduos estabelecidos pela AgÃncia Nacional de VigilÃncia SanitÃria para os pesticidas EDS, TBZ e FMT (0,01 a 10,0 mg kgâ1).Os valores dos percentuais de recuperaÃÃo calculados variaram de 70,89 a 117,32%, com desvio padrÃo relativo entre 0,18 e 7,58%. Portanto, os resultados obtidos comprovaram que as metodologias eletroanalÃticas desenvolvidas podem ser consideradas alternativas promissoras para a determinaÃÃo de pesticidas em matrizes alimentares e ambientais. / The present work emphasized the use of electrochemical sensors and biosensors for the determination of endosulfan (EDS, organochlorine), thiabendazole (TBZ, benzimidazole) and formetanate hydrochloride (FMT, carbamate) pesticides in sugar cane, tomato, mango, grape and natural waters samples. Furthermore, insights of redox mechanistic of EDS, TBZ and FMT pesticide were also presented. The hanging mercury drop electrode (HMDE), boron-doped diamond electrode (BDDE) and cobalt phthalocyanine with functionalyzed multi-walled carbon nanotube modified glassy carbon electrode (Naf.0.5%-PcCo-fMWCNT/GCE) sensors were used. For biossensors, Laccase enzyme (Lac) was imobilized via cross-linking onto a gold electrode previously modified with gold nanoparticles (Glu.2%-Lac-AuNp/Au) and onto a PcCo-fMWCNT modified electrode (Glu.2%-Lac/Naf.0.5%-PcCo-fMWCNT/GCE). EDS was reduced by quase-reversible process. TBC was oxidized by an irreversible process on a BDDE and Naf.0.5%-PcCo-fMWCNT/GCE. The electrochemical response of FMT on a BDDE showed the irreversible oxidation mechanism of the type chemical-electrochemical. However, the electrochemical-chemical-electrochemical mechanism was observed for FMT at Naf.0.5%-PcCo-fMWCNT/GCE with four oxidation process (one irreversible, two quase-reversible and one reversible processes). The detection limits (DL) and quantification limits (QL) calculated values were: DL = 0.121 mg kgâ1 and QL = 0.406 mg kgâ1 (EDS at HMDE), DL= 0.074 mg kgâ1 and QL = 0.247 mg kgâ1 (EDS at Glu.2%-Lac/Naf.0.5%-PcCo-fMWCNT/GCE), DL = 0.052 mg kgâ1 and QL = 0.177 mg kgâ1 (TBZ at BDDE), DL = 0.019 mg kgâ1 and QL = 0.064 mg kgâ1 (TBZ at Naf.0.5%-PcCo-fMWCNT/GCE), DL = 0.094 mg kgâ1 and QL = 0.311 mg kgâ1 (TBZ at Glu.2%-Lac/Naf.0.5%-PcCo-fMWCNT/GCE), DL = 0.094 mg kgâ1 and QL = 0.314 mg kgâ1 (FMT at BDDE), DL = 0.025 mg kgâ1 and QL = 0.083 mg kgâ1 (FMT at Naf.0.5%-PcCo-fMWCNT/GCE), DL = 0.088 mg kgâ1 and QL = 0.299 mg kgâ1 (FMT at Glu.2%-Lac-AuNp/Au). These values are according to maximum residue limits established by National Health Surveillance Agency for EDS, TBZ and FMT pesticides (0.01 a 10.0 mg kgâ1). The calculated recovery percentages varied from 70.89 to 117.32% with relative standard desviation from 0.18 to 7.58%. Thus, electrochemical sensors and biosensors can be considered as an alternative tool for pesticides determination in foods and environmental matrices.

