Non-destructive optical characterization of fruits in the red and near infrared.

Increasing attention is being paid to the possible development of non-invasive tests for the assessment of the quality of Fruits. We propose a novel non-destructive method for the measurement of the internal optical properties of fruits and vegetables by means of lime-resolved reflectance spectroscopy in the visible and NIR range. A Fully automated instrumentation for time-resolved reflectance measurements was developed. It is based on mode-locked laser sources and electronics for time-correlated single photon counting, and provides a time-resolution of 120-160 ps. The system was used to probe the optical properties of several species and varieties of Fruits and vegetables in the red and NIR range (650-1000 nm). In most Fruits, the absorption line shape is dominated by the absorption peak of water, centred around 970 nm. Generally, the absorption spectra also show the spectral features typical of chlorophyll, with maximum at 675 nm. In particular, for what concerns apples, variations in peak intensity are observed depending on the variety, the degree of ripeness as well as the position on the apple. For all the species and varieties considered, the transport scattering coefficient decreases progressively upon increasing the wavelength.

Optical detection of mealiness in apples using laser TDRS.

Mealiness is a textural attribute related to an internal fruit disorder that involves quality loss. It is characterised by the combination of abnormal softness of the fruit and absence of free juiciness in the mouth when eaten by the consumer. Recent research concluded with the development of precise instrumental procedure to measure a scale of mealiness based on the combination of several rheological properties and empirical magnitudes. In this line, time-domain laser reflectance spectroscopy (TDRS) is a new medical technology, used to characterise the optical properties of tissues, and to locate affected areas like tumours. Among its advantages compared to more traditional spectroscopic techniques, there is the feasibility to asses simultaneously and independently two optical parameters: the absorption of the light inside the irradiated body, and the scattering of the photons across the tissues, at each wavelength, generating two coefficients (µa, absorption coeff.; and µ's, transport scattering coeff.). If it is assumed that they are related respectively to chemical components and to physical properties of the sample, TDRS can be applied to the quantification of chemicals and the measurement of the rheological properties (i.e. mealiness estimation) at the same time. Using VIS & NIR lasers as light sources, TDRS was applied in this work to Golden Delicious and Cox apples (n=90), conforming several batches of untreated samples and storage-treated (20°C & 95%RH) to promote the development of mealiness. The collected database was clustered into different groups according to their instrumental test values (Barreiro et al, 1998). The optical coefficients were used as explanatory variables when building discriminant analysis functions for mealiness, achieving a classification score above 80% of correctly identified mealy versus fresh apples.

Detection of internal quality in kiwi with a new optical technique (TDRS)

A compact system based on time-resolved diffuse reflectance spectroscopy (TDRS) has been developed to measure internal fruit quality parameters and has been applied to the non-destructive estimation of firmness, sugar content and acidity of kiwifruits. This new optical technique, developed in medical applications and related areas, provides a complete optical characterisation of a diffusive sample as it estimates at the same time and independently the light absorption inside the tissues and the scattering across them. The working principle of the technique is the analysis of the attenuation and broadening of the time-distribution of the remitted light, and the correct interpretation with a proper theoretical model. This main advantage compared to conventional optical techniques (which are only able to register the global attenuation spectrum) added to the compact, portable prototype developed along a three-year work opens the possibilities of this new measurement method in the food industry.

Detección óptica de harinosidad en manzana mediante una nueva técnica láser.

Mealiness, a textural disorder that produces quality loss, combines softness and absence of juiciness. The only one (destructive) test to measure it, combines information from a mechanical test on fruit probes to classify the samples according to instrumental mealiness. Time-domain laser reflectance spectroscopy (TDRS) is able to assess simultaneously and independently the absorption of the light inside the irradiated body (µa coefficient) and the scattering of the photons across the tissues (µS, transport scattering coeff.) measured at each wavelength. Using VIS&NIR lasers as light sources, TDRS was applied to Golden Delicious and Cox apples (n=90), conforming batches of untreated samples and storage-treated (20°C&95%RH) to induce mealiness development. The collected database was clustered into different groups according to their instrumental mealiness. Optical variables were used to build discriminant functions, achieving classification scores 75-89% of correctly identified mealy apples.

