Este trabalho apresenta o desenvolvimento e a otimização de metodologias analíticas para avaliação da temperatura de transição vítrea (Tg) por DSC e determinação do teor de umidade e cinzas por TG/DTG de amostras de mel. Além disso, foi realizado também um estudo da variabilidade nestes parâmetros físico-químicos e na temperatura de transição vítrea de amostras de méis monoflorais de eucalipto e laranja de algumas regiões do Estado de São Paulo. Para a avaliação termogravimétrica das amostras de mel, inicialmente foi realizado um estudo do comportamento térmico de padrões de carboidratos por TG/DTG, DSC e DTA Os resultados obtidos permitiram diferenciar as etapas de decomposição térmica correspondentes aos açúcares dos demais componentes presentes no mel. A variabilidade nos conteúdos de umidade e cinzas de méis de eucalipto e laranja foram investigadas por planejamento hierárquico e pela análise de variância (ANOVA) e verificou-se que estes parâmetros físico-químicos são significativamente diferentes no nível de 95% de confiança. Para o desenvolvimento e otimização de metodologias analíticas para a determinação do teor de umidade e de cinzas em mel por TG/DTG foram utilizados os métodos oficiais e aplicados planejamentos experimentais e um teste-F para a comparação entre variâncias. Os resultados sugeriram que para a obtenção de conteúdos médios de umidade e cinzas em mel por TG/DTG, similares aos encontrados pelos métodos oficiais, é necessário utilizar cadinho de alumina (150 µL), taxas de aquecimento de 5ºC/min e papel de microfibra de vidro. Além disso, a comparação entre a variabilidade do método termogravimétrico com os métodos oficiais para estas determinações sugeriu que não existem diferenças significativas entre os métodos investigados. Para as amostras de méis monoflorais de laranja e eucalipto foram determinadas temperaturas de transição vítrea médias de -47 e -55ºC, respectivamente sugerindo uma diferença significativa nesta propriedade física para estes tipos de méis. Além disso, entre o conteúdo de umidade e a temperatura de transição vítrea destes tipos de méis foi verificada uma correlação linear negativa significativa no nível de 95% de confiança (r = - 0,916). Assim pode-se dizer, que os parâmetros fisico-químicos umidade e cinzas obtidos pelos métodos oficiais ou pelo método termogravimétrico e a temperatura de transição vítrea determinada por DSC podem ser utilizados para a caracterização da origem floral destes tipos de méis. / This work presents the optimization and development of analytical methodologies for evaluation of glass transition temperature (Tg) by DSC and for moisture and ash content determinations by TG/DTG of honey samples. Beyond this, a study of variability in these physicochemical parameters determined by conventional methods was realized for eucalyptus and citrus monofloral honeys of some regions of São Paulo State. For the thermogravimetric evaluation of honey samples, initially a study of thermal behavior of standard of carbohydrates was carried out by TG/DTG, DSC and DTA The results obtained allowed to distinguish the decomposition steps corresponding to the sugars in relation to other components present in honey. The variabilities in average moisture and ash contents of eucalyptus and citrus monofloral honeys were investigated by a hierarchical design and by an analysis of variance (ANOVA). These physicochemical parameters are significantly different at the 95% confidence level. For the development and optimization of analytical methodologies for moisture and ash contents in honey by TG/DTG conventional methods, experimental designs and a F-test for the comparison between variances were utilized. The results suggest that to get average moisture and ash contents in honey by TG/DTG similar to those found by conventional methods an alumine crucible (150 µL ), heating rates of 5ºC/min and microfiber glass paper should be used. Besides this, the comparison between the thermogravimetric method and the conventional ones for these determinations suggest that there are no significant differences between the methods investigated. For eucalyptus and citrus monofloral honeys average glass transition temperatures of -47 and -55ºC, respectively, were determined suggesting a significant difference in this physical property for these honey types. Besides this, a significant negative linear correlation at 95% confidence level (r = - 0.916) was verified between the moisture contents and glass transition temperatures of these honey types. So, it may be said that the physicochemical parameters, moisture and ash, obtained by conventional and thermogravimetric methods and the glass transition temperature determined by DSC can be utilized for the characterization of the floral origin of these types of honey.

