Creating greater value for biomass residues

Dissertation presented to obtain the Ph.D degree in Engineering Sciences and Technology

Applications of the indole scaffold in medicinal chemistry: development of new antioxidants, COX inhibitors and antitubercular agents

Dissertação para obtenção do Grau de Doutor em Química, especialidade Química Orgânica

Ionic liquids as catalysts of lignocellulosic biomass processing

The present work is devoted to study the pre-treatment of lignocellulosic biomass, especially wheat straw, by the application of the acidic ionic liquid (IL) such as 1-butyl-3-methylimidazolium hydrogen sulphate. The ability of this IL to hydrolysis and conversion of biomass was scrutinised. The pre-treatment with hydrogen sulphate-based IL allowed to obtain a liquor rich in hemicellulosic sugars, furans and organic acids, and a solid fraction mainly constituted by cellulose and lignin. Quantitative and qualitative analyses of the produced liquors were made by capillary electrophoresis and high-performance liquid chromatography. Pre-treatment conditions were set to produce xylose or furfural. Specific range of temperatures from 70 to 175 °C and residence times from 20.0 to 163.3 min were studied by fixing parameters such as biomass/IL ratio (10 % (w/w)) and water content (1.25 % (w/w)) in the pre-treatment process. Statistical modelling was applied to maximise the xylose and furfural concentrations. For the purpose of reaction condition comparison the severity factor for studied ionic liquid was proposed and applied in this work. Optimum conditions for xylose production were identified to be at 125 °C and 82.1 min, at which 16.7 % (w/w) xylose yield was attained. Furfural was preferably formed at higher pre-treatment temperatures and longer reaction time (161 °C and 104.5 min) reaching 30.7 % (w/w) maximum yield. The influence of water content on the optimum xylose formation was also studied. Pre-treatments with 5 and 10 % (w/w) water content were performed and an increase of 100 % and 140 % of xylose yield was observed, respectively, while the conversion into furfural maintained unchanged.

The chemistry of Brazilian leguminosae. LXI. (+)-Methyl Vouacapenate from Vouacapoua pallidior

Thz wood of Vouacapoua pallidior (Leguminosae-Caesalpinioideae) Contains (+)-methyl vouacapenate.

Observations of air composition in Brazil between the Equator and 20°s during the dry season.

Field measurement programs in Brazil during the dry season months of August and September in 1979 and 1980 have demonstrated the great importance of the continental tropics in global air chemistry. Especially in the mixed layer, the air composition over land is much different from that over the ocean and the land areas are clearly longe scale sources of many inportant trace gases. During the dry season much biomass, burning takes place especially in the cerrado regions leading to substantial emission of air pollutants, such as CO, NOx, N2O, CH4 and other hydrocarbons. Ozone concentrations are alsoenhanced due to photochemical reactions. Biogenic organic emissions from tropical forests play likewise an important role in the photochemistry of the atmosphere. Carbon monoxide was found to be present in high concentrations in the boundary layer of the tropical forest, but ozone concentrations were much lower than in the cerrado.

Curare - Botany, Chemistry, and Pharmacology

Some aspects of curare research carried out over the last 25 years are discussed. Accepting a pharmacological rather than purely ethnological definition means, that curares are not limited to South America but that they are also known from Central Africa and South-EastAsia. Among the criteria that have been suggested for classifying South American curares: type of container, geographical origin, botanical sourcesof the active, constituent!, and chemical composition. A combination of botanical and geographical criteria leads to much the same regional ;groupings a combination of criteria involving the type of container and the chemical composition. The active principles in curares may derive from members of thr Loganiaceae (Strychnos) and/or Menispermaceae mainly Chondrodendron and Curarea, but also Abuta,Anomospermum, Cissampelos, Sciadotenia, and Telitoxicum). Certain of the Strychnos dimeric indole alkaloids can undergo a variety of cleavages, oxidations, and isomerizations; hence., some of the compounds obtained by normal isolation procedures one almost certainly artefacts. The different genera of, Menispermaceae a wide range of bisbenzyl and other types of isoquinoline alkaloids. Many of the plant additives also contain a variety of isoquinoline bases, and this has to be taken into account in assessing the contribution these ingredients may make to the ovzJuxll activity of, curare. Loganiaceae-bated curares with toxiferinzas major alkaloid tend to be the most toxic. In the case of Menispermaceae-based products, there-is evidence that the process by which they are made may lead to a considerable increase in the toxicity of the finished poisons as compared with the original plant materials. The mechanism of action of the alkaloids it, outlined, and the role of curare alkaloids in the development of, present-day muscle-relaxant drugs used in surgery is indicated. Attention lb drawn to reported medicinal uses of some of the alkaloid-bearing plants incorporated into curares, suggesting that further evaluation of these plants may be of interest.