Relationship among slurry characteristics and gaseous emissions at different types of commercial Spanish pig farms

This study aimed to analyse several factors of variation of slurry composition and to establish prediction equations for potential methane (CH4) and ammonia (NH3) emissions. Seventy-nine feed and slurry samples were collected at two seasons (summer and winter) from commercial pig farms sited at two Spanish regions (Centre and Mediterranean). Nursery, growing-fattening, gestating and lactating facilities were sampled. Feed and slurry composition were determined, and potential CH4 and NH3 emissions measured at laboratory. Feed nutrient contents were used as covariates in the analysis. Near infrared reflectance spectroscopy (NIRS) was evaluated as a predicting tool for slurry composition and potential gaseous emissions. A wide variability was found both in feed and slurry composition. Mediterranean farms had a higher pH (p<0.001) and ash (p=0.02) concentration than those located at the Centre of Spain. Also, type of farm affected ether extract content of the slurry (p=0.02), with highest values obtained for the youngest animal facilities. Results suggested a buffer effect of dietary fibre on slurry pH and a direct relationship (p<0.05) with fibre constituents of manure. Dietary protein content did not affect slurry nitrogen content but decreased (p=0.003) total and volatile solids concentration. Prediction models of potential NH3 emissions (R2=0.89) and CH4 yield (R2=0.61) were obtained from slurry composition. Predictions from NIRS showed a high accuracy for most slurry constituents (R2>0.90) and similar accuracy of prediction of potential NH3 and CH4 emissions (R2=0.84 and 0.68, respectively) to models using slurry characteristics, which can be of interest to estimate emissions from commercial farms and establish mitigation strategies or optimize biogas production.

Ammonia and methane gas emissions from pig slurry: variability induced through feeding strategies

