[ES] El cacao es un producto de alto valor, no únicamente por sus características sensoriales, sino porque también presenta un alto contenido en antioxidantes y alcaloides estimulantes con efectos saludables. Debido a la alta demanda, la industria del cacao en polvo tiene el desafío de asegurar la calidad de grandes volúmenes de producción de una manera rápida y precisa, evitando la presencia de contaminantes o adulterantes en la materia prima, ofreciendo productos donde se preserven las propiedades saludables. La espectroscopia del infrarrojo cercano (NIR) es una tecnología rápida y no destructiva útil en el análisis de productos alimentarios. La presente tesis doctoral se centra en evaluar el potencial uso del NIR como una herramienta de control de calidad con el fin de poder resolver problemas que se presentan en la industria del cacao en polvo. Los problemas a resolver incluyen la detección de materiales no deseados o adulterantes en el cacao en polvo, y la monitorización rápida y precisa del contenido de flavanoles y metilxantinas del cacao en polvo durante el proceso de alcalinización. El primer capítulo evalúa la viabilidad del NIR, en combinación con análisis quimiométricos, en la detección de la presencia de materiales no deseados o adulterantes como son cascarilla de cacao o harina de algarroba. Para ello, diferentes muestras de cacao en polvo natural y con diferentes niveles de alcalinización (suave, medio y fuerte) fueron mezcladas con distintas proporciones de cascarilla de cacao (con cacao natural) o harina de algarroba (con cacao natural y alcalinizado). Los resultados obtenidos indican que el NIR, combinado con modelos estadísticos tales como el análisis discriminante por mínimos cuadrados parciales (PLS-DA) y la regresión parcial de mínimos cuadrados (PLS), es un método rápido y eficaz para identificar cualitativa y cuantitativamente materiales no deseados o adulterantes como la cascarilla y la algarroba en cacao en polvo, independientemente del grado de alcalinización o el nivel de tostado de la harina de algarroba. En el segundo capítulo, el análisis composicional del cacao en polvo se orientó al control de los cambios producidos en el contenido de flavanoles y metilxantinas debidos al proceso de alcalinización al que se somete el caco en polvo. Se determinó el contenido de catequina, epicatequina, cafeína y teobromina mediante cromatografía líquida de alta resolución (HPLC), correlacionándose los contenidos obtenidos para cada uno de estos compuestos con las determinaciones NIR. Se obtuvieron buenos modelos para la predicción de los compuestos mediante regresión PLS con valores superiores a 3 para la relación entre el rendimiento y la desviación (RDP), lo cual demuestra que los modelos obtenidos pueden ser utilizados para la rápida y fiable predicción del contenido de flavanoles y metilxantinas en cacaos naturales y con diferentes niveles de alcalinización. / [CAT] El cacau és un producte d'alt valor, no sols per les seues característiques sensorials, sinó perquè també presenta un elevat contingut en antioxidants i alcaloids estimulants amb efectes saludables. A conseqüència a l'alta demanda, l'industria del cacau en pols té el desafiament d'assegurar la qualitat de grans volums de producció d'una manera ràpida i precisa, evitant la presència de contaminants o adulterants en la matèria cosina, oferint productes a on se preserven les propietats saludables. L'espectroscòpia de l'infrarroig proper (NIR) és una tecnologia ràpida i no destructiva útil en l'anàlisi de productes alimentaris. La present tesis doctoral se centra en avaluar el potencial ús del NIR com una eina de control de qualitat amb l'objectiu de poder resoldre problemes que es presenten en l'industria del cacau en pols. Els problemes a resoldre inclouen la detecció de materials no desitjats o adulterants en el cacau en pols, i la monitorització ràpida i precisa del contingut de flavanols i metilxantines del cacau en pols durant el procés d'alcalinització. El primer capítol avalua la viabilitat del NIR, en combinació amb anàlisis quimiométrics, en la detecció de la presència de materials no desitjats o adulterants com són pellofa de cacau o farina de garrofa. Per a això, diferents mostres de cacau en pols natural i amb diferents nivells d'alcalinització (suau, mig i fort) foren barrejades en distintes proporcions de pellofa de cacau (en cacau natural) o farina de garrofa (en cacau natural i alcalinisat). Els resultats obtinguts per a NIR, combinats amb models estadístics com l'anàlisi discriminant per mínims quadrats parcials (PLS-DA) i la regressió parcial de mínims quadrats (PLS), és un mètode ràpid i eficaç per identificar materials no desitjats o adulterants com la pellofa de cacau o la farina de garrofa, amb independència del grau d'alcalinització del cacau o de torrat de la farina de garrofa. En el segon capítol, l'anàlisi composicional del cacau en pols s'orientà al control dels canvis produïts en el contingut de flavanols i metilxantines a causa del procés d'alcalinització al que se sotmet el cacau en pols. Es va determinar el contingut de catequina, epicatequina, cafeïna i teobromina mitjançant cromatografia líquida d'alta resolució (HPLC), i es van correlacionar els continguts obtinguts per a cadascun d'estos composts amb les determinacions NIR. Es van obtindré bons models per a la predicció dels composts mitjançant regressió PLS amb valors superiors a 3 per a la relació entre el rendiment i la desviació (RDP), la qual cosa demostra que els models obtinguts poden ser emprats per a la ràpida i fiable predicció del contingut de flavanols i metilxantines en cacaus naturals o amb diferents nivells d'alcalinització. / [EN] Cocoa is a product of high value, not only because of its sensory characteristics, but also because it has a high content of antioxidants and stimulating alkaloids with health effects. Due to the high demand, the cocoa powder industry has the challenge of ensuring the quality of large volumes of production in a