Submitted by FELIPE MANFROI FORTUNATO null (felipe.manfroi@hotmail.com) on 2017-03-12T18:59:44Z No. of bitstreams: 1 Tese - Felipe M Fortunato.pdf: 6655475 bytes, checksum: 3c80582e1359616323d24334fc381808 (MD5) / Approved for entry into archive by LUIZA DE MENEZES ROMANETTO (luizamenezes@reitoria.unesp.br) on 2017-03-17T14:14:13Z (GMT) No. of bitstreams: 1 fortunato_fm_dr_araiq.pdf: 6655475 bytes, checksum: 3c80582e1359616323d24334fc381808 (MD5) / Made available in DSpace on 2017-03-17T14:14:13Z (GMT). No. of bitstreams: 1 fortunato_fm_dr_araiq.pdf: 6655475 bytes, checksum: 3c80582e1359616323d24334fc381808 (MD5) Previous issue date: 2017-02-22 / Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP) / O objetivo desta Tese de Doutorado foi avaliar o método de adição de padrão interno empregando técnicas espectroscópicas. Inicialmente o método de adição de padrão interno foi aplicado no modo convencional na determinação de Ca e Mg em amostras biodiesel e urina por espectrometria de absorção atômica em chama de alta resolução e fonte contínua e na determinação de ureia em urina por espectroscopia Raman. Para fins comparativos, todas as amostras e materiais certificados foram também analisados pelos métodos de calibração externa, adição de padrão e padronização interna. Nitrato, Sr e Mn foram selecionados como padrões internos para ureia, Ca e Mg, respectivamente. Para avaliar a exatidão do método na determinação de Ca e Mg foram analisados nove materiais de referência certificados (CRM) e os resultados obtidos foram concordantes a 95% de confiança com os valores certificados (teste t). Para ureia a exatidão foi avaliada por meio de comparação dos resultados obtidos pelo método de adição de padrão interno e por um método de referência. Todos os resultados obtidos foram concordantes entre si (teste t pareado) ao nível de 95% de confiança. A exatidão do método também foi checada por meio de testes de adição e recuperação: Ca (93 – 119%), Mg (100 – 116%) e ureia (99 – 105%). A desvantagem do método de adição de padrão interno convencional foi o volume total de amostra utilizado, a quantidade de soluções analíticas empregadas e a baixa frequência analítica. No entanto, este problemas foram solucionados com o desenvolvimento de sistemas em fluxo e pelo uso de um gradiente de concentração. O método de adição de padrão interno por gradiente de concentração em fluxo foi avaliado na determinação de Na e K em amostras de biodiesel e urina por espectrometria de emissão atômica em chama e na determinação de etanol em gasolina por espectroscopia Raman. Lítio foi empregado como padrão interno para Na e K, e acetona foi utilizada como padrão interno para etanol. A exatidão do método na determinação de Na e K foi avaliada por meio da análise de cinco CRMs, e os resultados obtidos para Na foram concordantes a 95% de confiança com os valores certificados (teste t), para K os resultados apresentaram valores subestimados ao longo do trabalho (em torno de 80% de recuperação). Para determinação de etanol em gasolina a exatidão foi avaliada por meio da comparação dos resultados obtidos pelo método proposto e pelo método de referência, e todos os resultados obtidos foram concordantes entre si (teste t pareado) ao nível de 95% de confiança. A exatidão do método de adição de padrão interno por gradiente de concentração em fluxo também foi avaliada por meio de testes de adição e recuperação: Na (94 – 110%), K (73 – 86%) e etanol (99 – 104%). Os resultados obtidos utilizando o método de adição de padrão interno (convencional e em fluxo) em todas as aplicações apresentaram precisão e exatidão melhores ou comparáveis aos métodos de adição de padrão, padronização interna e calibração externa, mostrando ser uma estratégia de calibração eficiente para técnicas espectroscópicas. / The aim of this Doctoral Thesis was to evaluation of the internal standard addition method employing spectroscopic techniques. Initially, traditional standard addition method was applied for Ca and Mg determination in biodiesel and urine samples by high-resolution continuum source flame atomic absorption spectrometry and for urea determination in urine samples by Raman spectroscopy. For comparison purposes, all samples and certified materials were also analyzed by external calibration, standard addition and internal standardization methods. Nitrate, Sr and Mn were selected as internal standards for urea, Ca and Mg, respectively. In order to verify the accuracy for Ca and Mg determination were analyzed nine certified reference materials (CRM), the results were in agreement with certified values at the 95% confidence level (t-test). For urea, the accuracy was evaluated by comparison of the results obtained by internal standard addition and a reference method. All results were in agreement at 95% confidence level (paired t-test) with each other. The accuracy was also checked by addition and recovery tests: Ca (93 - 119%), Mg (100 - 116%) and urea (99 - 105%). The drawbacks of traditional internal standard addition were the total volume of sample used, the amount of analytical solutions employed and the lower sample throughput. However, these problems were solved with the development of flow systems and the use of a concentration gradient. The internal standard addition by flow gradient concentration was evaluated for Na and K determination in biodiesel and urine samples by flame emission atomic spectrometry and for ethanol determination in gasoline by Raman spectroscopy. Lithium was selected as internal standard for Na and K, and acetone was selected as internal standard for ethanol. The accuracy of the method for Na and K determination was evaluated by five CRMs analysis, and the results obtained for Na were in agreement with certified values at the 95% confidence level (t-test), for K the results presented underestimated values throughout the study (around 80% recovery). The accuracy for ethanol determination in gasoline was evaluated comparing the results obtained by the proposed method with the reference method. All results were in agreement at 95% confidence level (paired t-test) with each other. The accuracy of internal standard addition by flow gradient concertation method was also evaluated by addition and recovery tests: Na (94 - 110%), K (73 - 86%) e ethanol (99 - 104%). The results obtained by internal standard addition (traditional and flow modes) for all applications showed accuracy and precision better or comparable with traditional calibration methods (standard addition, internal standardization and external calibration), revealing to be an efficient calibration strategy for spectroscopic techniques. / FAPESP: 2012/23323-7

Conselho Nacional de Desenvolvimento CientÃfico e TecnolÃgico / A formaÃÃo de trihalometanos na Ãgua de abastecimento humano representa um grande problema para a saÃde pÃblica, visto que esses compostos sÃo suspeitos de serem carcinogÃnicos. A tÃcnica referenciada para determinaÃÃo de trihalometanos na Ãgua à a cromatografia gasosa, onde se utiliza o detector de captura de elÃtrons. Essa tÃcnica apresenta algumas desvantagens que inviabilizam sua implantaÃÃo em uma estaÃÃo de tratamento de Ãgua (ETA). Um mÃtodo espectrofotomÃtrico desenvolvido pela empresa Hach pode auxiliar a operaÃÃo de uma ETA quanto ao monitoramento dos trihalometanos, pois esse mÃtodo analÃtico tem menor custo, uma resposta imediata dos resultados e à de fÃcil implantaÃÃo e operaÃÃo quando se compara com a cromatografia gasosa. Nesta pesquisa, foi realizada uma avaliaÃÃo do mÃtodo espectrofotomÃtrico comercial por alguns parÃmetros do Instituto Nacional de Metrologia, NormalizaÃÃo e Qualidade Industrial (INMETRO) e foi dividida em trÃs etapas. Na primeira etapa, realizou-se um teste para certificar-se que o agente redutor neutralizava todo o cloro residual presente na Ãgua. Foi adicionado tiossulfato de sÃdio na Ãgua final da ETA GaviÃo e determinou-se concentraÃÃo de âzeroâ mg L-1 na determinaÃÃo de cloro residual. A segunda etapa consistiu na implantaÃÃo e operaÃÃo da anÃlise de trihalometanos por cromatografia gasosa. Foram realizadas duas curvas utilizando dois padrÃes diferentes: um padrÃo de clorofÃrmio e um padrÃo de uma mistura contendo os quatro trihalometanos, todos com a mesma concentraÃÃo. Nessa etapa, todas as curvas construÃdas apresentaram um Ãndice de correlaÃÃo dentro da faixa exigida pelas normas do INMETRO e do mÃtodo. A terceira etapa consistiu na construÃÃo de curvas utilizando novamente os dois padrÃes, porÃm utilizando a tÃcnica espectrofotomÃtrica. Foram realizadas duas curvas de cada padrÃo pelo mesmo analista e uma curva de cada padrÃo por outro analista. Com os dados obtidos, estudou-se a precisÃo, exatidÃo, robustez, seletividade, linearidade, faixa de trabalho e faixa linear. AlÃm disso, foram realizados testes de adiÃÃo de padrÃo e um teste para verificar a interferÃncia de diferentes matrizes na anÃlise. Constatou-se que o mÃtodo nÃo apresentou precisÃo, nem exatidÃo. Pequenas mudanÃas realizadas no procedimento analÃtico causaram alteraÃÃo no resultado, indicando falta de robustez do mÃtodo analÃtico, alÃm de ser extremamente suscetÃvel a erros aleatÃrios e, possivelmente, quantificar outros subprodutos da desinfecÃÃo / The formation of trihalomethanes in human water supply represents a big problem to the public health, since these compounds are suspected carcinogens. The technique referred for determination of trihalomethanes in water is gas chromatography, which uses an electron capture detector. This technique has some disadvantages that unfeasible the implantation in the water treatment plant. A spectrophotometry method