Esta Tesis doctoral fue desarrollada para estudiar las emisiones de amoniaco (NH3) y metano (CH4) en purines de cerdos, y los efectos ocasionados por cambios en la formulación de la dieta. Con este propósito, fueron llevados a cabo tres estudios. El experimento 1 fue realizado con el objetivo de analizar los factores de variación de la composición de purines y establecer ecuaciones de predicción para emisiones potenciales de NH3 y CH4. Fueron recogidas setenta y nueve muestras de piensos y purines durante dos estaciones del año (verano y invierno) de granjas comerciales situadas en dos regiones de España (Centro y Mediterráneo). Se muestrearon granjas de gestación, maternidad, lactación y cebo. Se determinó la composición de piensos y purines, y la emisión potencial de NH3 y CH4. El contenido de nutrientes de los piensos fue usado como covariable en el análisis. La espectroscopia de reflectancia del infrarrojo cercano (NIRS) se evaluó como herramienta de predicción de la composición y potencial emisión de gases del purín. Se encontró una amplia variabilidad en la composición de piensos y purines. Las granjas del Mediterráneo tenían mayor pH (P<0,001) y concentración de cenizas (P =0,02) en el purín que las del Centro. El tipo de granja también afectó al contenido de extracto etéreo (EE) del purín (P =0,02), observando los valores más elevados en las instalaciones de animales jóvenes. Los resultados sugieren un efecto tampón de la fibra de la dieta en el pH del purín y una relación directa (P<0,05) con el contenido de fibra fecal. El contenido de proteína del pienso no afectó al contenido de nitrógeno del purín, pero disminuyó (P=0,003) la concentración de sólidos totales (ST) y de sólidos volátiles (SV). Se obtuvieron modelos de predicción de la emisión potencial de NH3 (R2=0,89) y CH4 (R2=0,61) partir de la composición del purín. Los espectros NIRS mostraron una buena precisión para la estimación de la mayor parte de los constituyentes, con coeficientes de determinación de validación cruzada (R2cv) superiores a 0,90, así como para la predicción del potencial de emisiones de NH3 y CH4 (R2cv=0,84 y 0,68, respectivamente). El experimento 2 fue realizado para investigar los efectos del nivel de inclusión de dos fuentes de sub-productos fibrosos: pulpa de naranja (PN) y pulpa de algarroba (PA), en dietas iso-fibrosas de cerdos de cebo, sobre la composición del purín y las emisiones potenciales de NH3 y CH4. Treinta cerdos (85,4±12,3 kg) fueron alimentados con cinco dietas iso-nutritivas: control comercial trigo/cebada (C) y cuatro dietas experimentales incluyendo las dos fuentes de sub-productos a dos niveles (75 y 150 g/kg) en una estructura 2 × 2 factorial. Después de 14 días de periodo de adaptación, heces y orina fueron recogidas separadamente durante 7 días para medir la digestibilidad de los nutrientes y el nitrógeno (N) excretado (6 réplicas por dieta) en cerdos alojados individualmente en jaulas metabólicas. Las emisiones de NH3 y CH4 fueron medidas después de la recogida de los purínes durante 11 y 100 días respectivamente. La fuente y el nivel de subproductos fibrosos afectó a la eficiencia digestiva de diferentes formas, ya que los coeficientes de digestibilidad total aparente (CDTA) para la materia seca (MS), materia orgánica (MO), fracciones fibrosas y energía bruta (EB) aumentaron con la PN pero disminuyeron con la inclusión de PA (P<0,05). El CDTA de proteína bruta (PB) disminuyó con la inclusión de las dos fuentes de fibra, siendo más bajo al mayor nivel de inclusión. La concentración fecal de fracciones fibrosas aumentó (P<0,05) con el nivel de inclusión de PA pero disminuyó con el de PN (P<0,01). El nivel más alto de las dos fuentes de fibra en el pienso aumentó (P<0,02) el contenido de PB fecal pero disminuyó el contenido de N de la orina (de 205 para 168 g/kg MS, P<0,05) en todas las dietas suplementadas comparadas con la dieta C. Adicionalmente, las proporciones de nitrógeno indigerido, nitrógeno soluble en agua, nitrógeno bacteriano y endógeno excretado en heces no fueron afectados por los tratamientos. Las características iniciales del purín no difirieron entre las diferentes fuentes y niveles de fibra, excepto para el pH que disminuyó con la inclusión de altos niveles de sub-productos. La emisión de NH3 por kg de purín fue más baja en todas las dietas suplementadas con fibras que en la dieta C (2,44 vs.1,81g de promedio, P<0,05). Además, purines de dietas suplementadas con alto nivel de sub-productos tendieron (P<0,06) a emitir menos NH3 por kg de nitrógeno total y mostraron un potencial más bajo para emitir CH4, independientemente de la fuente de fibra. El experimento 3 investigó los efectos de la fuente de proteína en dietas prácticas. Tres piensos experimentales fueron diseñados para sustituir una mescla de harina y cascarilla de soja (SOJ) por harina de girasol (GIR) o por DDGS del trigo (DDGST). La proporción de otros ingredientes fue modificada para mantener los contenidos de nutrientes similares a través de las dietas. El cambio