fast and accurate way, avoiding the presence of contaminants or adulterants in the raw material, offering products where the healthy properties are preserved. The near infrared spectroscopy (NIR) is a rapid and non-destructive technology useful in the analysis of food products. The present doctoral thesis focuses on evaluating the potential use of NIR as a quality control tool in order to solve problems that arise in the cocoa industry powdered. The problems to solve include the detection of unwanted materials or adulterants in the cocoa powder, and the rapid and accurate monitorization of the flavanols and methylxanthines content in the cocoa powder during the alkalization process. The first chapter evaluates the viability of the NIR, in combination with chemometric analysis, in the detection of presence of unwanted materials or adulterants such as cocoa shell or carob flour. For this, different samples of natural cocoa powder and with different levels of alkalization (light, medium and strong) were mixed with different proportions of cocoa shell (with natural cocoa) or carob flour (with natural and alkalized cocoa). The results obtained indicate that the NIR combined with statistical models such as the partial least squares discriminant analysis (PLS-DA) and the partial least squares regression (PLS), is a fast and efficient method to identify qualitative and quantitative unwanted materials or adulterants such as shell and carob in cocoa powder, regardless of the degree of alkalization or level of roasting of carob flour. In the second chapter, the compositional analysis of cocoa powder was oriented to the control of the changes produced in the content of flavanols and methylxanthines due to the process of alkalization to which the cocoa powder is subjected. The content of catechin, epicatechin, caffeine and theobromine were determined by high performance liquid chromatography (HPLC), correlating the contents obtained for each of these compounds with the NIR determinations. Good models were obtained for the prediction of compounds by regression PLS with values above 3 for the ratio of performance to deviation (RDP), which shows that the obtained models can be used for the quick and reliable prediction of flavanol content and methylxanthines in natural cocoas and with different alkalization levels. / This Doctoral Thesis has been carried out thanks to a doctoral studies scholarship granted by the Ministry of Higher Education, Science, Technology and Innovation (SENESCYT) of the Republic of Ecuador / Quelal Vásconez, MA. (2019). Application of Infrared Spectroscopy and Chemometrics to the Cocoa Industry for Fast Composition Analysis and Fraud Detection [Tesis doctoral no publicada]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/135258 / TESIS

[pt] Corpos relativamente pequenos do sistema solar não possuem atmosfera (ou muito rarefeita, chamada exosfera) e nem campo magnético: encontram-se praticamente desprotegidos da influência do ambiente espacial no qual estão inseridos. Tais corpos (como a maioria dos asteroides, luas e cometas distantes do Sol), estão sujeitos aos efeitos do chamado intemperismo espacial. Com o objetivo de simular e estudar este fenômeno em laboratório, três amostras de meteoritos do tipo condrito ordinário foram irradiadas por feixes de H(positivo) com energia de 1,0 MeV. Uma das amostras foi, também, irradiada por feixe de N(positivo) de 2,0 MeV. Os efeitos da irradiação foram monitorados por espectroscopias Raman e UV-VIS-NIR. Os resultados Raman mostram variações sistemáticas do número de onda, da intensidade e da largura das bandas vibracionais estudadas, evidências de modificações estruturais. As seções de choque de destruição das ligações Si-O presentes nas estruturas cristalinas foram determinadas. A espectroscopia UV-VIS-NIR por refletância de esfera integrada foi usada para monitorar as modificações nas características espectrais. Os espectros obtidos mostram escurecimento e avermelhamento progressivos das amostras irradiadas; a amplitude destas modificações depende do conteúdo inicial de ferro na estrutura. É proposto que o avermelhamento observado com o aumento da fluência (ou dose) da irradiação deve-se ao aumento do coeficiente de absorção na faixa azul que, por sua vez, decorre da diminuição do gap óptico do material. Estes resultados são relevantes para a modelagem da evolução físico-química de asteroides expostos ao vento solar. / [en] Relatively small bodies in the solar system have no atmosphere (or very thin, called the exosphere) and no magnetic field: they are virtually unprotected from the influence of the space environment in which they are inserted. Such bodies (like most asteroids, moons, and comets far from the sun), are subject to the effects of so-called space weathering. To simulate and study this phenomenon in the laboratory, three samples of ordinary chondrite meteorites were irradiated by H(positive) beams with 1.0 MeV energy. One of the samples was also irradiated by a 2.0 MeV N(positive) beam. The effects of irradiation were monitored by Raman and UV-VIS-NIR spectroscopies. The Raman results show systematic variations in the wavenumber, intensity, and width of the studied vibrational bands, evidence of structural modifications. The shock sections of the destruction of Si-O bonds present in the crystalline structures were determined. Integrated sphere reflectance UV-VIS-NIR spectroscopy was used to monitor changes in spectral characteristics. The obtained spectra show progressive darkening and reddening of the irradiated samples; The extent of these modifications depends on the initial iron content in the structure. It is proposed that the redness observed with the increase of irradiation creep (or dose) is due to the increase in the absorption coefficient in the blue band, which, in turn, results from the decrease of the optical gap of the material. These results are relevant for modeling the physicochemical evolution of asteroids exposed to the solar Wind.