Content: Sheepskin, a by-product of the meat industry, is then often processed to leather, primarily for the clothing industry. Where the tanneries are distant from the abattoirs and freezing works, the raw skins have to be transported long distances to be processed. In warm weather, there is the potential for putrefaction of the skins which then have to be disposed of at a cost. Depilation, the first step of leather processing, is designed to remove the wool from the skin without damaging it. Conventional depilation involves the use of strong alkali and sulfides, that are harmful to both the environment and the personnel carrying out the process due to the potential production of hydrogen sulfide, a toxic, flammable gas. To solve this problem, scientists have been looking to depilate skins using enzymes as these are environmentally friendly. Various enzymes, such as collagenase, keratinase, protease and lipase have been shown to be able to remove hair from skin, but unfortunately usually damage it. Furthermore, at present, they are not cost effective at an industrial level. We have found a simple solution, a derivative of a dairy by-product, that prevents putrefaction, preserving the skin for days at room temperature. In addition, it allows easy removal of the wool from the skin. Scanning electron microscopy showed there was no obvious damage to the surface of the depilated skin and that the wool is cleanly removed from the hair follicle. To assess any less visible damage that may have occurred as a result of soaking the skin, biochemical analyses were carried out to measure the changes to the amino acid composition, collagen crosslinks and proteoglycan concentrations of the depilated skins. Sheepskin depilated with this method was processed to leather and its physical properties such as tear, and tensile strength analysed. Culture dependent methods were used to isolate the microorganisms present in the solution after depilation, showed that only four main species were consistently found in the depilation fluid and on the skins. Metagenomic analysis, confirmed these findings and was used to follow the changes in the microbiome during the course of depilation. This presentation will describe the progress that has been made to understand the science behind these observations and compare the properties of skins depilated using this method with those depilated using the traditional beamhouse process. Take-Away: We are using a natural product to depilate sheepskin. The sheepskin is also preserved while depilation. Microscopy, chemical analyses, physical tests, and metagenomics analysis were done to understand the process.

The diploma thesis is focused on the determination of basic nutritional properties of 26 samples of ground pepper from different countries and evaluates, whether the chemical composition of ground pepper is affected by the geographical origin. The amount of 19 nutritional properties were determined by advanced analytical methodes (ICP-OES, HPLC DAD, HPLC ELSD) together with other laboratory techniques. Final results were statistically processed by the methods of analysis of variance (ANOVA), cluster analysis, principal component analysis (PCA) and discriminant analysis (DA). Statistical evaluation confirmed, that the chemical composition is affected by the geographical origin. Analysis of variance (ANOVA) determined 14 parameters to statistically differ (p