Occurrence, body mass and biomass of Syntermes spp. (Isoptera: Termitidae) in Reserva Ducke, Central Amazonia

The leaf-feeding species Syntermes molestus and S. spinosus are two dominant termite species in Reserva Ducke in Central Amazonia; two other species (S. aculeosus, S. longiceps) exist in the area. All species except S. aculeosus were also found in urban areas. The workers of S. molestus and S. spinosus have average body dry weights of 4.5±0.2 and 13.1±1.4 mg, and the weight of their soldiers is 8.2±0.2 and 51.0±1.7 mg, respectively. Therefore, S. spinosus is among the largest termites of the world. In both species, fresh weight is about 4.7 higher than dry weight (a wider relation than in other termite species). The biomass of the populations of both species amounted to about 1 g m-2 (dry weight; indirect estimate), which rises previous assessments of the total termite biomass by about 36-45%, to a value of 3.0-3.5 g m-2.

Forest biomass and wood consumption In the lower course of the Amazon: a case study of rhe Urubueua Island

Várzea and terra-firme forests in the lower course of the Amazon were compared in terms of forest structure, wood volume increments and forest biomass. The wood volume of várzea forests was smaller than that of terra-firme forests, particularly when severe human intervention such as the cultivation of açaí palm occurred. The difference was even greater in the forest weight comparison because of the lower wood density of várzea trees. These trees are not directly influenced by water stress during the dry season, while late wood with a high density is formed in the terra-firme trees. The annual forest disappearance area due to firewood for tile factories was estimated to be about 276 ha on the island investigated, which had an area of 36,200 ha. Assuming that the forests are rotatively cultivated every 25 to 30 years, the total deforestation area is 6,870-6,948 ha in 25 years and 8,244~8,337 ha in 30 years. This result means that the balance between forest biomass and utilization is not in crisis, however, this balance might be lost as long as substitutive energy such as electricity is not supplied.

Using stated preference methods to assess environmental impacts of forest biomass power plants in Portugal

As a renewable energy source, the use of forest biomass for electricity generation is advantageous in comparison with fossil fuels, however the activity of forest biomass power plants causes adverse impacts, affecting particularly neighbouring communities. The main objective of this study is to estimate the effects of the activity of forest biomass power plants on the welfare of two groups of stakeholders, namely local residents and the general population and we apply two stated preference methods: contingent valuation and discrete choice experiments, respectively. The former method was applied to estimate the minimum compensation residents of neighbouring communities of two forest biomass power plants in Portugal would be willing to accept. The latter method was applied among the general population to estimate their willingness to pay to avoid specific environmental impacts. The results show that the presence of the selected facilities affects individuals’ well-being. On the other hand, in the discrete choice experiments conducted among the general population all impacts considered were significant determinants of respondents’ welfare levels. The results of this study stress the importance of performing an equity analysis of the welfare effects on different groups of stakeholders from the installation of forest biomass power plants, as their effects on welfare are location and impact specific. Policy makers should take into account the views of all stakeholders either directly or indirectly involved when deciding crucial issues regarding the sitting of new forest biomass power plants, in order to achieve an efficient and equitable outcome.

