Chemical characteristics and Kraft pulping of tension wood from Eucalyptus globulus labill

Tension (TW) and opposite wood (OW) of Eucalyptus globulus trees were analyzed for its chemical characteristics and Kraft pulp production. Lignin content was 16% lower and contained 32% more syringyl units in TW than in OW. The increase in syringyl units favoured the formation of β-O-4 bonds that was also higher in TW than in OW (84% vs. 64%, respectively). The effect of these wood features was evaluated in the production of Kraft pulps from both types of wood. At kappa number 16, Kraft pulps obtained from TW demanded less active alkali in delignification and presented slightly higher or similar pulp yield than pulps made with OW. Fiber length, coarseness and intrinsic viscosity were also higher in tension than in opposite pulps. When pulps where refined to 30°SR, TW pulps needed 18% more revolutions in the PFI mill to achieve the same beating degree than OW pulps. Strength properties (tensile, tear and burst indexes) were slightly higher or similar in tension as compared with opposite wood pulps. After an OD0(EO)D1 bleaching sequence, both pulps achieved up to 89% ISO brightness. Bleached pulps from TW presented higher viscosity and low amount of hexenuronic acids than pulps from OW. Results showed that TW presented high xylans and low lignin content that caused a decrease in alkali consumption, increase pulp strength properties and similar bleaching performance as compared with pulps from OW.

Chemical Biology Screen for Prostate Cancer Therapeutics

Prostate cancer initially responds to hormone-based therapeutics such as anti-androgen treatment or chemotherapeutics but eventually becomes resistant. Novel treatment options are therefore urgently needed. This thesis study applied a high-throughput screen of 4910 known drugs and drug-like small molecules to identify compounds that selectively inhibit growth of prostate cancer cells. In addition, the mechanisms underlying the cellular sensitivity to potent cancer selective compounds were addressed. Surprisingly, many of the compounds currently used in the clinics or studied in clinical trials were not cancer-selective. Only four drugs, aldehyde dehydrogenase inhibitor disulfiram (Antabus), antibiotic ionophore monensin, histone deacetylase inhibitor tricostatin A and fungicide thiram inhibited prostate cancer cell growth at nanomolar concentrations without major effects on non-malignant prostate epithelial cells. Disulfiram, monensin and a structurally similar compound to monensin, salinomycin, induced oxidative stress and inhibited aldehyde dehydrogenase activity. Moreover, monensin and salinomycin reduced androgen receptor signalling and steroidogenesis, enforced cell differentiation and reduced the overall levels of cancer stem cells. Taken together, novel and potentially prostate cancer-selective therapeutic agents were identified in this study, including the description of a multitude of intoxicating mechanisms such as those relating to oxidative stress. The results provide novel insights into prostate cancer biology and exemplify useful means of considering novel approaches to cancer treatment.

SOIL COVER AND CHEMICAL AND PHYSICAL ATTRIBUTES IN OXISOL IN THE ATLANTIC FOREST BIOME

ABSTRACT The objective of this study was to evaluate the chemical and physical attributes of different soil cover in a Oxisol with a strong wavy relief in the Atlantic Forest Biome, in which were selected three watersheds, employed with grazing (watershed P), forest (watershed M) and coffee (watershed C). Deformed and not deformed samples were collected in three depths for physical and chemical characterization. The chemical characteristics of soil in different watershed studies presented low levels of fertility. It was observed an elevation of pH in the soil and contents of Ca2+ and Mg2+ in the watersheds P and C in relation to the watershed M. Due to deforestation and the establishment of agriculture and livestock, there was a decrease in the contents of soil organic matter in the watershed P and C, not altering the physical characteristics of the soil in the watershed P. The implementation of coffee plantation is causing a reduction in the soil quality of watershed C in comparison to the watershed P and M, therefore indicating a need to adequate soil management in this area.