developed by Hach can assist the operation of a water treatment plant on the monitoring of trihalomethanes, since this analytical method has a lower cost, an immediate response by the results and is easy to implantation and operate when compared with gas chromatography. In this research, an evaluation of commercial spectrophotometry method was realized for some parameters of the Instituto Nacional de Metrologia, NormalizaÃÃo e Qualidade Industrial (INMETRO) and was divided into three stages. In the first stage, performed a test to make sure that the reducing agent neutralize any residual chlorine in the water. Sodium thiosulfate was added treated water of GaviÃoÂs water treatment plant, to determine the concentration of âzeroâ mg L-1 in the determination of residual chlorine. The second stage consists in the implantation and operation of the analysis of trihalomethanes by gas chromatography. Two curves were performed using two different standards: a standard of chloroform and a standard of a mixture containing the four trihalomethanes, all with the same concentration. At this stage, all curves constructed showed a correlation coefficient in the range required by the rules of the INMETRO and of the method. The third step was the construction of curves by using again the two standards, but using the spectrophotometric method. Two curves of each standard by the same analyst and a curve of each standard of the other analyst were performed. With the data obtained, was studied the precision, accuracy, robustness, selectivity, linearity, working range and linear range. In addition, a standard addition test and a test for interference in the analysis of different matrices were performed. It was found that the method no had precision and accuracy. Small changes made in the analytical procedure caused change in the result, indicating lack of robustness of the analytical method, besides being extremely susceptible to random errors and possibly quantify other disinfection byproducts

The global nitrogen cycle has been disrupted by large anthropogenic inputs of reactive nitrogen to the environment. Excess nitrogen underlies environmental problems such as eutrophication, and can negatively affect human health. Managing the natural microbial process of denitrification is advocated as a promising avenue to reduce excess nitrogen, and denitrifying bioreactors (DNBRs) are an emerging technology harnessing this biochemical process. Previous DNBR research has established successful nitrate removal, whereas this study examines the potential to expand DNBR functionality to address excess phosphorus and mitigate the production of nitrous oxide, a potent greenhouse gas. Results from a laboratory experiment supported the hypothesis that the addition of biochar, a charcoal-like soil amendment and novel organic carbon source in DNBR research, would increase nitrate and phosphorus removal as well as decrease the accumulation of nitrous oxide, an intermediate product of microbial denitrification. In order more closely examine the ratio of the products nitrous oxide and inert dinitrogen, development of a novel analytical method to quantify dissolved gases in environmental water samples using gas chromatography mass spectrometry was undertaken. Although static headspace analysis is a common technique for quantifying dissolved volatiles, the variation in sample preparation has recently been revealed to affect the determination of dissolved concentrations of permanent gases and convolute comparison between studies. This work demonstrates the viability of internal calibration with gaseous standard addition to make dissolved gas analysis more robust to variable sample processing and to correct for matrix effects on gas partitioning that may occur in environmental samples. / Master of Science

Šio darbo tikslas yra ištirti mažų koncentracijų matavimų vandeniniuose tirpaluose tikslumą, ypač monoizotopiniams elementams, taikant Element2 indukciniu būdu kuriamos plazmos masių spektrometrijos metodą, nustatyti pagrindines matavimų tikslumą ribojančias priežastis ir pabandyti sumažinti jų įtaką, įvertinti tokių matavimų taikymo galimybes medžiagų kilmės atpažinimui. / High resolution sector field ICP MS measurements of concentrations are widely used in modern analytical chemistry and applications. Two problems are concerned in the present work: improvement of accuracy of measurements of concentration of monoisotopic elements (As) and analysis of applicability of the multielement analytical data for classification of samples according to their origin. 