Neste trabalho foi realizado um estudo estatístico do desempenho analítico das técnicas eletroquímicas Voltametria de pulso diferencial (VPD), Voltametria de onda quadrada (VOQ) e Voltametria de múltiplas ondas quadradas (VMOQ) para a redução do herbicida paraquat em ultramicroeletrodo de ouro (UME-Au) e sua análise e quantificação em águas puras e naturais. Os estudos da redução eletroquímica do paraquat foram realizados em eletrólito de suporte Na2SO4 0,1 mol L-1 em pH = 5,5. Os resultados mostraram a presença de dois picos de redução bem definidos , com o pico 1 em -0,64 V e o pico 2 em -0,94 V vs Ag/AgCl 3,0 mol L-1. Para as análises foi utilizado o pico 1 que é referente a uma reação em solução, onde a superfície eletródica serve apenas como intermediadora na transferência eletrônica. Utilizando-se os parâmetros experimentais e voltamétricos otimizados, curvas de trabalho foram construídas em eletrólito de suporte preparado com água ultrapurificada. Para a VPD, VOQ e VMOQ, os limites de detecção encontrados utilizando-se o método descrito em Miller & Miller e considerando-se o pico 1 foram: 55,35 ± 0,18 &micro;g L-1 , 37,50 ± 0,32 &micro;g L-1 e 21,42 ± 0,51 &micro;g L-1, respectivamente. A metodologia foi aplicada em amostras de águas coletadas no Rio Mogi-Guaçu na cidade de São Carlos-SP. A variação da inclinação das curvas de trabalho obtida nas análises destas amostras foi praticamente insignificante em relação àquela obtida utilizando-se o eletrólito de suporte preparado com água ultrapurificada para as três técnicas utilizadas, mostrando pouca interferência da matéria orgânica presente nas amostras de águas naturais. Os menores valores de concentração mensuráveis de paraquat nas amostras de águas naturais foram inferiores ao valor máximo de resíduos permitido pela legislação brasileira para águas residuárias (100 &micro;g L-1), mostrando a viabilidade na aplicação da metodologia proposta. Os cálculos dos limites de detecção e quantificação, a avaliação dos erros experimentais e os limites de confiança foram realizados a partir do procedimento estatístico descrito em Miller & Miller. Os valores de limites de detecção encontrados apresentam um significado físico e realístico para esta grandeza, já que foram determinados por interpolação nas curvas analíticas, construídas a partir da relação entre as concentrações do pesticida e os sinais obtidos. Estes mesmos limites foram calculados utilizando-se o método recomendado pela IUPAC e os valores encontrados foram 29,43 &micro;g L-1 para VPD, 3,63 &micro;g L-1 para VOQ e 0,37 &micro;g L-1 para VMOQ. Estes resultados mostram diferenças de até 2 ordens de grandeza de uma técnica para outra, que se não forem bem avaliados podem levar o analista a conclusões equivocadas. / Statisctic studies of the analytical performance of Differential pulse voltammetry (DPV), Square wave voltammetry (SWV) and Multiple square wave voltammetry (MSWV) electrochemical techniques was performed for the electrochemical reduction of the paraquat herbicide on an gold ultramicroelectrode (Au-UME), aiming its analysis and quantification in pure and natural waters. The electrochemical reduction of paraquat was studied in 0.1 mol L-1 Na2SO4 support electrolyte in pH = 5.5 . The electrochemical responses showed two well-defined reduction peaks with potentials of -0.64 and -0.94 V vs Ag/AgCl 3.0 mol L-1 for peaks 1 and 2, respectively. The mathematical treatment was performed with data from peak 1, which is associated with a reversible solution reaction, where the electrode surface acts only as the electron transfer mediator. Working curves were obtained using the optimized experimental parameters in support electrolyte prepared with high purity water. To DPV, SWV and MSWV, the detection limits found for the peak currents associated to peak 1 were: 55.35 ± 0.18 &micro;g L-1, 37.50 ± 0.32 &micro;g L-1 and 21.42 ± 0.51 &micro;g L-1, respectively. An analogous analytical procedure was applied in water samples collected in Mogi-Guaçu River, in São Carlos County, state of São Paulo. The variation in slope values, between curves obtained from pure water and those from river waters were practically depreciable for the three analytical methods, showing that the organic components and others contaminants present in natural waters caused only a minor interference in the measurements. The lower measurable values for paraquat in water samples were smaller than the allowed maximum of residue established by the Brazilian legislation for waste waters (100 &micro;g L-1), indicating the developed methodology as convenient to such application. Calculations of detection and quantification limits, the evaluation of experimental errors and the limits of confidence were performed by the statistical procedure reported by Miller & Miller. The obtained detection limits values present a true physical significance, in a realistic order of magnitude, as they were determined by interpolation of the experimental analytical curves. The same analytical curves were submitted to the IUPAC methodology yielding the values of 29.43, 3.63 and 0.37 &micro;g L-1 para DPV, SWV and MSWV, respectively, for pure water measurements. These results showed a difference up to two orders of magnitude from those obtained by the statistical methodology and may promote false conclusions, if not properly evaluated.