Kenaf (Hibiscus cannabinus L.) is a highly productive crop that is cultivated worldwide for its fibre content which may be used to produce various commodities. The kenaf crop was commercially cultivated in South Africa in the 1950’s, but production was discontinued from the 1960’s up to the mid 2000’s. Production commenced again and kenaf emreged as a “new” fibre crop with the first kenaf processing factory in the country going into production in 2006 in KwaZulu-Natal. Due to the importance of kenaf in manufacturing of various commodities, there was a need to investigate the agronomic practices thereof to ensure sustainable yield. Therefore a two year study (2008/09 and 2009/10 summers) was conducted in Pretoria to investigate the influence of nitrogen, plant population, row spacing and water treatments on kenaf growth, yield, chemical quality and microscopic analysis of the fibre. In total, four field trials were conducted at the Hatfield Experimental Farm of the University of Pretoria. In 2008/09 a trial was conducted to investigate effects of plant population (200,000; 300,000 and 400,000 plants ha-1), nitrogen level (0, 50, 100 and 150 kg ha-1) and row spacing (0.17, 0.34 and 0.50 m) under rainfed conditions. Sampling for growth parameters were done at 85, 113 and 126 days after planting (DAP). The biomass and chemical analysis of bark fibre were conducted only at or after the final harvest, at 126 DAP. In general, no clear effect of different treatment was observed on either parameter studied. During 2009/10 three experiments were conducted. The first two had the same nitrogen levels as in the previous season, but were grown either under rainfed or irrigated conditions. The nitrogen was applied as two dressings of 0 and 50 kg ha-1 at planting and 0, 50 and 100 kg ha-1 at thinning (35 DAP). The third experiment investigated combinations of plant population (main plots) and row spacing (sub plots) under rainfed conditions. Due to increasing stem yield with increasing plant population during 2008/09, the lowest population of 200,000 plants ha-1 was left out and 500,000 and 600,000 plants ha-1 were added. The same three row spacings as in 2008/09 were used. Nitrogen was applied at 150 kg ha-1, with 50 kg ha-1 at planting and 100 kg ha-1 at thinning. Growth and biomass parameters, water use efficiency (WUE) (nitrogen trial only) were subsequently measured up to the end of the growth cycle. The chemical characteristics of bark fibre and nutrient removal (nitrogen trial only), nutrient use efficiency as well as the nitrogen contents of leaves and stems were determined only once at final harvest. The number of fibre rings and fibre bundles were assessed only once during the growth cycle. Growth and biomass parameters, WUE and both nutrient removal and nutrient use efficiency generally tended to increase with increase in nitrogen level under both rainfed and irrigated conditions. On the other hand, increasing plant population tended to result in a decrease in all growth parameters, while it increased biomass yield per hectare. Finally, the effect of row spacing was inconsistent for the same parameter from one sampling to another one, and from one parameter to another. The chemical characteristics of bark fibre showed inconsistent responses to all agronomic practices. The number of fibre rings and fibre bundles increased with increasing nitrogen level, decreased as plant population increased, but did not show clear trends with regard to row spacing. In general the plants grown under irrigated conditions performed better than those grown under rainfed conditions. The results of this study revealed that under the environmental conditions of Pretoria, nitrogen levels above 100 kg ha-1 applied in two dressings should result in best plant performance, but most benefit could be obtained under irrigated conditions. A plant population of 500,000 plants ha-1 or higher and row spacing wider than 0.34 m proved to be most suitable for both growth and biomass parameters. / Dissertation (MScAgric)--University of Pretoria, 2015. / tm2015 / Plant Production and Soil Science / MScAgric / Unrestricted

京都大学 / 0048 / 新制・課程博士 / 博士(社会健康医学) / 甲第19968号 / 社医博第73号 / 新制||社医||9(附属図書館) / 33064 / 京都大学大学院医学研究科社会健康医学系専攻 / (主査)教授 木原 正博, 教授 松原 和夫, 教授 中山 健夫 / 学位規則第4条第1項該当 / Doctor of Public Health / Kyoto University / DFAM

The Fremont tradition developed on the northern Colorado Plateau and eastern Great Basin between A.D. 1 and A.D. 1350 (Talbot 2000a). Research on exotics in the Fremont area, specifically turquoise and Olivella shell, has been sporadic until recently (Hughes and Bennyhoff 1986; McDonald 1994; Janetski 2002). In this thesis, I present new data on Olivella and turquoise artifacts found throughout the Fremont region, including the Parowan Valley sites, Nephi Mounds, and Kay's Cabin, as well as a spatial distribution of Olivella and turquoise in the Fremont area. I performed microprobe analysis on blue-green artifacts from Kay's Cabin and found most are turquoise, although other minerals including variscite, azurite, malachite, and possibly chrysocolla are also present. Also, various experimental methods were used to chemically characterize a turquoise artifact from Parowan Valley (see Appendix A). I analyzed over 350 Olivella artifacts (see Appendix B) and examined modern Olivella shells; therefore, I provide a discussion of the details and differences between the O. biplicata and O. dama species. Through testing Janetski's (2002) trade fair model, I readdress the question of whether or not Olivella and turquoise were distributed across the Fremont region via directional or down-the-line exchange. My research supports Janetski's model and shows that Fremont exotic exchange moved directionally, with Olivella and turquoise artifacts concentrated at central sites on the Fremont landscape. I also explore the possibility that the exchange of Olivella and turquoise to the Fremont area was conducted through different networks. It appears, based on high numbers of turquoise at certain sites and high frequencies of Olivella artifacts at other sites, that these ornaments were not traded together. I examine whether exotic artifacts were differentially distributed among sites in Parowan Valley and within the specific sites and I observed that Olivella and turquoise are most often associated with living areas.

