Potentiometric and conductimetric studies of chemical equilibria for pyridoxine hydrochloride in aqueous solutions: simple experimental determination of pKa values and analytical applications to pharmaceutical analysis

The combination of two low-cost classical procedures based on titrimetric techniques is presented for the determination of pyridoxine hydrochloride in pharmaceuticals samples. Initially some experiments were carried out aiming to determine both pKa1 and pKa2 values, being those compared to values of literature and theoretical procedures. Commercial samples containing pyridoxine hydrochloride were electrochemically analysed by exploiting their acid-base and precipitation reactions. Potentiometric titrations accomplished the reaction between the ionizable hydrogens present in pyridoxine hydrochloride, being NaOH used as titrant; while the conductimetric method was based on the chemical precipitation between the chloride of pyridoxine hydrochloride molecule and Ag+ ions from de silver nitrate, changing the conductivity of the solution. Both methods were applied to the same commercial samples leading to concordant results when compared by statistical tests (95 and 98% confidence levels). Recoveries ranging from 99.0 to 108.1% were observed, showing no significant interference on the results.

Development of chemical looping combustion process

Chemical looping combustion (CLC) provides a promising technology to help cut carbon dioxide emissions. CLC is based on separated oxidation and reduction processes. Oxygen carrier, which is made from metal and supporting material, is in continuous recirculation between the air and fuel reactors. The CLC process does not require separation unit for carbon dioxide. The fuel reactor can produce an almost pure carbon dioxide feed which decrease costs of carbon capture and storage (CCS). The CLC method is one of the most promising ones for energy efficient carbon capture. A large amount of literature was examined for this study and from it the most promising methods and designs were chosen. These methods and designs were combined as reactor system design which was then sized during the making of this thesis. Sizing was done with a mathematical model that was further improved during the study.

Detection, transmission, pathogenicity and chemical treatment of fungi in Ceiba speciosa seeds

The aim of this work was to evaluate fungus association, transmission and pathogenicity, besides chemical seed treatment in Ceiba speciosa seeds from different regions of southern Brazil. Seven seed samples were used to do the germination test, fungus detection by blotter test and potato-dextrose-agar (PDA), fungus transmission and pathogenicity tests; besides, chemical seed treatments were tested. Germination ranged from 0 to 59,5%. The following fungi were associated in the seeds: Fusarium sp., Alternaria sp., Colletotrichum sp., Curvularia sp. and Pestalotia sp.; in addition, Fusarium sp. was found in all the samples. Alternaria sp. and Fusarium sp. were transmitted by seeds. The isolates of Alternaria sp., Colletotrichum sp. and Fusarium sp., were pathogenic to seedlings and seeds. The seed treatment with methyl tiophanate and the combination captan + methyl tiophanate reduced Fusarium sp. incidence.

Impact of anthracnose on the yield of soybean subjected to chemical control in the north region of Brazil

ABSTRACT Losses due to soybean anthracnose, caused by Colletotrichum truncatum, have not been systematically quantified in the field, and the efficacy of chemical control of this disease is not known. This study shows an estimate of losses associated with the disease in soybean crops in the north of the country. Two trials with cv. M9144 RR were carried out in commercial fields in Tocantins State in the 2010/2011 and 2011/2012 growing seasons, in randomized blocks, with four replicates. Foliar applications were performed on plants at R1/R2 and R5.2 stages, employing CO2-pressurized equipment and application volume of 200 L ha-1. Nine fungicides and one untreated control were compared, and the disease gradients in the two seasons were obtained. The percentage of infected pods was calculated at the R6 stage. Grain yield ranged from 3,288 to 3,708 kg/ha in the untreated plots in 2010/2011 and 2011/2012, respectively, and from 3,282 to 4,110 kg/ha in the treated plots. In the 2010/2011 season, only azoxystrobin + cyproconazole significantly reduced the disease incidence, compared to untreated control plots, not differing from the remaining treatments. In the 2011/2012 season, there were no significant differences between treated and untreated plots. Highly significant correlations (p < 0.01) were found between yield and soybean anthracnose incidence on pods in both years (r = -0.85). For each 1% increment in the disease incidence, c. 90 kg/ha of soybean grain were lost. The current study determined that significant losses due to anthracnose occur in commercial crops in the north of the country and highlighted the limitation of chemical control as anthracnose management method.

Environmental behavior of soils and mixtures of soil-whitewash mud

The present study sought to observe the behavior of soils in natural state and in mixtures, in different ratios, with the industrial solid residue called whitewash mud. The work was conducted with samples of typical soils from the region of Alagoinhas, Bahia-Brazil. Wet chemical analysis and atomic absorption spectrophotometry were used in order to obtain the classification of the industrial solid residue. Solubilization and leaching tests were performed and X-ray diffraction and electron microscopy techniques were carried out. The results showed that the whitewash mud was classified as non-inert, but with great capacity of heavy metal retention largely owed to the kaolinite and goethite presence in the clay fraction of the soils, making it difficult to have heavy metals readily available for exchange.