<p> A method for the simultaneous preconcentration by solvent extraction of a group of trace metal ions from natural waters has been developed. The procedure makes use of a proprietary "liquid cation-exchanger", Kelex 100, the primary component of which is an alkylated oxine (8-quinolinol) derivative, 7-(4-ethyl-1-methyloctyl)-8-quinolinol (HL). After purification of HL from the commercial mixture, the extraction of ten environmentally-significant trace metal ions from artificial seawater into toluene solution was studied as a function of pH. From these investigations, the optimal conditions for the extraction of Cd(II), Co(II), Cu(II), Mn(II), Ni(II), Pb(II) and Zn(II) from natural waters were established. The conditions for quantitative back-extraction of the metal ions were then investigated. With the exception of cobalt, the metal ions were quantitatively back-extracted into a small volume of nitric acid, simplifying the matrix and providing additional analyte enrichment. The optimized forward- and back-extraction technique was subsequently applied to the determination of total (soluble) Cd, Cu, Mn, Ni and Pb in a coastal seawater reference standard by graphite-furnace atomic absorption spectroscopy (GFAAS). The quantitative recovery of the analytes and the uncomplicated matrix of analysis enabled quantitation to be carried out by external calibration. Compared to the method of standard additions, external calibration has advantages in overall analysis time and sample consumption. Satisfactory agreement was obtained between the experimental and reference values, although Cu(II) blanks were high due to trace Cu(II) contamination of HL and the stability of the Cu(II)-HL chelate.</p> <p> The lipophilicity of HL and its metal chelates provided high metal chelate distribution ratios which, in turn, permitted preconcentration factors of up to 500 in a single batch-extraction. Additionally, studies on the recovery of radiotracer spikes from lakewater and seawater suggested that HL is an effective extractant for stripping metal ions from variously-bound forms from natural waters.</p> / Thesis / Master of Science (MSc)

Neste trabalho foram desenvolvidas metodologias para a determinação de substâncias de interesse, como metais pesados (micronutrientes e contaminantes), macronutrientes e pesticidas em solo e águas naturais com ultramicroeletrodo de irídio recoberto com filme de Hg eletrodepositado (UME Ir-Hg) e técnicas voltamétricas, utilizando uma cápsula porosa de cerâmica como cela eletroquímica. As metodologias de medidas com os ultramicroeletrodos foram desenvolvidas inicialmente em condições controladas e posteriormente aplicadas a medidas in-situ, com experimentos com águas naturais e solos, conduzidos em laboratório e também com posteriores medidas em amostras reais. Segundo os resultados obtidos foi possível explorar as metodologias voltamétricas, principalmente as de pulso e redissolução anódica, como ferramentas para estudos in-situ dos metais Cd(II), Pb(II) e Cu(II) e do inseticida organofosforado paration metílico, substâncias de grande interesse, obtendo-se um bom nível de repetibilidade e sensibilidade, com limites de detecção em amostras reais de centenas de ppb\'s. / In this work a methodology for determination of metallic ions (micronutrients and contaminants), macronutrients and pesticides in soil and natural waters was developed using an Hg plated iridium based ultramicroelectrode and voltammetric techniques, using a ceramic capsule as an electrochemical cell. The measurement procedures were developed initially in controlled conditions and therefore applied to in-situ measurements, in soil and natural waters, performed in lab and with real field samples. Regarding the obtained results it was possible do explore the voltammetric techniques, mainly the pulsed and stripping ones, as tools for in-situ determination of Cd(II), Pb(II), Cu(II) and the insecticide methyl parathion, with good reproducibility and sensibility, with detection limits in the order of hundreds of parts per billion.

Neste trabalho foram desenvolvidas metodologias para a determinação de substâncias de interesse, como metais pesados (micronutrientes e contaminantes), macronutrientes e pesticidas em solo e águas naturais com ultramicroeletrodo de irídio recoberto com filme de Hg eletrodepositado (UME Ir-Hg) e técnicas voltamétricas, utilizando uma cápsula porosa de cerâmica como cela eletroquímica. As metodologias de medidas com os ultramicroeletrodos foram desenvolvidas inicialmente em condições controladas e posteriormente aplicadas a medidas in-situ, com experimentos com águas naturais e solos, conduzidos em laboratório e também com posteriores medidas em amostras reais. Segundo os resultados obtidos foi possível explorar as metodologias voltamétricas, principalmente as de pulso e redissolução anódica, como ferramentas para estudos in-situ dos metais Cd(II), Pb(II) e Cu(II) e do inseticida organofosforado paration metílico, substâncias de grande interesse, obtendo-se um bom nível de repetibilidade e sensibilidade, com limites de detecção em amostras reais de centenas de ppb\'s. / In this work a methodology for determination of metallic ions (micronutrients and contaminants), macronutrients and pesticides in soil and natural waters was developed using an Hg plated iridium based ultramicroelectrode and voltammetric techniques, using a ceramic capsule as an electrochemical cell. The measurement procedures were developed initially in controlled conditions and therefore applied to in-situ measurements, in soil and natural waters, performed in lab and with real field samples. Regarding the obtained results it was possible do explore the voltammetric techniques, mainly the pulsed and stripping ones, as tools for in-situ determination of Cd(II), Pb(II), Cu(II) and the insecticide methyl parathion, with good reproducibility and sensibility, with detection limits in the order of hundreds of parts per billion.