Identification of osseous materials is generally established on gross anatomical factors; however, highly fragmented or taphonomically altered materials are often problematic and alternative methods, such as biological, histological, or chemical analysis, must be utilized. Recently, chemical methods have been proposed to sort unknown materials according to their Ca/P ratios. Ubelaker and colleagues (2002) proposed using SEM/EDX to achieve this distinction and Christensen and colleagues (2012) have validated X-ray Fluorescence Spectrometry (XRF) for this application. An alternative method of analysis involves performing principal component analysis (PCA) on element spectra to classify unknown materials based on their trace element composition. Zimmerman (2013) proposed the validity of this method with data obtained using hand held XRF. Subsequently, performing PCA on elemental data obtained using SEM/EDX demonstrates potential for material differentiation. Elemental weight percent data were collected using SEM/EDX then processed in R, version 3.0.1, by the R Foundation for Statistical Computing using PCA and Fisher Linear Discriminant Analysis. A two-tiered analysis was undertaken to improve discrimination between sample groups. The first tier involved distinguishing between osseous and non-osseous materials. After outliers were removed overall correct classification was 98.02% with one of 1504 osseous and 39 of 520 non-osseous spectra misclassifying. Since forty spectra were collected for each sample, the single misclassifying spectra would not affect the overall classification of the sample, resulting in 100% correct classification with a 0% error rate for the osseous samples. The second tier assessed differentiation of human and non-human osseous materials but demonstrated a poor correct classification rate of 72.41%. Finally, a blind study was conducted using 20 samples to assess the applicability for using this method to classify unknown materials as osseous or non-osseous. All of the samples were correctly classified resulting in 100% correct classification, further demonstrating the efficiency of SEM/EDX and statistical analysis for differentiation of osseous and non-osseous materials. Due to its high specificity, small sample requirements, and relative non-destructive testing protocol, as well as its presence in most modern crime laboratories, SEM/EDX has been proposed as a laboratory method for chemical differentiation of osseous and non-osseous materials. Additionally, the proposed method does not require advanced training or knowledge of analytical chemistry as the SEM/EDX provides clear results that can be processed using publically available statistical analysis software. By assessing and improving chemical analysis methodologies used for material differentiation, forensic anthropologists might be able to identify osseous and non-osseous samples as a preemptive step in forensic investigations involving fragmentary and taphonomically modified materials, reducing time and cost investments spent on forensically insignificant samples.