This project utilised a novel solvent-free continuous cocrystallisation (SFCC) method to manufacture pharmaceutical co-crystals. The objectives were to optimize the process towards achieving high co-crystal yields and to understand the behaviour of co-crystals under different conditions. Particular attention was paid to the development of near infrared (NIR) spectroscopy as a process analytical technology (PAT). Twin screw, hot melt extrusion was the base technique of the SFCC process. Changing parameters such as temperature, screw speed and screw geometry was important for improving the co-crystal yield. The level of mixing and shear was directly influenced by the screw geometry, whilst the screw speed was an important parameter for controlling the residence time of the material during hot melt extrusion. Ibuprofen – nicotinamide 1:1 cocrystals and carbamazepine – nicotinamide 1:1 co-crystals were successfully manufactured using the SFCC method. Characterisation techniques were important for this project, and NIR spectroscopy proved to be a convenient, accurate analytical technique for identifying the formation of co-crystals along the extruder barrel. Separate thermal and model shear deformation studies were also carried out to determine the effect of temperature and shear on co-crystal formation for several different pharmaceutical co-crystal pairs. Finally, NIR spectroscopy was used to create two partial least squares regression models, for predicting the 1:1 co-crystal yield of ibuprofen – nicotinamide and carbamazepine – nicotinamide, when in a powder mixture with the respective pure API. It is believed that the prediction models created in this project can be used to facilitate future in-line PAT studies of pharmaceutical co-crystals during different manufacturing processes. / Engineering and Physical Sciences Research Council (EPSRC)

Noble metal nanoparticles such as gold and silver are of interest because of the unique electro-optical properties (e.g., localized surface plasmon resonance [LSPR]) that originate from the collective behavior of their surface electrons. These nanoparticles are commonly developed and used for biomedical and industrial application. A recent report has predicted that the global market for gold nanoparticles will be over 12.7 tons by year 2020. However, these surface-functionalized nanoparticles can be potential environmental persistent contaminants post-use due to their high colloidal stability in the aquatic systems. Despite, the environmental risks associated with these nanoparticles, just a few studies have investigated the effect of nanofeature factors such as size and shape on the overall fate/transport and organismal uptake of these nanomaterials in the aquatic matrices. This study presents a comprehensive approach to evaluate the colloidal stability, fate/transport, and organismal uptake of these nanoparticles while factoring in the size and shape related properties. We demonstrate the importance and effect of anisotropicity of a gold nanoparticle on the colloidal behavior and interaction with ecologically susceptible aquatic biota. We also show how readily available characterization techniques can be utilized to monitor and assess the fate/transport of this class of nanoparticles. We further describe and investigate the relationship between the aspect ratio (AR) of these elongated gold nanoparticles with clearance mechanisms and rates from the aquatic suspension columns including aggregation, deposition, and biopurification. We illustrate how a fresh water filter-feeder bivalve, Corbicula fluminea, can be used as a model organism to study the size and shape-selective biofiltration and nanotoxicity of elongated gold nanoparticles. The results suggest that biofiltration by C. fluminea increases with an increase in the size and AR of gold nanoparticle. We develop a simple nanotoxicity assay to investigate the short-term exposure nanotoxicity of gold nanoparticles to C. fluminea. The toxicity results indicate that for the tested concentration and exposure period that gold nanoparticles were not acutely toxic (i.e., not lethal). However, gold nanoparticles significantly inhibited the activities of some antioxidant enzymes in gill and digestive gland tissues. These inhibitions could directly affect the resistance of these organisms to a secondary stressor (temperature, pathogens, hypoxia etc.) and threaten organismal health. / Ph. D.

Neste trabalho estudou-se o processo de polimerização de estireno em miniemulsão, através do monitoramento in-line da conversão do monômero e do tamanho das partículas geradas durante o processo de polimerização, através das técnicas espectroscópicas de Infravermelho Próximo (Near Infra Red - NIR) e Raman. As medições off-line de conversão foram feitas através de gravimetria e do tamanho das partículas através de Espalhamento Dinâmico de Luz (Dynamic Light Scattering - DLS). Também foi objeto deste estudo a modelagem matemática do process de polimerização em miniemulsão, assim como sua simulação utilizando o programa Matlab. A metodologia adotada para a obtenção dos resultados envolveu o trabalho experimental de monitoramento da síntese de poliestireno em miniemulsão utilizando iniciador hidrossolúvel (persulfato de potássio), tensoativo (lauril sulfato de sódio) e co-estabilizantes (hexadecano e poliestireno) e equipamento rotor-estator, Ultra Turrax T25, para obtenção da miniemulsão. O modelo matemático envolveu a determinação de equações fenomenológicas representativas do sistema em questão, prevendo as possíveis variações na cinética e fenômenos físico-químicos, decorrentes de variações na formulação prevendo inclusive os mecanismos de nucleação existentes em função da concentração de tensoativo utilizado. Como resultado, este trabalho validou as metodologias avaliadas para monitoramento da conversão e diâmetro das partículas poliméricas e também, ao comparar as metodologias avaliadas, identificou a espectroscopia NIR como metodologia preferencial por não exigir preparação da amostra, fornecer respostas em tempo real, sem defasagem de tempo e também por permitir coletar espectros com pequenos intervalos de tempo, garante melhor precisão e evita a perda de informações do processo. / In this work, is the development of a detailed study of the miniemulsion polymerization process monitoring monomer conversion and particle size along process. Near Infrared Spectroscopy (Near Infra Red - NIR) and Raman Spectroscopy were used to conversion and diameter determination. Gravimetric analyses were used to conversion determination. Dynamic Light Scattering (Dynamic Light Scattering - DLS) to particle size determination. It was also object of this study the Mathematical Modeling of Miniemulsion Polymerization Reaction Kinetic, as well as it simulation using Matlab software. The methodology used to obtain the results involved experimental work to synthesize and monitor miniemulsion polystyrene using water-soluble initiator (potassium persulfate), stabilizer (sodium lauryl sulfate) and co-stabilizers (hexadecane and polystyrene) and rotor-stator equipment Ultra Turrax T25 for miniemulsion obtaining. The mathematical model involved the determination of representative phenomenological equations this system, anticipating the possible variations in kinetics and physical-chemical phenomena, resulting from formulation variations mainly by verifying the surfactant concentration [S] to determine the existing nucleation mechanism when compared with the same surfactant critical micelle concentration [CMC]. The provided mechanisms are: micellar nucleation to [S] [CMC], droplets nucleation and homogeneous nucleation to [S] < [CMC]. As a result, this study validated the proposed methods for monitoring conversion and polymer particles diameter and also compare the evaluated methodologies, identifying NIR spectroscopy as a differential method among others for not to require sample preparation, supply answers in real time, no time delay and also to perform in shorter intervals, preventing the loss of process information.

