Determination of sugars and organic acids in pulp samples by capillary electrophoresis with UV detection

This MSc work was done in the project of BIOMECON financed by Tekes. The prime target of the research was, to develop methods for separation and determination of carbohydrates (sugars), sugar acids and alcohols, and some other organic acids in hydrolyzed pulp samples by capillary electrophoresis (CE) using UV detection. Aspen, spruce, and birch pulps are commonly used for production of papers in Finland. Feedstock components in pulp predominantly consist of carbohydrates, organic acids, lignin, extractives, and proteins. Here in this study, pulps have been hydrolyzed in analytical chemistry laboratories of UPM Company and Lappeenranta University in order to convert them into sugars, acids, alcohols, and organic acids. Foremost objective of this study was to quantify and identify the main and by-products in the pulp samples. For the method development and optimization, increased precision in capillary electrophoresis was accomplished by calculating calibration data of 16 analytes such as D-(-)-fructose, D(+)-xylose, D(+)-mannose, D(+)-cellobiose, D-(+)-glucose, D-(+)-raffinose, D(-)-mannitol, sorbitol, rhamnose, sucrose, xylitol, galactose, maltose, arabinose, ribose, and, α-lactose monohydratesugars and 16 organic acids such as D-glucuronic, oxalic, acetic, propionic, formic, glycolic, malonic, maleic, citric, L-glutamic, tartaric, succinic, adipic, ascorbic, galacturonic, and glyoxylic acid. In carbohydrate and polyalcohol analyses, the experiments with CE coupled to direct UV detection and positive separation polarity was performed in 36 mM disodium hydrogen phosphate electrolyte solution. For acid analyses, CE coupled indirect UV detection, using negative polarity, and electrolyte solution made of 2,3 pyridinedicarboxylic acid, Ca2+ salt, Mg2+ salts, and myristyltrimethylammonium hydroxide in water was used. Under optimized conditions, limits of detection, relative standard deviations and correlation coefficients of each compound were measured. The optimized conditions were used for the identification and quantification of carbohydrates and acids produced by hydrolyses of pulp. The concentrations of the analytes varied between 1 mg – 0.138 g in liter hydrolysate.

Ion modulated organic transistors

I likhet med vanliga plaster är de π-konjugerade polymererna flexibla, lösliga och processbara vid låga temperaturer (< 150 ºC). Därutöver har de egenskapen att leda ström. Konduktivitetsintervallet är brett och omfattar nästintill metallisk ledningsförmåga å ena sidan, via halvledarkonduktiva till isolerande å andra sidan. Polymererna utgörs av regelbundna kedjor av kolatomer och associeras sålunda till organiska material. Sedan de första vetenskapliga rapporterna publicerades vid slutet av 1970-talet har π-konjugerade polymerer använts och utvecklats i exempelvis solceller, dioder, lysdioder och transistorer. Nobelpriset i kemi tilldelades år 2000 åt Hideki Shirakawa, Alan J. Heeger och Alan G. MacDiarmid för upptäckten och utvecklandet av ledande polymerer. I min avhandling har jag arbetat med att utveckla och förstå lågspännings jonmodulerade organiska transistorer. Två typer av jonmodulerade organiska transistorer studeras: (1) den jonmodulerade organiska fälteffekt transistorn (jonmodulerade OFETen), som utgör den centrala transistorn i avhandlingen, samt (2) den elektrokemiska transistorn. Den första typen fungerar som en konventionell OFET. Strömmen i halvledaren moduleras av det elektriska fältet över isolatorn. Med användandet av en elektrolyt ”isolator” orsakar polariseringen av jonerna däremot ett högt elektriskt fält vid elektrolyt/halvledargränssnittet och man åstadkommer modulering av strömmen redan vid några volts drivspänningar. I den andra typen utnyttjas elektrokemi för att medelst reduktion/oxidation modulera strömmen i den π-konjugerade polymeren. Ett viktigt ändamål i avhandlingen har också varit att kunna tillverka transistorerna med masstillverkningsmetoder. I avhandlingen presenteras de jonmodulerade organiska transistorernas möjlighet att framställas med masstillverkningsmetoder. Nya koncept introduceras och svagheter identifieras. Skillnaderna mellan OFETen, jonmodulerade OFETen och den elektrokemiska transistorn klargörs. Arbetet skall däremot inte anses fullbordat utan forskningen fortgår för att kringgå svagheterna, öka på transistorernas stabilitet och framförallt tillämpa dem i innovativa applikationer.