COMPARISON OF PROCEDURES FOR IMMEDIATE CHEMICAL ANALYSIS OF CHARCOAL

ABSTRACT The climate change, the quest for sustainability and the strong environmental pressures for alternatives to traditional fossil fuels have increased the interest in the search and use of renewable energy sources. Among them stands out the biomass of charcoal coming from renewable forests, widely used as a thermal reductant in the steel industry in the detriment of the use of mineral coal coke. This study aimed to compare different operating procedures of immediate chemical analysis of charcoal. Seven essays to immediate chemical analysis were compared, spread between procedures performed by Brazilian companies and laboratories, the test described by NBR 8112 and one realized with a thermogravimetric analyzer (TGA) using the parameters of the NBR 8112. There were significant differences in the volatiles matter content and consequently in the fixed carbon contents found. The differences between the procedures and the NBR 8112 were caused by an excess burning time, a mass sample above or below the standard or inappropriate container used for burning. It observed that the TGA appraisal of the volatiles content must be carried out with a burning time equal to 2 minutes to obtain results similar to those of the NBR 8112 norm. Moreover, the ash content values were statistically identical and the particles size did not influence the differences between means.

Surface chemistry of fibres and vessel elements in chemical and recycled pulps

Den viktigaste råvaran i papperstillverkning är pappersmassa. Massan innehåller (ved)fibrer men också finmaterial och andra typers (ved)celler, så som kärlceller. Hur dessa komponenter beter sig under arkformationen i pappersmaskinen eller hur de bidrar till egenskaperna hos det färdiga pappret avgörs till stor del av massakomponenternas ytkemiska sammansättning, fysiska struktur och mängden joniserbara grupper på ytan. I denna avhandling studerades ytegenskaperna hos fraktionerade kemiska massor och returfibermassor med avancerade analystekniker. Rester av avfärgningskemikalier identifierades på både returfibrer och på kärlceller. Dessa kan påverka arkformationen och arkstyrkan på returfiberpapper. Kärlcellernas cellväggsstruktur visade sig skilja sig från fibrernas. Resultaten kan främja utvecklingen av returfiberprosessen och användningen av kärlcellsrika lövvedsmassor.

Performance during post-harvest storage of banana cv. 'prata', 'maçã' and 'nanica' exposed to physical and chemical treatments

Banana is the most consumed fruit in the world and Brazil is the second largest producer. Despite its global position, Brazil has an average of 40% losses during the post-harvest period. So, this experiment aimed at evaluating the efficiency of post-harvest treatments to improve the storage of banana cultivars cv. 'Prata', 'Maçã' and 'Nanica'. The fruits were acquired at CEASA with green peel, and were submitted to six different treatments: T- immersion in drinking water for 3 minutes (control), H3 - hot water (50 °C for 3 minutes), H8 - hot water (50 °C for 8 minutes), HP - immersion in hypochlorite 0.2% for 3 minutes, OS - immersion in soybean oil 10% for 3 minutes, and OM - immersion in mineral oil 10% for 3 minutes. The fruits were stored at room temperature at about 21 °C for 14 days and evaluated in three periods (1, 7 and 14 days) comparing peel color, flesh/peel ratio, titratable acidity (TA), soluble solids (SS), SS/TA ratio, and pH. The fruits of cv. 'Prata' and 'Maçã' submitted to the treatments H3, H8 and HP ripened at the same time as the control for peel color, which showed increased soluble solids, flesh/peel ratio, acidity and a decrease in pH. On the other hand, the cv. 'Nanica' did not respond significantly different when compared to the applied treatments and the control. The fruits treated with OM and OS were kept green for a longer time for the cultivars 'Prata' and 'Nanica', but there were some changes on peel color due dark spots in 'Prata' banana and a softening aspect in 'Nanica', indicating some level of toxicity of these treatments. Fruits of the 'Maçã' cultivar continued green with the application of mineral oil, without toxicity symptoms. In conclusion, the treatments applied did not show any advantage for storage of these fruits.