Neste trabalho estudou-se o processo de polimerização de estireno em miniemulsão, através do monitoramento in-line da conversão do monômero e do tamanho das partículas geradas durante o processo de polimerização, através das técnicas espectroscópicas de Infravermelho Próximo (Near Infra Red - NIR) e Raman. As medições off-line de conversão foram feitas através de gravimetria e do tamanho das partículas através de Espalhamento Dinâmico de Luz (Dynamic Light Scattering - DLS). Também foi objeto deste estudo a modelagem matemática do process de polimerização em miniemulsão, assim como sua simulação utilizando o programa Matlab. A metodologia adotada para a obtenção dos resultados envolveu o trabalho experimental de monitoramento da síntese de poliestireno em miniemulsão utilizando iniciador hidrossolúvel (persulfato de potássio), tensoativo (lauril sulfato de sódio) e co-estabilizantes (hexadecano e poliestireno) e equipamento rotor-estator, Ultra Turrax T25, para obtenção da miniemulsão. O modelo matemático envolveu a determinação de equações fenomenológicas representativas do sistema em questão, prevendo as possíveis variações na cinética e fenômenos físico-químicos, decorrentes de variações na formulação prevendo inclusive os mecanismos de nucleação existentes em função da concentração de tensoativo utilizado. Como resultado, este trabalho validou as metodologias avaliadas para monitoramento da conversão e diâmetro das partículas poliméricas e também, ao comparar as metodologias avaliadas, identificou a espectroscopia NIR como metodologia preferencial por não exigir preparação da amostra, fornecer respostas em tempo real, sem defasagem de tempo e também por permitir coletar espectros com pequenos intervalos de tempo, garante melhor precisão e evita a perda de informações do processo. / In this work, is the development of a detailed study of the miniemulsion polymerization process monitoring monomer conversion and particle size along process. Near Infrared Spectroscopy (Near Infra Red - NIR) and Raman Spectroscopy were used to conversion and diameter determination. Gravimetric analyses were used to conversion determination. Dynamic Light Scattering (Dynamic Light Scattering - DLS) to particle size determination. It was also object of this study the Mathematical Modeling of Miniemulsion Polymerization Reaction Kinetic, as well as it simulation using Matlab software. The methodology used to obtain the results involved experimental work to synthesize and monitor miniemulsion polystyrene using water-soluble initiator (potassium persulfate), stabilizer (sodium lauryl sulfate) and co-stabilizers (hexadecane and polystyrene) and rotor-stator equipment Ultra Turrax T25 for miniemulsion obtaining. The mathematical model involved the determination of representative phenomenological equations this system, anticipating the possible variations in kinetics and physical-chemical phenomena, resulting from formulation variations mainly by verifying the surfactant concentration [S] to determine the existing nucleation mechanism when compared with the same surfactant critical micelle concentration [CMC]. The provided mechanisms are: micellar nucleation to [S] [CMC], droplets nucleation and homogeneous nucleation to [S] < [CMC]. As a result, this study validated the proposed methods for monitoring conversion and polymer particles diameter and also compare the evaluated methodologies, identifying NIR spectroscopy as a differential method among others for not to require sample preparation, supply answers in real time, no time delay and also to perform in shorter intervals, preventing the loss of process information.

Les entreprises pharmaceutiques ont progressivement adopté le concept de Process Analytical Technology (PAT) afin de contrôler et d'assurer en temps réel la qualité des produits pharmaceutiques au cours de leur production. Le PAT et un composant central du concept plus général de Quality-by-Design (QbD) promu par les agence régulatrices et visant à construire la qualité des produits via une approche scientifique et la gestion des risques.Une méthode basée sur la spectroscopie proche infrarouge (PIR) a été développée comme un outil du PAT pour contrôler en ligne la cristallisation d'un principe actif pharmaceutique. Au cours du procédé les teneurs en principe actif et en solvant résiduel doivent être déterminées avec précision afin d'atteindre un point d'ensemencement prédéfini. Une méthodologie basée sur les principes du QbD a guidé le développement et la validation de la méthode tout en assurant l'adéquation avec son utilisation prévue. Des modèles basés sur les moindres carrés partiels ont été construits à l'aide d'outils chimiométriques afin de quantifier les 2 analytes d'intérêt. La méthode a été totalement validée conformément aux requis officiels en utilisant les profils d'exactitude. Un suivi du procédé en temps réel a permis de prouver que la méthode correspond à son usage prévu.L'implémentation de cette méthode comme à l'échelle industrielle au lancement de ce nouveau procédé permettra le contrôle automatique de l'étape de cristallisation dans le but d'assurer un niveau de qualité prédéfini de l'API. D'autres avantages sont attendus incluant la réduction du temps du procédé, la suppression d'un échantillonnage difficile et d'analyses hors ligne fastidieuses. / Pharmaceutical companies are progressively adopting and introducing the Process Analytical Technology (PAT) concept to control and ensure in real-time product quality in development and manufacturing. PAT is a key component of the Quality-by-Design (QbD) framework promoted by the regulatory authorities, aiming the building of product quality based on both a strong scientific background and a quality risk management approach.An analytical method based on near infrared (NIR) spectroscopy was developed as a PAT tool to control on-line an API (active pharmaceutical ingredient) crystallization. During this process the API and residual solvent contents need to be precisely determined to reach a predefined seeding point. An original methodology based on the QbD principles was applied to conduct the development and validation of the NIR method and to ensure that it is fitted for its intended use. Partial least squares (PLS) models were developed and optimized through chemometrics tools in order to quantify the 2 analytes of interest. The method was fully validated according to the official requirements using the accuracy profile approach. Besides, a real-time process monitoring was added to the validation phase to prove and document that the method is fitted for purpose.Implementation of this method as an in-process control at industrial plant from the launch of this new pharmaceutical process will enable automatic control of the crystallization step in order to ensure a predefined quality level of the API. Other valuable benefits are expected such as reduction of the process time, and suppression of a difficult sampling and tedious off-line analyzes.