en la fuente de proteína dio lugar a diferencias en el contenido de fibra neutro detergente ligada a proteína bruta (FNDPB), fibra soluble (FS) y lignina ácido detergente (LAD) en la dieta. Veinticuatro cerdos (ocho por dieta), con 52,3 o 60,8 kg en la primera y segunda tanda respectivamente, fueron alojados individualmente en jaulas metabólicas. Durante un periodo de 7 días fue determinado el balance de MS, el CDTA de los nutrientes y la composición de heces y orina. Se realizó el mismo procedimiento del experimento 2 para medir las emisiones de NH3 y CH4 de los purines de cada animal. Ni la ingestión de MS ni el CDTA de la MS o de la energía fueron diferentes entre las dietas experimentales, pero el tipo de pienso afectó (P<0.001) la digestibilidad de la PB, que fue mayor para GIR (0,846) que para SOJ (0,775), mientras que la dieta DDGST mostró un valor intermedio (0,794). La concentración fecal de PB fue por tanto influenciada (P<0,001) por el tratamiento, observándose la menor concentración de PB en la dieta GIR y la mayor en la dieta SOJ. La proporción de N excretado en orina o heces disminuyó de 1,63 en la dieta GIR hasta 0,650 en la dieta SOJ, como consecuencia de perdidas más bajas en orina y más altas en heces, con todas las fracciones de nitrógeno fecales creciendo en paralelo a la excreción total. Este resultado fue paralelo a una disminución de la emisión potencial de NH3 (g/kg purín) en la dieta SOJ con respecto a la dieta GIR (desde 1,82 a 1,12, P<0,05), dando valores intermedios (1,58) para los purines de la dieta DDGST. Por otro lado, el CDTA de la FS y de la fibra neutro detergente (FND) fueron afectados (P<0,001 y 0,002, respectivamente) por el tipo de dieta, siendo más bajas en la dieta GIR que en la dieta SOJ; además, se observó un contenido más alto de FND (491 vs. 361g/kg) en la MS fecal para la dieta GIR que en la dieta SOJ, presentando la dieta DDGST valores intermedios. El grado de lignificación de la FND (FAD/FND x 100) de las heces disminuyó en el orden GIR>DDGST>SOJ (desde 0,171 hasta 0,109 y 0,086, respectivamente) en paralelo a la disminución del potencial de emisión de CH4 por g de SV del purín (desde 301 a 269 y 256 mL, respectivamente). Todos los purines obtenidos en estos tres experimentos y Antezana et al. (2015) fueron usados para desarrollar nuevas calibraciones con la tecnología NIRS, para predecir la composición del purín y el potencial de las emisiones de gases. Se observó una buena precisión (R2cv superior a 0,92) de las calibraciones cuando muestras de los ensayos controlados (2, 3 y Antezana et al., 2015) fueron añadidas, aumentando el rango de variación. Una menor exactitud fue observada para TAN y emisiones de NH3 y CH4, lo que podría explicarse por una menor homogeneidad en la distribución de las muestras cuando se amplía el rango de variación del estudio. ABSTRACT This PhD thesis was developed to study the emissions of ammonia (NH3) and methane (CH4) from pig slurry and the effects caused by changes on diet formulation. For these proposes three studies were conducted. Experiment 1 aimed to analyse several factors of variation of slurry composition and to establish prediction equations for potential CH4 and NH3 emissions. Seventy-nine feed and slurry samples were collected at two seasons (summer and winter) from commercial pig farms sited at two Spanish regions (Centre and Mediterranean). Nursery, growing-fattening, gestating and lactating facilities were sampled. Feed and slurry composition were determined, and potential CH4 and NH3 emissions measured. Feed nutrient contents were used as covariates in the analysis. Near infrared reflectance spectroscopy (NIRS) was evaluated as a predicting tool for slurry composition and potential gaseous emissions. A wide variability was found both in feed and slurry composition. Mediterranean farms had a higher pH (P<0.001) and ash (P=0.02) concentration than those located at the centre of Spain. Also, type of farm affected ether extract (EE) content of the slurry (P=0.02), with highest values obtained for the youngest animal facilities. Results suggested a buffer effect of dietary fibre on slurry pH and a direct relationship (P<0.05) with fibre constituents of manure. Dietary protein content did not affect slurry nitrogen content (N) but decreased (P=0.003) in total solid (TS) and volatile solids (VS) concentration. Prediction models of potential NH3 emissions (R2=0.89) and biochemical CH4 potential (B0) (R2=0.61) were obtained from slurry composition. Predictions from NIRS showed a high accuracy for most slurry constituents with coefficient of determination of cross validation (R2cv) above 0.90 and a similar accuracy of prediction of potential NH3 and CH4 emissions (R2cv=0.84 and 0.68, respectively) thus models based on slurry composition from commercial farms. Experiment 2 was conducted to investigate the effects of increasing the level of two sources of fibrous by-products, orange pulp (OP) and carob meal (CM), in iso-fibrous diets for growing-finishing pig, slurry