Nematicidal effect of volatile organic compounds (VOCs) on the plant-parasitic nematode Meloidogyne javanica

Previous studies have demonstrated that volatile organic compounds (VOCs), produced by the yeast Saccharomyces cerevisiae, were able to inhibit the development of phytopathogenic fungi. In this context, the nematicidal potential of the synthetic mixture of VOCs, constituted of alcohols and esters, was evaluated for the control of the root-knot nematode Meloidogyne javanica, which causes losses to crops of high economic value. The fumigation of substrate containing second-stage juveniles with VOCs exhibited nematicidal effect higher than 30% for the lowest concentration tested (33.3 µL g-1 substrate), whereas at 66.6 and 133.3 µL g-1 substrate, the nematode mortality was 100%. The present results stimulate other studies on VOCs for nematode management.

Influência da saturação por bases e do fósforo no crescimento de mudas de angico-branco

Este trabalho teve por objetivo avaliar o desempenho de mudas da espécie angico-branco (Anadenanthera colubrina (Vell.) Brenan), em condições diferenciadas de disponibilidade de fósforo no solo e de saturação por bases. Os tratamentos foram representados por um fatorial de seis níveis de P (0, 100, 200, 300, 400 e 500 mg/dm³) por cinco níveis de saturação por bases (original = 24, 40, 50, 60 e 70%), sendo dispostos no delineamento em blocos ao acaso, com cinco repetições. Aos 170 dias após a semeadura, foram feitas medições de altura e diâmetro do coleto de todas as plantas, as quais foram colhidas, separadas em raiz e parte aérea e postas a secar para obtenção do peso de matéria seca. A adição da mistura corretiva ao substrato não apresentou resposta significativa por parte da espécie estudada. Essa falta de resposta pode estar relacionada ao fato de que os teores de Ca (0,9 cmol c/dm³) e de Mg (0,4 cmol c/dm³) contidos no solo utilizado tenham sido suficientes para suprir as necessidades das plantas nessa fase. No entanto, observou-se que o angico-branco responde positivamente à aplicação de P. Considerando-se a saturação por bases de 40 e 60%, as doses de P que proporcionaram 90% de produção máxima, com base na produção de matéria seca da parte aérea, foram de 127 e 126 mg/dm³, respectivamente. De acordo com o modelo ajustado para P recuperado, em função do P adicionado, a dose que proporcionará essa disponibilidade de fósforo aos 170 dias é de 976,2 mg/dm³ para V=40% e de 1.277,3 mg/dm³ para V=60%. O nível crítico de P no solo, pelo extrator Mehlich-1, foi de 13,88 mg/dm³ (V=40%) e de 12,87 mg/dm³ (V=60%) e na parte aérea, de 0,14 dag/kg (V=40%) e de 0,12 dag/kg (V=60%).

Crescimento e qualidade de mudas de Anadenanthera macrocarpa (Benth.) brenan em resposta à saturação por bases do substrato

O presente trabalho foi desenvolvido com o objetivo de verificar a influência da saturação por bases do substrato sobre o crescimento e a qualidade de mudas de Anadenanthera macrocarpa (angico-vermelho). O delineamento experimental utilizado foi inteiramente casualizado, com quatro repetições por tratamento. Foram empregados três solos como substrato, e para cada um deles a saturação por bases original foi elevada aos seguintes valores: Latossolo Distrófico, 30,0; 50,0; e 70,0%; Latossolo Álico, 25,0; 45,0; e 65,0%; e Argissolo, 50,0; 60,0; e 70,0%. Foram avaliados os parâmetros morfológicos das mudas, suas relações e o índice de qualidade de Dickson. A saturação por bases não teve influência em nenhum dos parâmetros avaliados quando o substrato utilizado foi o argissolo. Exceto no diâmetro do coleto, a elevação da saturação por bases exerceu influência significativa, com padrão linear sobre os parâmetros morfológicos, suas relações e no índice de qualidade de Dickson para mudas produzidas no Latossolo Distrófico. No Latossolo Álico foi observado influência significativa com um comportamento quadrático sobre as características avaliadas, sendo os melhores crescimentos e qualidade encontrados quando a saturação por bases estava próxima de 50,0%.

Influência da saturação por bases e da relação Ca:Mg do substrato sobre o crescimento inicial de jacarandá-da-bahia (Dalbergia nigra (Vell.) Fr. All. ex Benth.)