Comparative environmental life-cycle analysis of concretes using biomass and coal fly ashes as partial cement replacement material

Nowadays, the concrete production sector is challenged by attempts to minimize the usage of raw materials and energy consumption, as well as by environmental concerns. Therefore, it is necessary to choose better options, e.g. new technologies or materials with improved life-cycle performance. One solution for using resources in an efficient manner is to close the materials' loop through the recycling of materials that result either from the end-of-life of products or from being the by-product of an industrial process. It is well known that the production of Portland cement, one of the materials most used in the construction sector, has a significant contribution to the environmental impacts, mainly related with carbon dioxide emission. Therefore, the study and utilization of by-products or wastes usable as cement replacement in concrete can supply more sustainable options, provided that these type of concrete produced has same durability and equivalent quality properties as standard concrete. This work studied the environmental benefits of incorporating different percentages of two types of fly ashes that can be used in concrete as cement replacement. These ashes are waste products of power and heat production sectors using coal or biomass as fuels. The results showed that both ashes provide a benefit for the concrete production both in terms of environmental impact minimization and a better environmental performance through an increase in cement replacement. It is possible to verify that the incorporation of fly ashes is a sustainable option for cement substitution and a possible path to improve the environmental performance of the concrete industry.

The ceramic artifacts in archaeological black earth (terra preta) from Lower Amazon Region, Brazil: chemistry and geochemical evolution

This paper carried out a chemical investigation of archaeological ceramic artifacts found in archaeological sites with Black Earth (ABE) in the Lower Amazon Region at Cachoeira-Porteira, State of Pará, Brazil. The ceramic artifacts, mostly of daily use, belong to Konduri culture (from 900 to 400 years BP). They are constituted of SiO2, Al2O3, Fe2O3, Na2O and P2O5; SiO2 and Al2O3 together add up to 80 % and indicate influence of acid rocks, transformed into clay minerals basically kaolinite. The relative high contents of P2O5 (2.37 % in average) come out as (Al,Fe)-phosphate, an uncommon fact in primitive red ceramics, but found in some roman and egyptian archaeological sites. The contents of the trace elements are similar or below the Earth's crust average. This chemical composition (except P2O5) detaches saprolite material derived acid igneous rocks or sedimentary ones as the main raw material of the ceramics. The contents of K, Na and Ca represent the feldspars and rock fragments possibly introduced into saprolitic groundmass, indicated by mineralogical studies. The presence of cauixi and cariapé as well as quartz sand was confirmed by optical microscope, SEM analyses and by the high silica contents of ceramic fragments. Phosphorus was possibly incorporated into groundmass during cooking of foods, and ABE soil profile formation developed on yellow Latosols. The raw materials and its tempers (cauixi, or cariapé, feldspar, crushed rocks, old ceramic artifacts and quartz fragments) are found close to the sites and therefore and certainly came from them.

Exploring TM image texture and its relationships with biomass estimation in Rondônia, Brazilian Amazon

Many texture measures have been developed and used for improving land-cover classification accuracy, but rarely has research examined the role of textures in improving the performance of aboveground biomass estimations. The relationship between texture and biomass is poorly understood. This paper used Landsat Thematic Mapper (TM) data to explore relationships between TM image textures and aboveground biomass in Rondônia, Brazilian Amazon. Eight grey level co-occurrence matrix (GLCM) based texture measures (i.e., mean, variance, homogeneity, contrast, dissimilarity, entropy, second moment, and correlation), associated with seven different window sizes (5x5, 7x7, 9x9, 11x11, 15x15, 19x19, and 25x25), and five TM bands (TM 2, 3, 4, 5, and 7) were analyzed. Pearson's correlation coefficient was used to analyze texture and biomass relationships. This research indicates that most textures are weakly correlated with successional vegetation biomass, but some textures are significantly correlated with mature forest biomass. In contrast, TM spectral signatures are significantly correlated with successional vegetation biomass, but weakly correlated with mature forest biomass. Our findings imply that textures may be critical in improving mature forest biomass estimation, but relatively less important for successional vegetation biomass estimation.

