Lignin chemistry and topochemistry during kraft delignification of Eucalyptus globulus genotypes with contrasting pulpwood characteristics

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

USE OF ADDITIVES IN THE WOOD BIODEGRADATION BY THE FUNGUS Ceriporiopsis subvermispora: EFFECT IN THE MANGANESE PEROXIDASE-DEPENDENT LIPID PEROXIDATION

USE OF ADDITIVES IN THE WOOD BIODEGRADATION BY THE FUNGUS Ceriporiopsis subvermispora: EFFECT IN THE MANGANESE PEROXIDASE-DEPENDENT LIPID PEROXIDATION. Ceriporiopsis subvermispora is a selective fungus in the wood delignification and the most promising in biopulping. Through the lipid peroxidation initiated by manganese peroxidase (MnP), free radicals can be generated, which can act in the degradation of lignin nonphenolic structures. This work evaluated the prooxidant activity (based in lipid peroxidation) of enzymatic extracts from wood biodegradation by this fungus in cultures containing exogenous calcium, oxalic acid or soybean oil. It was observed that MnP significant activity is required to promote lipid peroxidation and wood delignification. Positive correlation between prooxidant activity x MnP was observed up to 300 IU kg(-1) of wood.

IDENTIFICATION OF ETHANOLIC WOOD EXTRACTS USING ELECTRONIC ABSORPTION SPECTRUM AND MULTIVARIATE ANALYSIS

IDENTIFICATION OF ETHANOLIC WOOD EXTRACTS USING ELECTRONIC ABSORPTION SPECTRUM AND MULTIVARIATE ANALYSIS. The application of multivariate analysis to spectrophotometric (UV) data was explored for distinguishing extracts of cachaca woods commonly used in the manufacture of casks for aging cachacas (oak, cabretiva-parda, jatoba, amendoim and canela-sassafras). Absorbances close to 280 nm were more strongly correlated with oak and jatoba woods, whereas absorbances near 230 nm were more correlated with canela-sassafras and cabretiva-parda. A comparison between the spectrophotometric model and the model based on chromatographic (HPLC-DAD) data was carried out. The spectrophotometric model better explained the variance data (PC1 + PC2 = 91%) exhibiting potential as a routine method for checking aged spirits.

Alkaline sulfite/anthraquinone pretreatment followed by disk refining of Pinus radiata and Pinus caribaea wood chips for biochemical ethanol production

BACKGROUND: Alkaline sulfite/anthraquinone (ASA) cooking of Pinus radiata and Pinus caribaea wood chips followed by disk refining was used as a pretreatment for the production of low lignified and high fibrillated pulps. The pulps produced with different delignification degrees and refined at different energy inputs (250, 750 and 1600 Wh) were saccharified with cellulases and fermented to ethanol with Saccharomyces cerevisiae using separated hydrolysis and fermentation (SHF) or semi-simultaneous saccharification and fermentation (SSSF) processes. RESULTS: Delignification of ASA pulps was between 25% and 50%, with low glucans losses. Pulp yield was from 70 to 78% for pulps of P. radiata and 60% for the pulp of P. caribaea. Pulps obtained after refining were evaluated in assays of enzymatic hydrolysis. Glucans-to-glucose conversion varied from 20 to 70%, depending on the degree of delignification and fibrillation of the pulps. The best ASA pulp of P. radiata was used in SHF and SSSF experiments of ethanol production. Such experiments produced maximum ethanol concentration of 20 g L-1, which represented roughly90% of glucose conversion and an estimated amount of 260 L ethanol ton(-1) wood. P. caribaea pulp also presented good performance in the enzymatic hydrolysis and fermentation but, due to the low amount of cellulose present, only 140 L ethanol would be obtained from each ton of wood. CONCLUSION: ASA cooking followed by disk refining was shown to be an efficient pretreatment process, which generated a low lignified and high-fibrillated substrate that allowed the production of ethanol from the softwoods with high conversion yields. (C) 2012 Society of Chemical Industry

Multivariate analyses of UV-Vis absorption spectral data from cachaca wood extracts: a model to classify aged Brazilian cachacas according to the wood species used