Physical, chemical and microbiological properties of a Dystrophic Yellow Latosol using manipueira

The study aimed to evaluate chemical, microbiological and hydro-physical changes of a Dystrophic Yellow Latosol, receiver of different levels of manipueira (cassava wastewater) application, in the cultivation of 'Terra Maranhão' banana. The experimental design was a randomized block with three replications in a factorial scheme 3 x 4, in which it was considered three soil depths and four levels of manipueira. It was evaluated the weighted mean diameter of the aggregate, the percentage of aggregation at different periods, soil density, particle density, porosity and soil saturated hydraulic conductivity, in addition to pH of P (mg dm -3), K (mg dm-3), Ca (cmolc dm-3), Mg (cmolc dm-3), Ca+Mg (cmolc dm-3), Al (cmolc dm-3), Na (cmolc dm -3), H+Al (cmolc dm-3), CEC (cmolc dm-3), V%, OM (g kg-1), soil microbial biomass (Ug Cg-1 dry soil), acid phosphatase (Ug PNP g-1 h-1). The use of manipueira influenced some physical characteristic of the soil, but it was not possible to specify the effect of increasing application dosage. Therefore, the application did not affect the biological indicators assessed in the soil or its pH. The use of manipueira as a fertilizer in the doses used in this study showed low increase of K, P, H+Al and Al in the soil and a good increase of Mg, Ca and Ca+Mg, Na, CEC and V%.

Tabular cusum control charts of chemical variables applied to the control of surface water quality

The aim of this study was to evaluate the application possibility of tabular CUSUM control charts in the quality control of chemical variables in surface water. It was performed bibliographic and field research to collect water samples from 2003 to 2009, totaling 30 samples, some monthly and others semi-annual in order to observe the variables that regulate water quality. It was found that these charts may be applied to control the quality of river water; showing to be effective in the perception of changes during the process, especially for small samples (n=1) which there is no repetition as in this research. It was also concluded that the Mandurim River does not presents significant levels of pollution.

Management zones definition using soil chemical and physical attributes in a soybean area

Several equipments and methodologies have been developed to make available precision agriculture, especially considering the high cost of its implantation and sampling. An interesting possibility is to define management zones aim at dividing producing areas in smaller management zones that could be treated differently, serving as a source of recommendation and analysis. Thus, this trial used physical and chemical properties of soil and yield aiming at the generation of management zones in order to identify whether they can be used as recommendation and analysis. Management zones were generated by the Fuzzy C-Means algorithm and their evaluation was performed by calculating the reduction of variance and performing means tests. The division of the area into two management zones was considered appropriate for the present distinct averages of most soil properties and yield. The used methodology allowed the generation of management zones that can serve as source of recommendation and soil analysis; despite the relative efficiency has shown a reduced variance for all attributes in divisions in the three sub-regions, the ANOVA did not show significative differences among the management zones.

Physical-chemical characterization and wet milling yield of four maize hybrids

The influence of physical-chemical characteristics of maize grains and lactic acid concentrations on byproduct yields, generated by conventional wet milling, was studied during steeping, for four maize hybrids and two lactic acid concentrations (0.55 and 1.00%). For physical-chemical characterization, grain dimensions (length, thickness, and width) were determined, as well as mass of 100 grains, percentage of floating grains, volumetric mass, and centesimal composition. Statistical differences were found for percentage of floating grains (2.33 to 24.67%), volumetric mass (0.814 to 0.850 kg.L-1), mass of 100 grains (0.033 to 0.037 kg), water content (11.86 to 12.20%), proteins (8.21 to 9.06%), lipids (3.00 to 4.77%), and ashes (1.07 to 1.26%). There were no relationships of wet milling yields with maize appearance and physical-chemical characteristics. The addition of 1.00% lactic acid did not statistically improve byproduct yields; however, it favored separation of the grain components.

Chemical attributes of soil and dry mass accumulation of maize fertilized with cassava wastewater

The aim of this study was to evaluate chemical attributes alterations of a clay-loam textured soil and dry mass accumulation of maize submitted to application of cassava wastewater doses in three assessment periods. The experiment was conducted under greenhouse using a completely randomized experimental design in a factorial 5 × 3, with four replicates. The analyzed factors of research were doses of cassava wastewater (0; 12.6; 25.2; 50.4; 75.6 m3 ha-1) andassessment periods (20, 40 and 52 days after germination). The following parameters were determined: electric conductivity of soil saturation extract, pH in water, content of available P, content of exchangeable K+, Ca2+, Mg2+ and Na+of soil, dry mass of leaves and stem. The application of cassava wastewater on soil enables increase of pH, electric conductivity of saturation extract, contents of available P, contents of exchangeable K+ and Na+ and dry mass of leaves and stem. However, only pH and content of exchangeable K+ of soil, the electric conductivity of saturation extract and dry mass of leaves and stem are influenced by assessment period.