66Zn, 77Se and 94Mo were used as internal standards to measure the concentration of As in water by the method of additions. Application of 77Se as internal standard resulted in the best accuracy of analysis. Drift of the measured signal ratios was identified as the main source of uncertainty limiting the accuracy of the mass fraction measurements at relative expanded uncertainty of 2% (k=2). The information as well as the level of inherent noise characterizes the quality of application of the multivariate analysis of multielement data for classification of samples. The role of noise increases if large number of parameters is needed. Stepwise approach is tested dividing the wine origin classification test into some steps to simplify the problem. Outcomes of the approach in comparison to the straightforward test are studied on the basis of the chemical analytical data obtained for 25 elements in 65 wines from 8 countries. Bivariate Gaussian distribution is used to evaluate the reproducibility of the discrimination between countries of origin and reliability of classification of the samples. In... [to full text]

Submitted by Tony Rogerio de Lima Dadamos null (tonyrlrl@yahoo.com.br) on 2018-02-20T16:25:35Z No. of bitstreams: 1 Tese_AU_TRLD_2018.pdf: 2071412 bytes, checksum: ba59227c90cba94171f8548d07346f1a (MD5) / Approved for entry into archive by Elza Mitiko Sato null (elzasato@ibilce.unesp.br) on 2018-02-21T19:00:37Z (GMT) No. of bitstreams: 1 dadamos_trl_dr_sjrp.pdf: 2071412 bytes, checksum: ba59227c90cba94171f8548d07346f1a (MD5) / Made available in DSpace on 2018-02-21T19:00:37Z (GMT). No. of bitstreams: 1 dadamos_trl_dr_sjrp.pdf: 2071412 bytes, checksum: ba59227c90cba94171f8548d07346f1a (MD5) Previous issue date: 2018-01-24 / Este trabalho apresenta metodologias de desenvolvimento, otimização, e validação de procedimentos de medição eletroquímica de parâmetros bioquímicos em fluidos biológicos. As ferramentas desenvolvidas foram aplicadas à medição voltamétrica, simples e de baixo custo de ácido úrico (AU) em soro humano que se apresenta como uma alternativa confiável às medições realizadas pelo método de referência espectrofométrico. Foi estudada a medição de AU no soro visto a ser utilizada no diagnóstico de várias doenças, tais como gota, doenças cardiovasculares e neoplasias. O eletrodo de trabalho modificado desenvolvido e otimizado é composto por 25 % de lignina, 60 % de nanografite, 15 % de óleo mineral e cobre metálico eletrodepositado. As medições foram realizadas por um método de adição cumulativa de padrão (MAP-C), recorrendo a um novo tratamento estatístico dos dados de calibração, que permite a calibração da instrumentação num pequeno volume de soro. A incerteza da medição foi estimada recorrendo a diversas abordagens bottom-up desenvolvidas e usando abordagens pragmáticas top-down apresentadas na bibliografia. As componentes de incerteza foram combinadas usando a Lei de Propagação de Incertezas ou os métodos numéricos de Kragten e Monte Carlo. Procedeu-se igualmente a uma avaliação bayesiana da incerteza da medição que envolve a atualização de dados da prevalência de ácido úrico na população com o resultado da medição do soro específico analisado. Os modelos metrológicos desenvolvidos foram implementados em folhas de cálculo MSExcel de fácil utilização pelo analista. As avaliações bottom-up da incerteza da medição recorreram a estimativas da incerteza de extrapolação produzidas pelo modelo de regressão ou usando simulações de Monte Carlo aplicáveis quando os pressupostos do modelo de regressão não são cumpridos. O método de adição cumulativa de padrão foi aplicado com sucesso à análise de soro humano pela adição de 1,0, 3,0, 5,0, 7,0 e 9,0 mg dL-1 de AU a 5 mL de soro. A adequação da qualidade das medições eletroquímicas foi avaliada comparando sua incerteza com um valor alvo de 0,56 mg dL-1 (uma oitava parte das faixas de AU de indivíduos saudáveis) e avaliado a compatibilidades das medições com determinações realizadas pelo procedimento de referência. As medições realizadas revelaram-se válidas e com menor custo do que as produzidas pelo método de referência. As ferramentas desenvolvidas para a construção e otimização de eletrodos de trabalho são aplicáveis à medição de outras espécies de análise e em outras matrizes. O método de adição cumulativa de padrão desenvolvido, bem como os modelos de medição respectivos desenvolvidos, são aplicáveis a qualquer tipo de medição instrumental não destrutiva de soluções. / This work presents methodologies for the development, optimization and validation of procedures for the electrochemical measurement of biochemical parameters in biological fluids. The developed tools were applied to voltammetric, simple and low-cost measurements of uric acid (AU) in human serum, which proved to be a reliable alternative to the spectrophotometric reference method. It was studied the measurement of AU in serum since it is used in the diagnosis of various diseases, such as gout, cardiovascular diseases and neoplasms. The developed and optimized modified working