Biomass accumulation, photochemical efficiency of photosystem II, nutrient contents and nitrate reductase activity in young rosewood plants (Aniba rosaeodora Ducke) submitted to different NO3-:NH4+ ratios

The rosewood (Aniba rosaeodora Ducke) is a native tree species of Amazon rainforest growing naturally in acidic forest soils with reduced redox potential. However, this species can also been found growing in forest gaps containing oxide soils. Variations in the forms of mineral nitrogen (NO3- or NH4+) may be predicted in these different edaphic conditions. Considering that possibility, an experiment was carried out to analyze the effects of different NO3-:NH4+ ratios on the growth performance, mineral composition, chloroplastid pigment contents, photochemical efficiency photosystem II (PSII), and nitrate redutase activity (RN, E.C.1.6.6.1) on A. rosaeodora seedlings. Nine-month-old seedlings were grown in pots with a washed sand capacity of 7.5 kg and submitted to different NO3-:NH4+ ratios (T1 = 0:100%, T2 = 25:75%, T3 = 50:50%, T4 = 75:25%, and T5 = 100:0%). The lowest relative growth rate was observed when the NO3-:NH4+ ratio was equal to 0:100%. In general, high concentrations of NO3- rather than NH4+ favored a greater nutrient accumulation in different parts of the plant. For the chloroplastid pigment, the highest Chl a, Chl b, Chl tot, Chl a/b and Chl tot/Cx+c contents were found in the treatment with 75:25% of NO3-:NH4+, and for Chl b and Cx+c it was observed no difference. In addition, there was a higher photochemical efficiency of PSII (Fv/Fm) when high NO3- concentrations were used. A linear and positive response for the nitrate reductase activity was recorded when the nitrate content increased on the culture substrate. Our results suggest that A. rosaeodora seedlings have a better growth performance when the NO3- concentrations in the culture substrate were higher than the NH4+ concentrations.

Biomass equations for forest regrowth in the eastern Amazon using randomized branch sampling

Forest regrowth occupies an extensive and increasing area in the Amazon basin, but accurate assessment of the impact of regrowth on carbon and nutrient cycles has been hampered by a paucity of available allometric equations. We develop pooled and species-specific equations for total aboveground biomass for a study site in the eastern Amazon that had been abandoned for 15 years. Field work was conducted using randomized branch sampling, a rapid technique that has seen little use in tropical forests. High consistency of sample paths in randomized branch sampling, as measured by the standard error of individual paths (14%), suggests the method may provide substantial efficiencies when compared to traditional procedures. The best fitting equations in this study used the traditional form Y=a×DBHb, where Y is biomass, DBH is diameter at breast height, and a and b are both species-specific parameters. Species-specific equations of the form Y=a(BA×H), where Y is biomass, BA is tree basal area, H is tree height, and a is a species-specific parameter, fit almost as well. Comparison with previously published equations indicated errors from -33% to +29% would have occurred using off-site relationships. We also present equations for stemwood, twigs, and foliage as biomass components.

Biomass production and essential oil yield from leaves, fine stems and resprouts using pruning the crown of Aniba canelilla (H.B.K.) (Lauraceae) in the Central Amazon

Aniba canelilla (H.B.K.) Mez. is a tree species from Amazon that produces essential oil. The oil extraction from its leaves and stems can be an alternative way to avoid the tree cutting for production of essential oil. The aim of this study was to analyse factors that may influence the essential oil production and the biomass of resprouts after pruning the leaves and stems of A. canelilla trees. The tree crowns were pruned in the wet season and after nine months the leaves and stems of the remaining crown and the resprouts were collected, in the dry season. The results showed that the essential oil yield and chemical composition differed among the stems, leaves and resprouts. The stems' essential oil production differed between the seasons and had a higher production in the resprouting stems than the old stems of the remaining crown. The production of essential oil and leaf biomass of resprouts were differently related to the canopy openness, indicating that light increases the production of the essential oil and decreases the biomass of resprouting leaves. This study revealed that plant organs differ in their essential oil production and that the canopy openness must be taken into account when pruning the A. canelilla tree crown in order to achieve higher oil productivity.