Com o objetivo de verificar a influência da saturação por bases do substrato sobre o crescimento e qualidade de mudas de Dalbergia nigra (jacarandá-da-bahia), desenvolveu-se este trabalho. O delineamento experimental utilizado foi inteiramente casualizado com quatro repetições por tratamento, e cada vaso com uma planta foi considerado uma repetição. Foram utilizados três tipos de solo como substrato (dois latossolos e um argissolo), e em cada um deles a saturação por bases original foi elevada para os seguintes valores: latossolo distrófico: 30,0, 50,0 e 70,0%; Latossolo álico: 25,0; 45,0; e 65,0%; Argissolo: 50,0; 60,0; e 70,0%. Para avaliar os efeitos das diferentes relações Ca:Mg do corretivo, elevou-se a saturação por bases do solo para 60,0% no argissolo, 50,0% no latossolo distrófico e 45,0% no latossolo álico, utilizando como corretivo uma mistura de CaCO3 e MgCO3 nas seguintes relações estequiométricas: 1:0, 1:1, 2:1, 3:1 e 4:1. Foram avaliados os parâmetros morfológicos das mudas, suas relações e o índice de qualidade de Dickson. Observou-se uma resposta linear quando as diferentes relações Ca:Mg do corretivo foram analisadas em função da variação do peso de matéria seca da parte aérea, bem como o peso de matéria seca total quando o substrato era o Argissolo, porém nos demais substratos e características não houve influência significativa. Pode-se concluir que, quando a saturação original do solo for igual ou superior a 14,0% no Latossolo distrófico e 4% no Latossolo álico, não há necessidade de se proceder à correção do solo, enquanto no Argissolo as mudas de melhor qualidade são obtidas quando a saturação está em torno de 60,0%.

Immobilization of Burkholderia cepacia Lipase: Kinetic Resolution in Organic Solvents, Ionic Liquids and in Their Mixtures

Immobilization of Burkholderia cepacia Lipase: Kinetic Resolution in Organic Solvents, Ionic Liquids and in Their Mixtures Biocatalysis opens the door to green and sustainable processes in synthetic chemistry allowing the preparation of single enantiomers, since the enzymes are chiral and accordingly able to catalyze chemical reactions under mild conditions. Immobilization of enzymes enhances process robustness, often stabilizes and activates the enzyme, and enables reuse of the same enzyme preparation in multiple cycles. Although hundreds of variations of immobilization methods exist, there is no universal method to yield the highly active, selective and stable enzyme catalysts. Therefore, new methods need to be developed to obtain suitable catalysts for different substrates and reaction environments. Lipases are the most widely used enzymes in synthetic organic chemistry. The literature part together with the experimental part of this thesis discusses of the effects of immobilization methods mostly used to enhance lipase activity, stability and enantioselectivity. Moreover, the use of lipases in the kinetic resolution of secondary alcohols in organic solvents and in ionic liquids is discussed. The experimental work consists of the studies of immobilization of Burkholderia cepacia lipase (lipase PS) using three different methods: encapsulation in sol-gels, cross-linked enzyme aggregates (CLEAs) and supported ionic liquids enzyme catalysts (SILEs). In addition, adsorption of lipase PS on celite was studied to compare the results obtained with sol-gels, CLEAs and SILEs. The effects of immobilization on enzyme activity, enantioselectivity and hydrolysis side reactions were studied in kinetic resolution of three secondary alcohols in organic solvents, in ionic liquids (ILs), and in their mixtures. Lipase PS sol-gels were shown to be active and stable catalysts in organic solvents and solvent:IL mixtures. CLEAs and SILEs were highly active and enantioselective in organic solvents. Sol-gels and SILEs were reusable in several cycles. Hydrolysis side reaction was suppressed in the presence of sol-gels and CLEAs.

Influência da saturação por bases do substrato no crescimento e qualidade de mudas Machaerium nictitans (Vell.) Benth.

Este trabalho foi desenvolvido com o objetivo de verificar a influência da saturação por bases do substrato no crescimento e qualidade de mudas de Machaerium nictitans. O delineamento utilizado foi em blocos ao acaso com quatro repetições. Como substrato foram empregados três diferentes solos, sendo em cada um deles a saturação por bases original elevada para os seguintes valores: Argissolo Vermelho-Amarelo 50, 60 e 70%, Latossolo Vermelho-Amarelo distrófico 30, 50 e 70% e Latossolo Vermelho-Amarelo álico 25, 45 e 65%. Foram avaliadas as características morfológicas das mudas, altura da parte aérea e diâmetro do coleto; peso de matéria seca da parte aérea, raízes e total, bem como as relações entre a altura da parte área e o diâmetro do coleto, altura da parte aérea e seu peso de matéria seca, peso de matéria seca da parte aérea e peso de matéria seca das raízes; e o índice de qualidade de Dickson. Com base nos dados, foi possível concluir que: as melhores mudas de Machaerium nictitans no Argissolo Vermelho-Amarelo foram obtidas na saturação por bases de 60%, no Latossolo Vermelho-Amarelo distrófico na saturação por bases de 70% e no Latossolo Vermelho-Amarelo álico na saturação por bases de 40%.