Spatial influence of physical and chemical parameters on management zone definition in apple orchards

ABSTRACT Precision agriculture adoption in Brazilian apple orchards is still incipient. This study aimed at evaluating the spatial variability of certain soil properties as soil density, soil penetration resistance, electrical conductivity, yield, and fruit quality in an apple orchard through digital mapping, as well as assessing the correlation between these factors by means of geostatistics, establishing management zones. Forty representative points were set within 2.5 hectares of apple orchard, wherein soil samples were collected and analyzed, besides measurements of fruit quality (Brix degree, size or diameter, pulp firmness and color) to generate an overall index quality. We concluded that the fruit quality indexes, when isolated, did not show strong spatial dependence, unlike the index of fruit quality (FQI), derived from a combination of these parameters, allowing orchard planning according to management zones based on quality.

Fractionation of Hen Egg and Oat Lipids with supercritical Fluids Chemical and functional Properties of Fractions

Hen eggs and oats (Avena Sativa) are important materials for the food industry. Today, instead of merely satisfying the feeling of hunger, consumers are asking for healthier, biologically active and environmentally friendly products. The growing awareness of consumers’ increasing demands presents a great challenge to the food industry to develop more sustainable products and utilise modern and effective techniques. The modification of yolk fatty acid composition by means of feed supplements is well understood. Egg yolk phospholipids are polar lipids and are used in several applications including food, cosmetics, pharmaceuticals, and special nutrients. Egg yolk phospholipids are excellent emulsifiers, typically sold as mixtures of phospholipids, triacylglycerols, and cholesterol. However, highly purified and characterised phospholipids are needed in several sophisticated applications. Industrial fractionation of phospholipids is usually based on organic solvents. With these fractionation techniques, some harmful residues of organic solvents may cause problems in further processing. The objective of the present study was to investigate the methods to improve the functional properties of eggs, to develop techniques to isolate the fractions responsible for the specific functional properties of egg yolk lipids, and to apply the developed techniques to plant-based materials, too. Fractionation techniques based on supercritical fluids were utilised for the separation of the lipid fractions of eggs and oats. The chemical and functional characterisation of the fractions were performed, and the produced oat polar lipid fractions were tested as protective barrier in encapsulation processes. Modifying the fatty acid compositions of egg yolks with different types of oil supplements in feed had no affect on their functional or sensory properties. Based on the results of functional and sensory analysis, it is evident that eggs with modified fatty acid compositions are usable in several industrial applications. These applications include liquid egg yolk products used in mayonnaise and salad dressings. Egg yolk powders were utilised in different kinds of fractionation processes. The precipitation method developed in this study resembles the supercritical anti-solvent method, which is typically used in the pharmaceutical industry. With pilot scale supercritical fluid processes, non-polar lipids and polar lipids were successfully separated from commercially produced egg yolk powder and oat flakes. The egg and oat-based polar lipid fractions showed high purities, and the corresponding delipidated fractions produced using supercritical techniques offer interesting starting materials for the further production of bioactive compounds. The oat polar lipid fraction contained especially digalactosyadiacylglycerol, which was shown to have valuable functional properties in the encapsulation of probiotics.