Extensive deforestations, particularly in the (sub)tropics, have led to intense soil degradation and erosion with concomitant reduction in soil fertility. Reforestations or plantations on those degraded sites may provide effective measures to mitigate further soil degradation and erosion, and can lead to improved soil quality. However, a change in land use from, e.g., grassland to forest may have a crucial impact on water balance. This may affect water availability even under humid tropical climate conditions where water is normally not a limiting factor. In this context, it should also be considered that according to climate change projections rainfall may decrease in some of these regions. To mitigate climate change related problems (e.g. increases in erosion and drought), reforestations are often carried out. Unfortunately, those measures are seldom completely successful, because the environmental conditions and the plant specific requirements are not appropriately taken into account. This is often due to data-scarcity and limited financial resources in tropical regions. For this reason, innovative approaches are required that are able to measure environmental conditions quasi-continuously in a cost-effective manner. Simultaneously, reforestation measures should be accompanied by monitoring in order to evaluate reforestation success and to mitigate, or at least to reduce, potential problems associated with reforestation (e.g. water scarcity). To avoid reforestation failure and negative implications on ecosystem services, it is crucial to get insights into the water balance of the actual ecosystem, and potential changes resulting from reforestation. The identification and prediction of water balance changes as a result of reforestation under climate change requires the consideration of the complex feedback system of processes in the soil-vegetation-atmosphere continuum. Models that account for those feedback system are Soil-Vegetation-Atmosphere-Transfer (SVAT) models. For the before-mentioned reasons, this study targeted two main objectives: (i) to develop and test a method combination for site evaluation under data scarcity (i.e. study requirements) (Part I) and (ii) to investigate the consequences of prediction uncertainty of the SVAT model input parameters, which were derived using geophysical methods, on SVAT modeling (Part II). A water balance modeling approach was set at the center of the site evaluation approach. This study used the one-dimensional CoupModel, which is a SVAT model. CoupModel requires detailed spatial soil information for (i) model parameterization, (ii) upscaling of model results and accounting for local to regional-scale soil heterogeneity, and (iii) monitoring of changes in soil properties and plant characteristics over time. Since traditional approaches to soil and vegetation sampling and monitoring are time consuming and expensive (and therefore often limited to point information), geophysical methods were used to overcome this spatial limitation. For this reason, vis-NIR spectroscopy (visible to near-infrared wavelength range) was applied for the measurement of soil properties (physical and chemical), and remote sensing to derive vegetation characteristics (i.e. leaf area index (LAI)). Since the estimated soil properties (mainly texture) could be used to parameterize a SVAT model, this study investigated the whole processing chain and related prediction uncertainty of soil texture and LAI, and their impact on CoupModel water balance prediction uncertainty. A greenhouse experiment with bamboo plants was carried out to determine plant-physiological characteristics needed for CoupModel parameterization. Geoelectrics was used to investigate soil layering, with the intent of determining site-representative soil profiles for model parameterization. Soil structure was investigated using image analysis techniques that allow the quantitative assessment and comparability of structural features. In order to meet the requirements of the selected study approach, the developed methodology was applied and tested for a site in NE-Brazil (which has low data availability) with a bamboo plantation as the test site and a secondary forest as the reference (reference site). Nevertheless, the objective of the thesis was not the concrete modeling of the case study site, but rather the evaluation of the suitability of the selected methods to evaluate sites for reforestations and to monitor their influence on the water balance as well as soil properties. The results (Part III) highlight that one needs to be aware of the measurement uncertainty related to SVAT model input parameters, so for instance the uncertainty of model input parameters such as soil texture and leaf area index influences meaningfully the simulated model water balance output. Furthermore, this work indicates that vis-NIR spectroscopy is a fast and cost-efficient method for soil measurement, mapping, and monitoring of soil physical (texture) and chemical (N, TOC, TIC, TC) properties, where the quality of soil prediction depends on the instrument (e.g. sensor resolution), the sample properties (i.e. chemistry), and the site characteristics (i.e. climate). Additionally, also the sensitivity of the CoupModel with respect to texture prediction uncertainty with respect to surface runoff, transpiration, evaporation, evapotranspiration, and soil water content depends on site conditions (i.e. climate and soil type). For this reason, it is recommended that SVAT model sensitivity analysis be carried out prior to field spectroscopic measurements to account for site specific climate and soil conditions. Nevertheless, mapping of the soil properties estimated via spectroscopy using kriging resulted in poor interpolation (i.e. weak variograms) results as a consequence of a summation of uncertainty arising from the method of field measurement to mapping (i.e. spectroscopic soil prediction, kriging error) and site-specific ‘small-scale’ heterogeneity. The selected soil evaluation method (vis-NIR spectroscopy, structure comparison using image analysis, traditional laboratory analysis) showed that there are significant differences between the bamboo soil and the adjacent secondary forest soil established on the same soil type (Vertisol). Reflecting on the major study results, it can be stated that the selected method combination is a way forward to a more detailed and efficient way to