Estruturação topológica de grandes bases de dados de bacias hidrográficas

O presente trabalho teve como objetivo avaliar o método para delimitação da bacia de contribuição à montante de um ponto selecionado sobre o hidrografia e a obtenção das respectivas características morfométricas, a partir de bases de dados estruturadas topologicamente. Para tanto, utilizou-se o aplicativo Hidrodata 2.0, desenvolvido para o ArcINFO workstation, comparando os seus resultados com os do processo convencional. Os resultados comprovaram que o tempo de processamento demandado para delimitação de bacias e extração de suas características morfométricas a partir de uma base de dados estruturada topologicamente se manteve baixo e constante. Concluiu-se que o método apresentado poderá ser aplicado em qualquer bacia hidrográfica, independentemente do seu tamanho, mesmo com o uso de computadores de configuração mais modesta.

Soil organic matter pools in a tropical savanna under agroforestry system in Northeastern Brazil

This study aimed at quantifying total organic carbon stocks and its pools in Acrisol under agroforestry systems with six (AFS6) and thirteen years old (AFS13), slash-and-burn agriculture (SBA) and savanna native forest (SNF) in northeastern Brazil. Soil samples were collected at 0-0.05 m, 0.05-0.10 m, 0.10-0.20 m and 0.20-0.40 m depths in the dry and rainy seasons to evaluate total organic carbon (TOC) stocks and labile carbon (LC), fulvic acid fraction (C-FAF), humic acid fraction (C-HAF), humin (C-HF) and microbial biomass carbon (Cmic) contents. Additionally, carbon management index (CMI) was determined. Higher TOC stocks (97.7 and 81.8 Mg ha-1 for the 0-0.40 m depth in the dry and rainy seasons, respectively) and LC, humic substances and Cmic contents were observed in the AFS13 in all the depths. CMI also was higher in the AFS13 (0-0. 05 m: 158 and 86; 0.05-0.10 m: 171 and 67, respectively for the dry and rainy seasons) especially when compared to the SBA (0-0.05 m: 5.6 and 5.4; 0.05-0.10 m: 5.3 and 5.8, respectively for dry and rainy seasons). The agroforestry systems increased soil quality through the conservation of organic matter and can be considered an excellent strategy to assurance sustainability in tropical soil of Northeastern Brazil

INTERACTIONS OF BIOCHAR AND ORGANIC COMPOUND FOR SEEDLINGS PRODUCTION OF Magonia pubescens A. St.-Hil.

ABSTRACTThe objective of this study was to test the hypothesis that biochar, applied with cattle manure, promotes better development of seedlings of Magonia pubescens St. Hil. The experiment was conducted at the State University of Mato Grosso, Nova Xavantina, Brazil, in 2011. We used a completely randomized design, with twelve treatments and three replications. The substrates formed by the higher levels of cattle manure plus biochar (30%) provided better results of height, diameter and aerial biomass. However, the Dickson Quality Index has not confirmed the quality of seedlings in these treatments. We also observed that the doses of biochar (20 and 30%) when added separately to the Latosol, are not efficient for the growth improvement of the seedlings. Based on the present results, we validate the hypothesis that substrates formed with a mixture of cattle manure and biochar are effective to improve the production of seedlings of M. pubescens.