electrode is composed of 25 % lignin, 60 % nanocarbon, 15 % mineral oil and electrodeposited copper. The measurements were performed using a cumulative standard addition method (MAP-C), using a new statistical treatment of the calibration data, which allows the calibration of the instrumentation in a small volume of serum. The measurement uncertainty was estimated using developed bottom-up approaches and using pragmatic top-down approaches presented in the literature. The uncertainty components were combined using the Uncertainty Propagation Law or the numerical Kragten and Monte Carlo methods. A bayesian evaluation of the measurement uncertainty was performed, involving the updating of uric acid prevalence in the population with the result of the measurement of AU in the specific serum sample. The developed metrological models were implemented in user-friendly MS-Excel spreadsheets. The bottom-up assessments of measurements uncertainty involve the estimation of the extrapolation uncertainty from the regression model or using Monte Carlo simulations applicable to when the assumptions of the regression model are not valid. The cumulative standard addition method was successfully applied to the analysis of human serum by adding 1.0, 3.0, 5.0, 7.0 and 9.0 mg dL-1 of AU to 5 mL of serum. The adequacy of the electrochemical measurements was assessed by comparing their uncertainty with a target value of 0.56 mg dL-1 (one-eighth of the range of AU in healthy individuals) and by evaluating the compatibility of measurements with determinations performed by the reference procedure. The performed measurements are valid and significantly cheaper than those produced by the reference method. The tools developed for the construction and optimization of working electrodes are applicable to the measurement of other analytes and matrices. The developed cumulative standard addition method and respective measurement models, are applicable to any kind of non-destructive chemical measurement of a solution.

No description available.

L’application de la photoluminescence suscite un intérêt croissant de la part des chercheurs et ceci dans de nombreux domaines. Dans notre cas, différents complexes à base de lanthanide seront détectés par une méthode spectrophotométrique avancée, la fluorescence résolue en temps. Ces derniers peuvent être ainsi détectés même à l’état de traces au sein des milieux complexes tel que ceux rencontrés dans l’industrie pétrolière (saumures, traces de pétrole, éléments solides en suspension, etc.). L'utilisation de la détection de fluorescence résolue en temps combinée à des complexes de lanthanides a été démontrée comme une stratégie simple et efficace pour éliminer la fluorescence de fond des matrices présentes dans le milieu étudié et fournir un rapport signal sur bruit élevé. Le sujet de cette thèse consiste à répondre avec les outils précédents à différentes problématique existants au sein de l’industrie pétrolière, de l’extraction du pétrole au processus de marquage de différents produits raffinés à des fins commerciales. Dans la première partie du manuscrit décrira différents protocoles capables d’extraire de l’information de différents additifs chimiques employés sur les champs pétrolifères lors de l’extraction de pétrole et de gaz. Les additifs en questions peuvent être des inhibiteurs de dépôts minéraux, des inhibiteurs de corrosion, des polymères viscoélastiques, dans différentes eaux de synthèse et de production issues de différentes plateformes. Les impacts de certains facteurs ont été analysés afin d’améliorer la sensibilité et les performances. Nous démontrerons la possibilité de quantifier avec succès la teneur résiduelle de différents types d'additifs chimiques. L'effet de matrice de l’échantillon a été limité par le développement de deux stratégies d'addition standard. Nous montrerons par ailleurs qu’il est possible de quantifier la présence non seulement d’un additif mais encore, dans certaines situations optimisées, de deux additifs en mélange. Outre la détermination de la concentration en additifs chimiques, nous présenterons également une méthode permettant de déterminer l’anionicité d’un polymère en milieu complexe. Dans la deuxième partie du document, nous détaillerons le développement de complexes de lanthanides utilisés en tant que marqueurs ainsi que la méthode de détection par fluorescence résolue en temps visant à la lutte contre la contrefaçon de différents pétroles bruts et de carburants raffinés. La synthèse et le processus d’incorporation de trois types de marqueurs de photoluminescence et leur stabilité dans différents carburants seront ensuite discutés. Les résultats obtenus démontrent qu’il est possible, à l’aide de cette technologie de marquage, de détecter efficacement les fraudes à la taxe dans les carburants, même