evaluate the suitability of a specific site for reforestation. The results of this study provide insights into where and when during soil and vegetation measurements a high measurement accuracy is required to minimize uncertainties in SVAT modeling. / Umfangreiche Abholzungen, besonders in den (Sub-)Tropen, habe zu intensiver Bodendegradierung und Erosion mit einhergehendem Verlust der Bodenfruchtbarkeit geführt. Eine wirksame Maßnahme zur Vermeidung fortschreitender Bodendegradierung und Erosion sind Aufforstungen auf diesen Flächen, die bisweilen zu einer verbesserten Bodenqualität führen können. Eine Umwandlung von Grünland zu Wald kann jedoch einen entscheidenden Einfluss auf den Wasserhaushalt haben. Selbst unter humid-tropischen Klimabedingungen, wo Wasser in der Regel kein begrenzender Faktor ist, können sich Aufforstungen negativ auf die Wasserverfügbarkeit auswirken. In diesem Zusammenhang muss auch berücksichtigt werden, dass Klimamodelle eine Abnahme der Niederschläge in einigen dieser Regionen prognostizieren. Um die Probleme, die mit dem Klimawandel in Verbindung stehen zu mildern (z.B. Zunahme von Erosion und Dürreperioden), wurden und werden bereits umfangreiche Aufforstungsmaßnahmen durchgeführt. Viele dieser Maßnahmen waren nicht immer umfassend erfolgreich, weil die Umgebungsbedingungen sowie die pflanzenspezifischen Anforderungen nicht angemessen berücksichtigt wurden. Dies liegt häufig an der schlechten Datengrundlage sowie an den in vielen Entwicklungs- und Schwellenländern begrenzter verfügbarer finanzieller Mittel. Aus diesem Grund werden innovative Ansätze benötigt, die in der Lage sind quasi-kontinuierlich und kostengünstig die Standortbedingungen zu erfassen und zu bewerten. Gleichzeitig sollte eine Überwachung der Wiederaufforstungsmaßnahme erfolgen, um deren Erfolg zu bewerten und potentielle negative Effekte (z.B. Wasserknappheit) zu erkennen und diesen entgegenzuwirken bzw. reduzieren zu können. Um zu vermeiden, dass Wiederaufforstungen fehlschlagen oder negative Auswirkungen auf die Ökosystemdienstleistungen haben, ist es entscheidend, Kenntnisse vom tatsächlichen Wasserhaushalt des Ökosystems zu erhalten und Änderungen des Wasserhaushalts durch Wiederaufforstungen vorhersagen zu können. Die Ermittlung und Vorhersage von Wasserhaushaltsänderungen infolge einer Aufforstung unter Berücksichtigung des Klimawandels erfordert die Berücksichtigung komplex-verzahnter Rückkopplungsprozesse im Boden-Vegetations-Atmosphären Kontinuum. Hydrologische Modelle, die explizit den Einfluss der Vegetation auf den Wasserhaushalt untersuchen sind Soil-Vegetation-Atmosphere-Transfer (SVAT) Modelle. Die vorliegende Studie verfolgte zwei Hauptziele: (i) die Entwicklung und Erprobung einer Methodenkombination zur Standortbewertung unter Datenknappheit (d.h. Grundanforderung des Ansatzes) (Teil I) und (ii) die Untersuchung des Einflusses der mit geophysikalischen Methoden vorhergesagten SVAT-Modeleingangsparameter (d.h. Vorhersageunsicherheiten) auf die Modellierung (Teil II). Eine Wasserhaushaltsmodellierung wurde in den Mittelpunkt der Methodenkombination gesetzt. In dieser Studie wurde das 1D SVAT Model CoupModel verwendet. CoupModel benötigen detaillierte räumliche Bodeninformationen (i) zur Modellparametrisierung, (ii) zum Hochskalierung von Modellergebnissen unter Berücksichtigung lokaler und regionaler Bodenheterogenität, und (iii) zur Beobachtung (Monitoring) der zeitlichen Veränderungen des Bodens und der Vegetation. Traditionelle Ansätze zur Messung von Boden- und Vegetationseigenschaften und deren Monitoring sind jedoch zeitaufwendig, teuer und beschränken sich daher oft auf Punktinformationen. Ein vielversprechender Ansatz zur Überwindung der räumlichen Einschränkung sind die Nutzung geophysikalischer Methoden. Aus diesem Grund wurden vis-NIR Spektroskopie (sichtbarer bis nah-infraroter Wellenlängenbereich) zur quasi-kontinuierlichen Messung von physikalischer und chemischer Bodeneigenschaften und Satelliten-basierte Fernerkundung zur Ableitung von Vegetationscharakteristika (d.h. Blattflächenindex (BFI)) eingesetzt. Da die mit geophysikalisch hergeleiteten Bodenparameter (hier Bodenart) und Pflanzenparameter zur Parametrisierung eines SVAT Models verwendet werden können, wurde die gesamte Prozessierungskette und die damit verbundenen Unsicherheiten und deren potentiellen Auswirkungen auf die Wasserhaushaltsmodellierung mit CoupModel untersucht. Ein Gewächshausexperiment mit Bambuspflanzen wurde durchgeführt, um die zur CoupModel Parametrisierung notwendigen pflanzenphysio- logischen Parameter zu bestimmen. Geoelektrik wurde eingesetzt, um die Bodenschichtung der Untersuchungsfläche zu untersuchen und ein repräsentatives Bodenprofil zur Modellierung zu definieren. Die Bodenstruktur wurde unter Verwendung einer Bildanalysetechnik ausgewertet, die die qualitativen Bewertung und Vergleichbarkeit struktureller Merkmale ermöglicht. Um den Anforderungen des gewählten Standortbewertungsansatzes gerecht zu werden, wurde die Methodik auf einem Standort mit einer Bambusplantage und einem Sekundärregenwald (als Referenzfläche) in NO-Brasilien (d.h. geringe Datenverfügbarkeit) entwickelt und getestet. Das Ziel dieser Arbeit war jedoch nicht die Modellierung dieses konkreten Standortes, sondern die Bewertung der Eignung des gewählten Methodenansatzes zur Standortbewertung für Aufforstungen und deren zeitliche Beobachtung, als auch die Bewertung des Einfluss von Aufforstungen auf den Wasserhaushalt und die Bodenqualität. Die Ergebnisse (Teil III) verdeutlichen, dass es notwendig ist, sich den potentiellen Einfluss der Messunsicherheiten der SVAT Modelleingangsparameter auf die Modellierung bewusst zu sein. Beispielsweise zeigte sich, dass die Vorhersageunsicherheiten der Bodentextur und des BFI einen bedeutenden Einfluss auf die Wasserhaushaltsmodellierung mit CoupModel hatte. Die Arbeit zeigt weiterhin, dass vis-NIR Spektroskopie zur schnellen und kostengünstigen Messung, Kartierung und Überwachung boden-physikalischer (Bodenart) und -chemischer (N, TOC, TIC, TC) Eigenschaften geeignet ist. Die Qualität der Bodenvorhersage hängt vom Instrument (z.B. Sensorauflösung), den Probeneigenschaften (z.B. chemische Zusammensetzung) und den Standortmerkmalen (z.B. Klima) ab. Die Sensitivitätsanalyse mit CoupModel zeigte, dass der Einfluss der spektralen Bodenartvorhersageunsicherheiten auf den mit CoupModel simulierten Oberflächenabfluss, Evaporation, Transpiration