Natural nanominerals are abundant in Earth's critical zone and important in innumerable environmental processes that affect water quality. The chemical behavior of many natural nanominerals is related to their extreme small size (<10 nm) and high surface area. Atomic structural and chemical heterogeneity are also important factors affecting nanoparticle reactivity, and are a consequence of the mechanisms and complex (natural) conditions by which they form. The relationships between these factors remain poorly understood and limit our ability to predict the formation, transformation, and chemical behavior of natural nanominerals in the environment. We are using a poorly crystalline ferric hydroxysulfate nanomineral, schwertmannite, as a model system to understand the effect of formation conditions, specifically solution chemistry, on its physico-chemical characteristics. Previous studies indicate schwertmannite has highly variable bulk sulfate (Fe/S molar from 3-15) and water contents (Caraballo et al., 2013). In addition, both natural and synthetic schwertmannites have recently been described as "polyphasic" (i.e., consisting of sulfate-poor, goethite-like ordered domains embedded in a sulfate-rich, amorphous material) from observations using transmission electron microscopy (French et al., 2012). We hypothesize that solution chemistry at the time of schwertmannite formation directly affect its composition and structure. Using a factorial experiment design, we investigated the effects of increasing solution sulfate concentration ([SO4]/[Fe] at 1, 2, 3 and 5) and pH (2.4-5.6) on the crystallinity and composition of the products. Ferric hydroxide and hydroxysulfate solids were precipitated in batches by the rapid oxidation of Fe(II) by hydrogen peroxide, similar to what is seen in natural environmental systems. Sulfate and hydroxide concentrations were varied by addition of NaSO4 and NaOH, respectively. Solids were characterized using synchrotron X-ray diffraction (XRD), thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), inductively coupled plasma-mass spectrometry (ICP-MS), scanning electron microscopy (SEM), and high resolution- transmission electron microscopy (HR-TEM). Our results show that schwertmannite is the only precipitate formed at low pH and that goethite rapidly becomes dominant at pH > 3.5. High-resolution TEM showed our synthetic schwertmannite samples consist of poorly crystalline goethite-like nanodomains within an amorphous solid, similarly seen in previous results. ICP-MS results reveal a narrow Fe/S molar ratio of 4.5 ±0.1 for our synthetic schwertmannite, which suggests that schwertmannite chemical composition does not depend strongly on pH or initial solution sulfate concentration. Increasing pH from 2.4 to 3.2 also has little effect on the crystallinity, bulk Fe/S ratio and water contents of schwertmannite. Increasing solution [SO4]/[Fe] also has little to no impact on crystallinity, water content or the amount of sulfate incorporated in schwertmannite. Thus, schwertmannite crystallinity and composition is not affected by initial solution sulfate and concentration under our experimental conditions. Thermal analysis allows us to independently measure OH and SO4 content in synthetic schwertmannite. In doing so, we propose a more accurate chemical formula (Fe8Oz(OH)24-2z-2x(SO4)x). The average stoichiometry based on thermal analysis of schwertmannite precipitated at [SO4]/[Fe] = 1 and pH ranging from ~2.4 2.9 is Fe8O6.51(OH)8.4(SO4)1.28. Interestingly, the calculated number of moles of oxygen is less than 8, which suggests that the standard formula Fe8O8(OH)8-2x(SO4)x is incorrect. These results for synthetic samples provide important constraints for future studies aimed at better understanding the formation, compositional variability and chemical behavior of natural schwertmannite. / Master of Science

<p> A textural and mineralogical study of the magnetite, hemoilmenite and minor sulfide phases of the Whitestone anorthosite, Dunchurch, Ontario, was carried out. The composition of magnetite and hemo-ilmenite was determined by chemical analysis, X-ray diffraction and electron probe microanalysis. A modification of the solvus shape in the hematite-ilmenite system consistent with the composition of hemo-ilmenite lamellae, as well as a mechanism for formation of metamorphic magnetite porphyroblasts from ferrianilmenite is proposed. Buddington and Lindsley's experimental data cannot be used directly to obtain f02 and T of formation of the anorthosite because compositions fall in the highly oxidizing and as yet undetermined portion of their diagram. </p> / Thesis / Master of Science (MSc)

Microelectromechanical systems (MEMS) technology allows the realization of mechanical parts, sensors, actuators and electronics on silicon substrate. An attractive utilization of MEMS is to develop micro instruments for chemical analysis. An example is gas chromatography (GC) which is widely used in food, environmental, pharmaceutical, petroleum/refining, forensic/security, and flavors and fragrances industries. A MEMS-based micro GC (µGC) provides capabilities for quantitative analysis of complex chemical mixtures in the field with very short analysis time and small amounts of consumables. The aim of this research effort is to enhance the sensitivity and selectivity of µGC instruments by implementing chemical amplification method known as preconcentration. A micro preconcentrator (µPC) extracts the target analytes from the sample matrix, concentrates them, and injects them into the separation column for analysis. This work resulted in the development of silicon-glass bonded chips consisting of 7 mm x 7 mm x 0.38 mm multiport cavity with thousands of embedded 3D microstructures (to achieve high surface-to-volume ratio) coated with polymeric thin film adsorbents. Deep reactive ion etching (DRIE) was the enabling technology for the realization of µPCs. Several coating methods, such as inkjet printing of polymers and polymer precipitation from solution have been utilized to coat complex geometrical structures. One major outcome was the development of cobweb adsorbent structure. Moreover, the porous polymeric adsorbent Tenax TA in the film form was characterized, for the first time, for μPC application and shown to have similar properties to that of the granular form. Several μPC designs were experimentally evaluated for their performance in concentrating volatile organic compounds, including cancer biomarkers, Propofol (anesthetic agent), environmental pollutants, and chemical warfare simulants. The possibility of utilizing the μPCs in practical applications such breath analysis was also demonstrated. / Ph. D.