à haute dilution. Ces travaux présente potentiellement un fort impact dans les domaines académiques comme industriels. Toutes les études se concentrent sur la mise au point d’une procédure simple, qui fournit une sensibilité élevée permettant de réduire le coût de production et qui repose sur l’emploi du fluorimètre résolu en temps Inibox™ développé pendant ma thèse pour porter sur le terrain les technologies développé au laboratoire / The application of photoluminescence is receiving an increasing interest from researchers coming from many fields. The previous laboratory works introduced a time-resolved fluorescence (TRF) detection method for the quantification of chemicals in complex medium (petroleum, production brine, and synthetic sea water) tagged with lanthanides, the additives form complexes that exhibit specific TRF signal which overcomes autofluorescence of sample and provide a high signal to noise ratio. The subject of this thesis concerns the development of specific methods based on patented technique to answer problematics arising in the oil industry from the extraction of crude product to the distribution of fuels. In the first part of the document, we focus on the monitoring of residual amount of chemical additives such as scale inhibitors, corrosion inhibitors, viscoelastic polymers in different synthetic and production waters. The impacts of some key factors were analyzed in order to improve the sensitivity and performance, also proves that under optimized conditions it is possible to quantify simultaneously two products in the same matrix. We successfully quantified various types of chemical additives with satisfying precision. Furthermore, the matrix effect was controlled by the development of two standard addition strategies. In addition to the determination of the concentration of chemical additives, we will also introduce a method to determine the anionicity of a polymer in difficult conditions. In the second part of the manuscript we follow the development of lanthanide complex markers and their detection for anti-counterfeiting on different crude oils and refined fuels. The synthesis, incorporation process and stability of three types of photoluminescence markers in different fuels have been discussed. The obtained results will prove that the technology can be used to detect fraud on fuels. This work has a potential great impact for both the academic and industrial domains. All studies focus on the creation of a simple procedure, with high sensitivity and low cost. All method are relying in the end on a specific field apparatus developed during my thesis to support the exportation of the technologies from the laboratory to the industry: The Inibox™

Se desarrolló cinco sistemas automatizados utilizando análisis por inyección secuencial (SIA) y análisis por inyección en flujo multijeringa (MSFIA). Se desarrolló un SI-analizador para la determinación de formaldehído utilizando la reacción de Hantzsch. El analizador fue aplicado a la monitorización en un cultivo de P. pastoris. Se desarrolló un SI-analizador para la determinación de glicerol y sorbitol. Se utilizó periodato para la reacción de Malaprade. El formaldehído generado fue cuantificado con la reacción de Hantzsch. El sistema incluyó la dilución de la muestra y procedimientos seleccionado por decisión inteligente del programa o por el usuario. Se lo aplicó a la monitorización en cultivos de P. pastoris.Se desarrolló un sistema de electroforesis capilar (CE) acoplado a un SIA aplicado a la separación de nitrofenoles. Se acopló por primera vez MSFIA con CE para pre-concentración en fase sólida y separación de nitrofenoles. Ambos sistemas mostraban recuperaciones satisfactorias para aguas ambientales. / Five analytical systems using Sequential Injection Analysis (SIA) and Multisyringe Flow Injection Analysis (MSFIA) were developed and applied with satisfactory analytical performance. A SI-analyzer for formaldehyde was developed automating Hantzsch reaction. It was successfully applied to formaldehyde monitoring in continuous medium filtrate of P. pastoris cultivation. A second SI-analyzer was developed for the determination of glycerol and sorbitol. Periodate was used as additional reagent to carry out Malaprade reaction and formaldehyde generated by polyalcohol oxidation was quantified. The system included automated sample dilution and procedures for two working ranges, selected by smart software decision or user-input. It was applied to monitoring of P. pastoris cultivations.A capillary electrophoresis (CE) system was developed and coupled to SIA. It was applied to the determination of nitrophenols. MSFIA and CE were coupled for the first time. Solid phase concentration and separation of nitrophenols were automated. The systems were applied to environmental water samples.