und Evapotranspiration ebenfalls von den Standortbedingungen (z.B. Klima, Bodentyp) abhängt. Aus diesem Grund wird empfohlen eine SVAT Model Sensitivitätsanalyse vor der spektroskopischen Feldmessung von Bodenparametern durchzuführen, um die Standort-spezifischen Boden- und Klimabedingungen angemessen zu berücksichtigen. Die Anfertigung einer Bodenkarte unter Verwendung von Kriging führte zu schlechten Interpolationsergebnissen in Folge der Aufsummierung von Mess- und Schätzunsicherheiten (d.h. bei spektroskopischer Feldmessung, Kriging-Fehler) und der kleinskaligen Bodenheterogenität. Anhand des gewählten Bodenbewertungsansatzes (vis-NIR Spektroskopie, Strukturvergleich mit Bildanalysetechnik, traditionelle Laboranalysen) konnte gezeigt werden, dass es bei gleichem Bodentyp (Vertisol) signifikante Unterschiede zwischen den Böden unter Bambus und Sekundärwald gibt. Anhand der wichtigsten Ergebnisse kann festgehalten werden, dass die gewählte Methodenkombination zur detailreicheren und effizienteren Standortuntersuchung und -bewertung für Aufforstungen beitragen kann. Die Ergebnisse dieser Studie geben einen Einblick darauf, wo und wann bei Boden- und Vegetationsmessungen eine besonders hohe Messgenauigkeit erforderlich ist, um Unsicherheiten bei der SVAT Modellierung zu minimieren. / Extensos desmatamentos que estão sendo feitos especialmente nos trópicos e sub-trópicos resultam em uma intensa degradação do solo e num aumento da erosão gerando assim uma redução na sua fertilidade. Reflorestamentos ou plantações nestas áreas degradadas podem ser medidas eficazes para atenuar esses problemas e levar a uma melhoria da qualidade do mesmo. No entanto, uma mudança no uso da terra, por exemplo de pastagem para floresta pode ter um impacto crucial no balanço hídrico e isso pode afetar a disponibilidade de água, mesmo sob condições de clima tropical úmido, onde a água normalmente não é um fator limitante. Devemos levar também em consideração que de acordo com projeções de mudanças climáticas, as precipitações em algumas dessas regiões também diminuirão agravando assim, ainda mais o quadro apresentado. Para mitigar esses problemas relacionados com as alterações climáticas, reflorestamentos são frequentemente realizados mas raramente são bem-sucedidos, pois condições ambientais como os requisitos específicos de cada espécie de planta, não são devidamente levados em consideração. Isso é muitas vezes devido, não só pela falta de dados, como também por recursos financeiros limitados, que são problemas comuns em regiões tropicais. Por esses motivos, são necessárias abordagens inovadoras que devam ser capazes de medir as condições ambientais quase continuamente e de maneira rentável. Simultaneamente com o reflorestamento, deve ser feita uma monitoração a fim de avaliar o sucesso da atividade e para prevenir, ou pelo menos, reduzir os problemas potenciais associados com o mesmo (por exemplo, a escassez de água). Para se evitar falhas e reduzir implicações negativas sobre os ecossistemas, é crucial obter percepções sobre o real balanço hídrico e as mudanças que seriam geradas por esse reflorestamento. Por este motivo, esta tese teve como objetivo desenvolver e testar uma combinação de métodos para avaliação de áreas adequadas para reflorestamento. Com esse intuito, foi colocada no centro da abordagem de avaliação a modelagem do balanço hídrico local, que permite a identificação e estimação de possíveis alterações causadas pelo reflorestamento sob mudança climática considerando o sistema complexo de realimentação e a interação de processos do continuum solo-vegetação-atmosfera. Esses modelos hidrológicos que investigam explicitamente a influência da vegetação no equilíbrio da água são conhecidos como modelos Solo-Vegetação-Atmosfera (SVAT). Esta pesquisa focou em dois objetivos principais: (i) desenvolvimento e teste de uma combinação de métodos para avaliação de áreas que sofrem com a escassez de dados (pré-requisito do estudo) (Parte I), e (ii) a investigação das consequências da incerteza nos parâmetros de entrada do modelo SVAT, provenientes de dados geofísicos, para modelagem hídrica (Parte II). A fim de satisfazer esses objetivos, o estudo foi feito no nordeste brasileiro,por representar uma área de grande escassez de dados, utilizando como base uma plantação de bambu e uma área de floresta secundária. Uma modelagem do balanço hídrico foi disposta no centro da metodologia para a avaliação de áreas. Este estudo utilizou o CoupModel que é um modelo SVAT unidimensional e que requer informações espaciais detalhadas do solo para (i) a parametrização do modelo, (ii) aumento da escala dos resultados da modelagem, considerando a heterogeneidade do solo de escala local para regional e (iii) o monitoramento de mudanças nas propriedades do solo e características da vegetação ao longo do tempo. Entretanto, as abordagens tradicionais para amostragem de solo e de vegetação e o monitoramento são demorados e caros e portanto muitas vezes limitadas a informações pontuais. Por esta razão, métodos geofísicos como a espectroscopia visível e infravermelho próximo (vis-NIR) e sensoriamento remoto foram utilizados respectivamente para a medição de propriedades físicas e químicas do solo e para derivar as características da vegetação baseado no índice da área foliar (IAF). Como as propriedades estimadas de solo (principalmente a textura) poderiam ser usadas para parametrizar um modelo SVAT, este estudo investigou toda a cadeia de processamento e as incertezas de previsão relacionadas à textura de solo e ao IAF. Além disso explorou o impacto destas incertezas criadas sobre a previsão do balanço hídrico simulado por CoupModel. O método geoelétrico foi aplicado para investigar a estratificação do solo visando a determinação de um perfil representante. Já a sua estrutura foi explorada usando uma técnica de análise de imagens que permitiu a avaliação quantitativa e a comparabilidade dos aspectos estruturais. Um experimento realizado em uma estufa com plantas de bambu (Bambusa vulgaris) foi criado a fim de determinar as caraterísticas fisiológicas desta espécie que posteriormente seriam utilizadas como parâmetros para o CoupModel. Os resultados do estudo (Parte III) destacam que é preciso estar consciente das incertezas relacionadas à medição de parâmetros de entrada do modelo SVAT. A incerteza presente em alguns parâmetros de entrada como por exemplo, textura de solo e o IAF