SOIL ORGANIC CARBON, CARBON STOCK AND THEIR RELATIONSHIPS TO PHYSICAL ATTRIBUTES UNDER FOREST SOILS IN CENTRAL AMAZONIA

ABSTRACT The soil carbon under Amazonian forests has an important roles in global changing, making information on the soil content and depths of these stocks are considerable interest in efforts to quantify soil carbon emissions to the atmosphere.This study quantified the content and soil organic carbon stock under primary forest up to 2 m depth, at different topographic positions, at Cuieiras Biological Reserve, Manaus/ ZF2, km 34, in the Central Amazon, evaluating the soil attributes that may influence the permanence of soil carbon. Soil samples were collected along a transect of 850 m on topographic gradient Oxisol (plateau), Ultisol (slope) and Spodosol (valley). The stocks of soil carbon were obtained by multiplying the carbon content, soil bulk density and trickiness of soil layers. The watershed was delimited by using STRM and IKONOS images and the carbon contend obtained in the transects was extrapolated as a way to evaluate the potential for carbon stocks in an area of 2678.68 ha. The total SOC was greater in Oxisol followed by Spodosol and Ultisol. It was found direct correlations between the SOC and soil physical attributes. Among the clay soils (Oxisol and Ultisol), the largest stocks of carbon were observed in Oxisol at both the transect (90 to 175.5 Mg C ha-1) as the level of watershed (100.2 to 195.2 Mg C ha-1). The carbon stocks under sandy soil (Spodosol) was greater to clay soils along the transect (160-241 Mg C ha-1) and near them in the Watershed (96.90 to 146.01 Mg C ha-1).

Removal of organic matter and nutrients from slaughterhouse wastewater by using Eichhornia crassipes and evaluation of the generated biomass composting

The objective of this research was to evaluate the performance of the aquatic macrophyte Eichhornia crassipes applied in situ in a slaughter house treatment system, located in the west of the Paraná state, Brazil, regarding the nutrients removal and organic matter. Moreover, it aimed to obtain data from the production, management and composting practices of the biomass generated in the system. During 11 months of macrophytes development, physic and chemical parameters were monitored and plant density was controlled by periodical removal of excess biomass, which was weekly monitored and it is expressed in kg of aquatic plant per m² covered area. The degradation of the macrophytes removed from the treatment system was evaluated at the pilot scale in eight composting piles of 0.60 m³ that underwent four different treatments and two repetitions: T1 - water hyacinth (Eichhornia crassipes); T2 - water hyacinth and swine excrement (7:1), T3 - water hyacinth, swine excrement and earth (7:1:0,67), and T4 - water hyacinth, swine excrement and cellulosic gut (7:1:0,67), for a period of 90 days. The results indicated maximum removal efficiencies of 77.2% for COD; 77.8% for BOD, 87.9% for total nitrogen, 47.5% for ammonia nitrogen and 38.9% for total phosphorus for a five-day retention time. For biomass stabilization by composting, considering the C:N ratio as an indicator of compost maturity, it was observed that treatment T4 resulted in the shortest stabilization period (60 days). No difference was verified in the biostabilization rates at 5% level by the F test.

Recycling of nutrients with application of organic waste in degraded pasture

The utilization of organic wastes represents an alternative to recover degraded pasture. The experiment aimed to assess the changes caused by the provision of different organic waste (poultry litter, turkey litter and pig manure) in a medium-textured Oxisol in Brazilian Savanna under degraded pasture. It was applied different doses of waste compared to the use of mineral fertilizers and organic mineral and evaluated the effect on soil parameters (pH, organic matter, phosphorus and potassium) and leaf of Brachiariadecumbens (crude protein, phosphorus and dry mass production). It was observed that application of organic waste did not increase the level of soil organic matter and pH in the surface layer, and the application of turkey litter caused acidification at depths of 0.20-0.40 m and 0.40-0.60 m. There was an increase in P and K in the soil with the application of poultry litter and swine manure. All organic wastes increased the productivity of dry matter and crude protein and phosphorus. The recycling of nutrients via the application of organic waste allows efficiency of most parameters similar to those observed with the use of mineral sources, contributing to improving the nutritional status of soil-plantsystem.

Nitrogen fertilization by deep-bedding swine production and its effects on the properties of a Quartzarenic Neosol

The objective of this study was to evaluate the effects of the nitrogen fertilization in the form of swine deep bed in the properties of a quartz-sand neosol. The organic compound used was the deep bed made with rice hulls, from a commercial swine finishing system farm. Deep bed samples have been collected at various points in the installation in order to obtain a representative composite sample which has been fractionated in a 2.0 mm sieve and submitted to a 50-day maturation period. Then, agronomic value analyses were done. The experimental design was completely randomized. The treatments consisted of 0; 75; 150 and 300 mg dm-3 of N doses of deep bed as well as an additional treatment with ammonium sulfate at a 150 mg dm-3 of N. The experimental period in the greenhouse was 45 days, where the soil was cultivated with maize. After the experiment completion, further soil properties analyses were done. From the results, it was noted that the organic fertilization with deep bed provided a significant increase in the levels of potassium, in the sum of the bases, in the effective CEC, in the CEC at pH 7.0 and in the percentage of saturation.