Element speciation and behaviour in metal-rich Boreal river and estuarine systems using ultrafiltration and chemical modelling

The bioavailability of metals and their potential for environmental pollution depends not simply on total concentrations, but is to a great extent determined by their chemical form. Consequently, knowledge of aqueous metal species is essential in investigating potential metal toxicity and mobility. The overall aim of this thesis is, thus, to determine the species of major and trace elements and the size distribution among the different forms (e.g. ions, molecules and mineral particles) in selected metal-enriched Boreal river and estuarine systems by utilising filtration techniques and geochemical modelling. On the basis of the spatial physicochemical patterns found, the fractionation and complexation processes of elements (mainly related to input of humic matter and pH-change) were examined. Dissolved (<1 kDa), colloidal (1 kDa-0.45 μm) and particulate (>0.45 μm) size fractions of sulfate, organic carbon (OC) and 44 metals/metalloids were investigated in the extremely acidic Vörå River system and its estuary in W Finland, and in four river systems in SW Finland (Sirppujoki, Laajoki, Mynäjoki and Paimionjoki), largely affected by soil erosion and acid sulfate (AS) soils. In addition, geochemical modelling was used to predict the formation of free ions and complexes in these investigated waters. One of the most important findings of this study is that the very large amounts of metals known to be released from AS soils (including Al, Ca, Cd, Co, Cu, Mg, Mn, Na, Ni, Si, U and the lanthanoids) occur and can prevail mainly in toxic forms throughout acidic river systems; as free ions and/or sulfate-complexes. This has serious effects on the biota and especially dissolved Al is expected to have acute effects on fish and other organisms, but also other potentially toxic dissolved elements (e.g. Cd, Cu, Mn and Ni) can have fatal effects on the biota in these environments. In upstream areas that are generally relatively forested (higher pH and contents of OC) fewer bioavailable elements (including Al, Cu, Ni and U) may be found due to complexation with the more abundantly occurring colloidal OC. In the rivers in SW Finland total metal concentrations were relatively high, but most of the elements occurred largely in a colloidal or particulate form and even elements expected to be very soluble (Ca, K, Mg, Na and Sr) occurred to a large extent in colloidal form. According to geochemical modelling, these patterns may only to a limited extent be explained by in-stream metal complexation/adsorption. Instead there were strong indications that the high metal concentrations and dominant solid fractions were largely caused by erosion of metal bearing phyllosilicates. A strong influence of AS soils, known to exist in the catchment, could be clearly distinguished in the Sirppujoki River as it had very high concentrations of a metal sequence typical of AS soils in a dissolved form (Ba, Br, Ca, Cd, Co, K, Mg, Mn, Na, Ni, Rb and Sr). In the Paimionjoki River, metal concentrations (including Ba, Cs, Fe, Hf, Pb, Rb, Si, Th, Ti, Tl and V; not typical of AS soils in the area) were high, but it was found that the main cause of this was erosion of metal bearing phyllosilicates and thus these metals occurred dominantly in less toxic colloidal and particulate fractions. In the two nearby rivers (Laajoki and Mynäjoki) there was influence of AS soils, but it was largely masked by eroded phyllosilicates. Consequently, rivers draining clay plains sensitive to erosion, like those in SW Finland, have generally high background metal concentrations due to erosion. Thus, relying on only semi-dissolved (<0.45 μm) concentrations obtained in routine monitoring, or geochemical modelling based on such data, can lead to a great overestimation of the water toxicity in this environment. The potentially toxic elements that are of concern in AS soil areas will ultimately be precipitated in the recipient estuary or sea, where the acidic metalrich river water will gradually be diluted/neutralised with brackish seawater. Along such a rising pH gradient Al, Cu and U will precipitate first together with organic matter closest to the river mouth. Manganese is relatively persistent in solution and, thus, precipitates further down the estuary as Mn oxides together with elements such as Ba, Cd, Co, Cu and Ni. Iron oxides, on the contrary, are not important scavengers of metals in the estuary, they are predicted to be associated only with As and PO4.

Self-Assessment Report for International Accreditation - Chemical Engineering

Kemiantekniikan kandidaatin ja diplomi-insinöörin tutkinto-ohjelmien itsearviointiraportissa käsitellään tutkinto-ohjelmien osaamistavoitteita ja niiden saavuttamista. Raportissa käydään läpi myös käytössä olevat resurssit sekä tutkinto-ohjelmiin liittyviä tunnuslukuja. Itsearviointi on toteutettu kansainvälisen akkreditointijärjestön kriteerien mukaisesti (ASIIN ja EUR-ACE).