influencia significantemente a modelagem do balanço hídrico. Mesmo assim, esta pesquisa indica que vis-NIR espectroscopia é um método rápido e economicamente viável para medir, mapear e monitorar as propriedades físicas (textura) e químicas (N, TOC, TIC, TC) do solo. A precisão da previsão dessas propriedades depende do tipo de instrumento (por exemplo da resolução do sensor), da propriedade da amostra (a composição química por exemplo) e das características das condições climáticas da área. Os resultados apontam também que a sensitividade do CoupModel à incerteza da previsão da textura de solo em respeito ao escoamento superficial, transpiração, evaporação, evapotranspiração e ao conteúdo de água no solo depende das condições gerais da área (por exemplo condições climáticas e tipo de solo). Por isso, é recomendado realizar uma análise de sensitividade do modelo SVAT prior a medição espectral do solo no campo, para poder considerar adequadamente as condições especificas do área em relação ao clima e ao solo. Além disso, o mapeamento de propriedades de solo previstas pela espectroscopia usando o kriging, resultou em interpolações de baixa qualidade (variogramas fracos) como consequência da acumulação de incertezas surgidas desde a medição no campo até o seu mapeamento (ou seja, previsão do solo via espectroscopia, erro do kriging) e heterogeneidade especifica de uma pequena escala. Osmétodos selecionados para avaliação das áreas (vis-NIR espectroscopia, comparação da estrutura de solo por meio de análise de imagens, análise de laboratório tradicionais) revelou a existência de diferenças significativas entre o solo sob bambu e o sob floresta secundária, apesar de ambas terem sido estabelecidas no mesmo tipo de solo (vertissolo). Refletindo sobre os principais resultados do estudo, pode-se afirmar que a combinação dos métodos escolhidos e aplicados representam uma forma mais detalhada e eficaz de avaliar se uma determinada área é adequada para ser reflorestada. Os resultados apresentados fornecem percepções sobre onde e quando, durante a medição do solo e da vegetação, é necessário se ter uma precisão mais alta a fim de minimizar incertezas potenciais na modelagem com o modelo SVAT.

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<p>To apply Industry 4.0 technologies and accelerate the modernization of continuous pharmaceutical manufacturing, digital twin (DT) and advanced process control (APC) strategies are indispensable. The DT serves as a virtual representation that mirrors the behavior of the physical process system, enabling real-time monitoring and predictive capabilities. Consequently, this facilitates the feasibility of real-time release testing (RTRT) and enhances drug product development and manufacturing efficiency by reducing the need for extensive sampling and testing. Moreover, APC strategies are required to address variations in raw material properties and process uncertainties while ensuring that desired critical quality attributes (CQAs) of in-process materials and final products are maintained. When deviations from quality targets are detected, APC must provide optimal real-time corrective actions, offering better control performance than the traditional open loop-control method. The progress in DT and APC is beneficial in shifting from the paradigm of Quality-by-Test (QbT) to that of Quality-by-Design (QbD) and Quality-by-Control (QbC), which emphasize the importance of process knowledge and real-time information to ensure product quality.</p> <p><br></p> <p>This study focuses on four key elements and their applications in a continuous dry granulation tableting process, including feeding, blending, roll compaction, ribbon milling and tableting unit operations. Firstly, the necessity of a digital infrastructure for data collection and integration is emphasized. An ISA-95-based hierarchical automation framework is implemented for continuous pharmaceutical manufacturing, with each level serving specific purposes related to production, sensing, process control, manufacturing operations, and business planning. Secondly, investigation of process analytical technology (PAT) tools for real-time measurements is highlighted as a prerequisite for effective real-time process management. For instance, the measurement of mass flow rate, a critical process parameter (CPP) in continuous manufacturing, was previously limited to loss-in-weight (LIW) feeders. To overcome this limitation, a novel capacitance-based mass flow sensor, the ECVT sensor, has been integrated into the continuous direct compaction process to capture real-time powder flow rates downstream of the LIW feeders. Additionally, the use of near-infrared (NIR)-based sensor for real-time measurement of ribbon solid fraction in dry granulation processes is explored. Proper spectra selection and pre-processing techniques are employed to transform the spectra into useful real-time information. Thirdly, the development of quantitative models that establish a link between CPPs and CQAs is addressed, enabling effective product design and process control. Mechanistic models and hybrid models are employed to describe the continuous direct compaction (DC) and dry granulation (DG) processes. Finally, applying APC strategies becomes feasible with the aid of real-time measurements and model predictions. Real-time optimization techniques are used to combine measurements and model predictions to infer unmeasured states or mitigate the impact of measurement noise. In this work, the moving horizon estimation-based nonlinear model predictive control (MHE-NMPC) framework is utilized. It leverages the capabilities of MHE for parameter updates and state estimation to enable adaptive models using data from the past time window. Simultaneously, NMPC ensures satisfactory setpoint tracking and disturbance rejection by minimizing the error between the model predictions and setpoint in the future time window. The MHE-NMPC framework has been implemented in the tableting process and demonstrated satisfactory control performance even when plant model mismatch exists. In addition, the application of MHE enables the sensor fusion framework, where at-line measurements and online measurements can be integrated if the past time window length is sufficient. The sensor fusion framework proves to be beneficial in extending the at-line measurement application from just validation to real-time decision-making.</p>