composition and potential NH3 and CH4 emissions. Thirty pigs (85.4±12.3 kg) were fed five iso-nutritive diets: a commercial control wheat/barley (C) and four experimental diets including two sources of fibrous by-products OP and CM and two dietary levels (75 and 150 g/kg) in a 2 × 2 factorial arrangement. After a 14-day adaptation period, faeces and urine were collected separately for 7 days to measure nutrient digestibility and the excretory patterns of N from pigs (6 replicates per diet) housed individually in metabolic pens. For each animal, the derived NH3 and CH4 emissions were measured in samples of slurry over an 11 and 100-day storage periods, respectively. Source and level of the fibrous by-products affected digestion efficiency in a different way as the coefficients of total tract apparent digestibility (CTTAD) for dry matter (DM), organic matter (OM), fibre fractions and gross energy (GE) increased with OP but decreased with CM (P<0.05). Crude protein CTTAD decreased with the inclusion of both sources of fibre, being lower at the highest dietary level. Faecal concentration of fibre fractions increased (P<0.05) with the level of inclusion of CM but decreased with that of OP (P<0.01). High dietary level for both sources of fibre increased (P<0.02) CP faecal content but urine N content decreased (from 205 to 168 g/kg DM, P<0.05) in all the fibre-supplemented compared to C diet. Additionally, the proportions of undigested dietary, water soluble, and bacterial and endogenous debris of faecal N excretion were not affected by treatments. The initial slurry characteristics did not differ among different fibre sources and dietary levels, except pH, which decreased at the highest by-product inclusion levels. Ammonia emission per kg of slurry was lower in all the fibre-supplemented diets than in C diet (2.44 vs. 1.81g as average, P<0.05). Additionally, slurries from the highest dietary level of by-products tended (P<0.06) to emit less NH3 per kg of initial total Kjeldahl nitrogen (TKN) and showed a lower biochemical CH4 potential , independently of the fibre source. Experiment 3 investigated the effects of protein source in practical diets. Three experimental feeds were designed to substitute a mixture of soybean meal and soybean hulls (SB diet) with sunflower meal (SFM) or wheat DDGS (WDDGS). The proportion of other ingredients was also modified in order to maintain similar nutrient contents across diets. Changes in protein source led to differences in dietary content of neutral detergent insoluble crude protein (NDICP), soluble fibre (SF) and acid detergent lignin (ADL). Twenty-four pigs (eight per diet), weighing 52.3 or 60.8 kg at the first and second batch respectively, were housed individually in metabolic pens to determine during a 7-day period DM balance, CTTAD of nutrients, and faecal and urine composition. Representative slurry samples from each animal were used to measure NH3 and CH4 emissions over an 11 and or 100-day storage period, respectively. Neither DM intake, nor DM or energy CTTAD differed among experimental diets, but type of feed affected (P<0.001) CP digestibility, which was highest for SFM (0.846) than for SB (0.775) diet, with WDDGS-based diet giving an intermediate value (0.794). Faecal DM composition was influenced (P<0.001) accordingly, with the lowest CP concentration found for diet SFM and the highest for SB. The ratio of N excreted in urine or faeces decreased from SFM (1.63) to SB diet (0.650), as a consequence of both lower urine and higher faecal losses, with all the faecal N fractions increasing in parallel to total excretion. This result was parallel to a decrease of potential NH3 emission (g/kg slurry) in diet SB with respect to diet SFM (from 1.82 to 1.12, P<0.05), giving slurry from WDDGS-based diet an intermediate value (1.58). Otherwise, SF and insoluble neutral detergent fibre (NDF) CTTAD were affected (P<0.001 and P=0.002, respectively) by type of diet, being lower for SFM than in SB-diet; besides, a higher content of NDF (491 vs. 361 g/kg) in faecal DM was observed for SFM with respect to SB based diet, with WDDGS diet being intermediate. Degree of lignification of NDF (ADL/NDF x 100) of faeces decreased in the order SFM>WDDGS>SB (from 0.171 to 0.109 and 0.086, respectively) in parallel to a decrease of biochemical CH4 potential per g of VS of slurry (from 301 to 269 and 256 ml, respectively). All slurry samples obtained from these three experiments and Antezana et al. (2015) were used to develop new calibrations with NIRS technology, to predict the slurry composition and potential gaseous emissions of samples with greater variability in comparison to experiment 1. Better accuracy (R2cv above 0.92) was observed for calibrations when samples from controlled trials experiments (2, 3 and Antezana et al., 2015) were included, increasing the range of variation. A lower accuracy was observed for TAN, NH3 and CH4 gaseous emissions, which might be explained by the less homogeneous distribution with a wider range of data.