Recovery and refining of manganese as by-product from hydrometallurgical processes

The consumption of manganese is increasing, but huge amounts of manganese still end up in waste in hydrometallurgical processes. The recovery of manganese from multi-metal solutions at low concentrations may not be economical. In addition, poor iron control typically prevents the production of high purity manganese. Separation of iron from manganese can be done with chemical precipitation or solvent extraction methods. Combined carbonate precipitation with air oxidation is a feasible method to separate iron and manganese due to the fast kinetics, good controllability and economical reagents. In addition the leaching of manganese carbonate is easier and less acid consuming than that of hydroxide or sulfide precipitates. Selective iron removal with great efficiency from MnSO4 solution is achieved by combined oxygen or air oxidation and CaCO3 precipitation at pH > 5.8 and at a redox potential of > 200 mV. In order to avoid gypsum formation, soda ash should be used instead of limestone. In such case, however, extra attention needs to be paid on the reagents mole ratios in order to avoid manganese coprecipitation. After iron removal, pure MnSO4 solution was obtained by solvent extraction using organophosphorus reagents, di-(2-ethylhexyl)phosphoric acid (D2EHPA) and bis(2,4,4- trimethylpentyl)phosphinic acid (CYANEX 272). The Mn/Ca and Mn/Mg selectivities can be increased by decreasing the temperature from the commonly used temperatures (40 –60oC) to 5oC. The extraction order of D2EHPA (Ca before Mn) at low temperature remains unchanged but the lowering of temperature causes an increase in viscosity and slower phase separation. Of these regents, CYANEX 272 is selective for Mn over Ca and, therefore, it would be the better choice if there is Ca present in solution. A three-stage Mn extraction followed by a two-stage scrubbing and two-stage sulfuric acid stripping is an effective method of producing a very pure MnSO4 intermediate solution for further processing. From the intermediate MnSO4 some special Mn- products for ion exchange applications were synthesized and studied. Three types of octahedrally coordinated manganese oxide materials as an alternative final product for manganese were chosen for synthesis: layer structured Nabirnessite, tunnel structured Mg-todorokite and K-kryptomelane. As an alternative source of pure MnSO4 intermediate, kryptomelane was synthesized by using a synthetic hydrometallurgical tailings. The results show that the studied OMS materials adsorb selectively Cu, Ni, Cd and K in the presence of Ca and Mg. It was also found that the exchange rates were reasonably high due to the small particle dimensions. Materials are stable in the studied conditions and their maximum Cu uptake capacity was 1.3 mmol/g. Competitive uptake of metals and acid was studied using equilibrium, batch kinetic and fixed-bed measurements. The experimental data was correlated with a dynamic model, which also accounts for the dissolution of the framework manganese. Manganese oxide micro-crystals were also bound onto silica to prepare a composite material having a particle size large enough to be used in column separation experiments. The MnOx/SiO2 ratio was found to affect significantly the properties of the composite. The higher the ratio, the lower is the specific surface area, the pore volume and the pore size. On the other hand, higher amount of silica binder gives composites better mechanical properties. Birnesite and todorokite can be aggregated successfully with colloidal silica at pH 4 and with MnO2/SiO2 weight ratio of 0.7. The best gelation and drying temperature was 110oC and sufficiently strong composites were obtained by additional heat-treatment at 250oC for 2 h. The results show that silica–supported MnO2 materials can be utilized to separate copper from nickel and cadmium. The behavior of the composites can be explained reasonably well with the presented model and the parameters estimated from the data of the unsupported oxides. The metal uptake capacities of the prepared materials were quite small. For example, the final copper loading was 0.14 mmol/gMnO2. According to the results the special MnO2 materials are potential for a specific environmental application to uptake harmful metal ions.

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.

Lannoitetehtaan prosessivesien käsittelyvaihtoehtojen soveltuvuuden arviointi

Phosphorus and nitrogen cause eutrophication of water bodies, causing severe damage to the ecosystem. Eutrophication of the waters causes oxygen depletion, which in turn increases fish mortality, releasing toxins in waters. The released toxins can cause damage to animals and humans, which is the reason in many countries to set emission limits for waste water. Nutrients exist naturally, but due to human activities there is high nutrient leaching to water bodies. Human activity is one of the main reasons to the eutrophication. The aim of this thesis was to estimate the suitability of different water treatment options for Yara Finland’s fertilizer plant’s process waters in Siilinjärvi. The fertilizer plant process waters are high concentrate and especially nitrogen concentrations are high, which bring challenge to the treatment. At the theoretical part was investigated conventional and as well advanced wastewater treatment methods like reverse osmosis, adsorption and ion exchange. Beside different treatment methods corporate environmental requirements, responsibility and strategies were researched. At the empirical part of the thesis the goal was to find out possibil-ities to intensify the efficiency of purification at lamella clarifier with chemical precipitation. In addition possibility to use already existing chemical purifying plant for process waters was estimated. As a result of the research Yara has a possibility to intensify lamella clarifier’s action by addi-tion of calcium hydroxide and thus to obtain the phosphorus and fluorine to precipitate out of the water. But in practice this would be too expensive. It is possible to eliminate nitrogen compounds by adsorption or ammonia stripping, both methods requires additional testing. It is possible to process waters in chemical purifying plant, if ammonium nitrogen has been reduced before. Reverse osmosis is possible to exploit for the phosphoric acid plant’s waters.

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.

Sensibility analysis of the pearl model for pesticide leaching in the State of Mato Grosso do Sul, Brazil

For an accurate use of pesticide leaching models it is necessary to assess the sensitivity of input parameters. The aim of this work was to carry out sensitivity analysis of the pesticide leaching model PEARL for contrasting soil types of Dourados river watershed in the state of Mato Grosso do Sul, Brazil. Sensitivity analysis was done by carrying out many simulations with different input parameters and calculating their influence on the output values. The approach used was called one-at-a-time sensitivity analysis, which consists in varying independently input parameters one at a time and keeping all others constant with the standard scenario. Sensitivity analysis was automated using SESAN tool that was linked to the PEARL model. Results have shown that only soil characteristics influenced the simulated water flux resulting in none variation of this variable for scenarios with different pesticides and same soil. All input parameters that showed the greatest sensitivity with regard to leached pesticide are related to soil and pesticide properties. Sensitivity of all input parameters was scenario dependent, confirming the need of using more than one standard scenario for sensitivity analysis of pesticide leaching models.

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%.