Application of remote sensing and GIS in mineral resource mapping - An overview

Remote sensing, as a direct adjunct to field, lithologic and structural mapping, and more recently, GIS have played an important role in the study of mineralized areas. A review on the application of remote sensing in mineral resource mapping is attempted here. It involves understanding the application of remote sensing in lithologic, structural and alteration mapping. Remote sensing becomes an important tool for locating mineral deposits, in its own right, when the primary and secondary processes of mineralization result in the formation of spectral anomalies. Reconnaissance lithologic mapping is usually the first step of mineral resource mapping. This is complimented with structural mapping, as mineral deposits usually occur along or adjacent to geologic structures, and alteration mapping, as mineral deposits are commonly associated with hydrothermal alteration of the surrounding rocks. In addition to these, understanding the use of hyperspectral remote sensing is crucial as hyperspectral data can help identify and thematically map regions of exploration interest by using the distinct absorption features of most minerals. Finally coming to the exploration stage, GIS forms the perfect tool in integrating and analyzing various georeferenced geoscience data in selecting the best sites of mineral deposits or rather good candidates for further exploration.

Genetic and environmentally derived variation in the cell wall composition of miscanthus and implications for thermo-chemical conversion

Fifteen Miscanthus genotypes grown in five locations across Europe were analysed to investigate the influence of genetic and environmental factors on cell wall composition. Chemometric techniques combining near infrared reflectance spectroscopy and conventional chemical analyses were used to construct calibration models for determination of acid detergent lignin, acid detergent fibre, and neutral detergent fibre from sample spectra. The developed equations were shown to predict cell wall components with a good degree of accuracy and significant genetic and environmental variation was identified. The influence of nitrogen and potassium fertiliser on the dry matter yield and cell wall composition of M. x giganteus was investigated. A detrimental affect on feedstock quality was observed to result from application of these inputs which resulted in an overall reduction in concentrations of cell wall components and increased accumulation of ash within the biomass. Pyrolysis-gas chromatography-mass spectrometry and thermo-gravimetric analysis indicates that genotypes other than the commercially cultivated M. x giganteus have potential for use in energy conversion processes and in the bio-refining. The yields and quality parameters of the pyrolysis liquids produced from Miscanthus compared favourably with that produced from SRC willow and produced a more stable pyrolysis liquid with a higher lower heating value. Overall, genotype had a more significant effect on cell wall composition than environment. This indicates good potential for dissection of this trait by QTL analysis and also for plant breeding to produce new genotypes with improved feedstock characteristics for energy conversion.

Effect of extrusion and photo-oxidation on polyethylene/clay nanocomposites

Polyethylene (a 1:1 blend of m-LLDPE and z-LLDPE) double layer silicate clay nanocomposites were prepared by melt extrusion using a twin screw extruder. Maleic anhydride grafted polyethylene (PEgMA) was used as a compatibiliser to enhance the dispersion of two organically modified monmorilonite clays (OMMT): Closite 15A (CL15) and nanofill SE 3000 (NF), and natural montmorillonite (NaMMT). The clay dispersion and morphology obtained in the extruded nanocomposite samples were fully characterised both after processing and during photo-oxidation by a number of complementary analytical techniques. The effects of the compatibiliser, the organoclay modifier (quartenary alkyl ammonium surfactant) and the clays on the behaviour of the nanocomposites during processing and under accelerated weathering conditions were investigated. X-ray diffraction, transmission electron microscopy (TEM), scanning electron microscopy (SEM), rheometry and attenuated reflectance spectroscopy (ATR-FTIR) showed that the nanocomposite structure obtained is dependent on the type of clay used, the presence or absence of a compatibiliser and the environment the samples are exposed to. The results revealed that during processing PE/clay nanocomposites are formed in the presence of the compatibiliser PEgMA giving a hybrid exfoliated and intercalated structures, while microcomposites were obtained in the absence of PEgMA; the unmodified NaMMT-containing samples showed encapsulated clay structures with limited extent of dispersion in the polymer matrix. The effect of processing on the thermal stability of the OMMT-containing polymer samples was determined by measuring the additional amount of vinyl-type unsaturation formed due to a Hoffman elimination reaction that takes place in the alkyl ammonium surfactant of the modified clay at elevated temperatures. The results indicate that OMMT is responsible for the higher levels of unsaturation found in OMMT-PE samples when compared to both the polymer control and the NaMMT-PE samples and confirms the instability of the alkyl ammonium surfactant during melt processing and its deleterious effects on the durability aspects of nanocomposite products. The photostability of the PE/clay nanocomposites under accelerated weathering conditions was monitored by following changes in their infrared signatures and mechanical properties. The rate of photo-oxidation of the compatibilised PE/PEgMA/OMMT nanocomposites was much higher than that of the PE/OMMT (in absence of PEgMA) counterparts, the polymer controls and the PE–NaMMT sample. Several factors have been observed that can explain the difference in the photo-oxidative stability of the PE/clay nanocomposites including the adverse role played by the thermal decomposition products of the alkyl ammonium surfactant, the photo-instability of PEgMA, unfavourable interactions between PEgMA and products formed in the polymer as a consequence of the degradation of the surfactant on the clay, as well as a contribution from a much higher extent of exfoliated structures, determined by TEM, formed with increasing UV-exposure times.

Genotypic and environmentally derived variation in the cell wall composition of Miscanthus in relation to its use as a biomass feedstock

Fifteen Miscanthus genotypes grown in five locations across Europe were analysed to investigate the influence of genetic and environmental factors on cell wall composition. Chemometric techniques combining near infrared reflectance spectroscopy (NIRS) and conventional chemical analyses were used to construct calibration models for determination of acid detergent lignin (ADL), acid detergent fibre (ADF), and neutral detergent fibre (NDF) from sample spectra. Results generated were subsequently converted to lignin, cellulose and hemicellulose content and used to assess the genetic and environmental variation in cell wall composition of Miscanthus and to identify genotypes which display quality traits suitable for exploitation in a range of energy conversion systems. The NIRS calibration models developed were found to predict concentrations with a good degree of accuracy based on the coefficient of determination (R2), standard error of calibration (SEC), and standard error of cross-validation (SECV) values. Across all sites mean lignin, cellulose and hemicellulose values in the winter harvest ranged from 76–115 g kg-1, 412–529 g kg-1, and 235–338 g kg-1 respectively. Overall, of the 15 genotypes Miscanthus x giganteus and Miscanthus sacchariflorus contained higher lignin and cellulose concentrations in the winter harvest. The degree of observed genotypic variation in cell wall composition indicates good potential for plant breeding and matching feedstocks to be optimised to different energy conversion processes.

Size-controlled TiO2 nanoparticles on porous hosts for enhanced photocatalytic hydrogen production

Nanocystalline TiO2 particles were successfully synthesized on porous hosts (SBA-15 and ZSM-15) via a sol-gel impregnation method. Resulting nanocomposites were characterized by XRD, TEM, BET surface analysis, Raman and UV-vis diffuse reflectance spectroscopy, and their photocatalytic activity for H2 production evaluated. XRD evidences the formation of anatase nanoparticles over both ZSM-5 and SBA-15 porous supports, with TEM highlighting a strong particle size dependence on titania precursor concentration. Photocatalytic activities of TiO2/ZSM-5 and TiO2/SBA-15 composites were significantly enhanced compared to pure TiO2, owing to the smaller TiO2 particle size and higher surface area of the former. TiO2 loadings over the porous supports and concomitant photocatalytic hydrogen production were optimized with respect to light absorption, available surface reaction sites and particle size. 10%TiO2/ZSM-5 and 20%TiO2/SBA-15 proved the most active photocatalysts, exhibiting extraordinary hydrogen evolution rates of 10,000 and 8800μmolgTiO2 -1 h-1 under full arc, associated with high external quantum efficiencies of 12.6% and 5.4% respectively under 365nm irradiation.

Template-free and eco-friendly synthesis of hierarchical Ag3PO4 microcrystals with sharp corners and edges for enhanced photocatalytic activity under visible light

Herein, we demonstrate a template-free and eco-friendly strategy to synthesize hierarchical Ag3PO4 microcrystals with sharp corners and edges via silver–ammine complex at room temperature. The as-synthesized hierarchical Ag3PO4 microcrystals were characterized by X-ray diffraction, field-emission scanning electron microscope (FESEM), UV–vis diffuse reflectance spectroscopy (UV–vis DRS), BET surface area analyzer, and photoluminescence analysis (PL). Our results clearly indicated that the as-synthesized Ag3PO4 microcrystals possess a hierarchical structure with sharp corners and edges. More attractively, the adsorption ability and visible light photocatalytic activity of the as-synthesized hierarchical Ag3PO4 is much higher than that of conventional Ag3PO4.

Caracterização e avaliação da atividade fotocatalítica de catalisadores baseados no TiO2, sintetizados mediante hidrólise em uma mistura de solventes

This study involved the synthesis of photocatalysts based on titanium dioxide (TiO2). The photocatalysts were synthesized by the sol-gel method using three different proportions of acetone (25%, 50% and 75% v/v) in water/acetone mixtures, in order to control the hydrolysis of the precursor of titanium (titanium tetraisopropoxide). Aiming to investigate the structural, morphological and electronic changes provoked by the use of the solvent mixtures, different methodologies were used to characterize the oxides, such as X-ray diffraction (XRD), RAMAN spectroscopy, UV-Vis diffuse reflectance spectroscopy, and measurements of specific surface area (BET). XRD combined to RAMAN analyses revealed that the products are two-phase highly crystalline oxides involving anatase as main phase and brookite. Besides, the refined XRD using the method of Rietveld demonstrated that the presence of acetone during the synthesis influenced in the composition of the crystalline phases, increasing the proportion of the brookite phase between 13 and 22%. The band gap energy of these oxides practically did not suffer changes as function of the synthesis conditions. As shown by the isotherm, these photocatalysts are mesoporous materials with mean diameter of pores of 7 nm and approximately 20% of porosity. The surface area of the oxides prepared by hydrolysis in presence of acetone was 12% higher compared to the bare oxide. After characterized, these oxides had their photocatalytic activities evaluated by photodegradation of the azo dyes Ponceau 4R (P4R), Tartrazine (TTZ) and Reactive Red 120 (RR120), and also by the ability to mediate the photocatalytic production of hydrogen. Using the most efficient photocatalyst, the mineralization achieved for the dyes P4R, RR120 and TTZ was of respectively 83%, 79% and 56% in 120 minutes of reaction, while the discoloration of P4R e RR120 reached 100% and 94% for TTZ. In addition, the same photocatalyst in the presence of 0.5% w/w of Platinum and suspended in a 5:1 v/v water/methanol mixture, produced 56 mmol of gaseous hydrogen in five hours of experiment, corresponding to a specific rate of hydrogen production of 139.5 mmol h-1 g-1.

Preparation, Characterization, and Photocatalytic Applications of MWCNTs/TiO2 Composite

The multiwall carbon nanotubes (MWCNTs)/titanium dioxide (P25) composite in different ratios was prepared using simple evaporation and drying process. The composite was characterized by Raman spectroscopy, X-ray diffraction (XRD), UV-visible diffuse reflectance spectroscopy, and scanning electron microscopy (SEM). The photocatalytic activity of this composite was investigated using degradation of the Bismarck brown R dye (BBR). An optimal MWCNTs/TiO2 ratio of 0.5% (w/w) was found to achieve the maximum rate of BBR degradation. It was observed that the composite exhibits enhanced photocatalytic activity compared with TiO2. The enhancement in photocatalytic activity performance of the MWCNTs/P25 composite is explained in terms of recombination of photogenerated electron-hole pairs. In addition, MWCNTs act as a dispersing support to control the morphology of TiO2 particles in the MWCNTs/TiO2 composite.

The fingerprinting of the materials used in portuguese illuminated manuscripts: origin, production and specificities of the 16th century Anttiphonary paints from the Biblioteca Pública de Évora

This thesis focuses on the characterization of materials utilized within the illuminations of Codex 116c of Manizola, a large 16th century antiphonal housed in the Biblioteca Pública de Évora (BPE). Using various spectroscopic techniques (XRF, FTIR, Raman and SEM-EDS), a selection of illuminations were analyzed for pigment and binder identification. The manuscript was further analyzed using fiber optic reflectance spectroscopy (FORS), a non-invasive and portable analysis method ideal for use in illuminations. Using historical documentation and results gained from more extensive analysis of the manuscript, a collection of reference paint samples were created to be analyzed using this method. These samples serve as a reference not only to assist in the identification of pigments used within the manuscript, but also for future studies on similar materials allowing for a better understanding of manuscript production during the 16th century; RESUMO: O presente trabalho é dedicado à caracterização dos materiais utilizados na produção das iluminuras do Codex 116c da Manziola do espólio da Biblioteca Pública de Évora (BPE). Trata-se de um antifonário de grandes dimensões produzido no séc XVI que deverá ter pertencido à Livraria de São Bento de Cástris. A identificação dos materiais utilizados na produção das iluminuras pode ser feita através de análises científicas. No entanto, alguns dos componentes das tintas utilizadas, especialmente os pigmentos orgânicos (lacas) e algumas misturas, apresentam obstáculos à sua identificação por métodos não invasivos. Através de várias técnicas espectroscópicas (XRF, FTIR, Raman e SEM-EDS), foi analisado um conjunto representativo de iluminuras, de modo a identificar os pigmentos e os ligantes presentes nas tintas. O manuscrito foi também analisado por FORS, um método portátil e não invasivo, ideal para a análise de iluminuras. Com base em documentos históricos e nos resultados analíticos, foi criado um conjunto de amostras de referência para ser analisado com FORS. Com esta abordagem, pretende-se que estas amostras, especialmente as de lacas, sirvam de referência não só na identificação dos pigmentos no manuscrito como em estudos sobre materiais semelhantes, contribuindo para um conhecimento mais aprofundado sobre a produção de manuscritos no séc XVI.