Multivariate analyses of UV-Vis spectral data from cachaca wood extracts provide a simple and robust model to classify aged Brazilian cachacas according to the wood species used in the maturation barrels. The model is based on inspection of 93 extracts of oak and different Brazilian wood species by a non-aged cachaca used as an extraction solvent. Application of PCA (Principal Components Analysis) and HCA (Hierarchical Cluster Analysis) leads to identification of 6 clusters of cachaca wood extracts (amburana, amendoim, balsamo, castanheira, jatoba, and oak). LDA (Linear Discriminant Analysis) affords classification of 10 different wood species used in the cachaca extracts (amburana, amendoim, balsamo, cabreuva-parda, canela-sassafras, castanheira, jatoba, jequitiba-rosa, louro-canela, and oak) with an accuracy ranging from 80% (amendoim and castanheira) to 100% (balsamo and jequitiba-rosa). The methodology provides a low-cost alternative to methods based on liquid chromatography and mass spectrometry to classify cachacas aged in barrels that are composed of different wood species.

From Folke Medicine to Medicine Chemistry: Study, Using in Vitro and Cellular Assays, of Receptors Mechanism Involved in the Activities of Natural Compounds

My Doctorate Research has been focused on the evaluation of the pharmacological activity of a natural extract of chestnut wood (ENC) towards the cardiovascular and gastrointestinal system and on the identification of the active compounds. The ENC has been shown to contain more than 10% (w/w) of phenolic compounds, of which tannins as Vescalgin and Castalgin are the more representative. ENC cardiovascular effects have been investigated in guinea pig cardiac preparations; furthermore its activity has been evalueted in guinea pig aorta strips. ENC induced transient negative chronotropic effect in isolated spontaneously beating right atria and simultaneously positive inotropic effect in left atria driven at 1 Hz. Cardiac cholinergic receptors are not involved in the negative chronotropic effect and positive inotropic effects are not related to adrenergic receptors. In vascular smooth muscle, natural extract of chestnut did not significantly change the contraction induced by potassium (80 mM) or that induced by noradrenaline (1μM). In guinea pig ileum, ENC reduced the maximum response to carbachol in a concentrationdependent manner and behaved as a reversible non competitive antagonist. In guinea pig ileum, the antispasmodic activity of ENC showed a significant antispasmodic activity against a variety of different spasmogenic agents including histamine, KCl, BaCl2. In guinea pig proximal colon, stomach and jejunum, ENC reduced the maximum response to carbachol in a concentrationdependent manner and behaved as a reversible non competitive antagonist. ENC contracted gallbladder guinea pig in a reversible and concentration-dependent manner. This effect does not involve cholinergic and cholecystokinin receptors and it is reduced by nifedipine. ENC relaxed Oddi sphincter smooth muscle. The cholecystokinetic and Oddi sphincter relaxing activities occurred also in guinea pigs fed a lithogenic diet. The cholecystokinetic occurred also in human gallbladder. The Fractionation of the extract led to the identification of the active fraction.

Photodegradation and photostabilization of weathered wood flour filled polyethylene composites

Wood plastic composites (WPCs) have gained popularity as building materials because of their usefulness in replacing solid wood in a variety of applications. These composites are promoted as being low-maintenance, high-durability products. However, it has been shown that WPCs exposed to weathering may experience a color change and/or loss in mechanical properties. An important requirement for building materials used in outdoor applications is the retention of their aesthetic qualities and mechanical properties during service life. Therefore, it is critical to understand the photodegradation mechanisms of WPCs exposed to UV radiation and to develop approaches to stabilize these composites (both unstabilized and stabilized) as well as the effect of weathering on the color fade and the retention of mechanical properties were characterized. Since different methods of manufacturing WPCs lead to different surface characteristics, which can influence weathering, the effect of manufacturing method on the photodegradation of WPCs was investigated first. Wood flour (WF) filled high-density polyethylene (HDPE) composite samples were either injection molded, extruded, or extruded and then planed. Fourier transform infrared (FTIR) spectroscopy was used to monitor the surface chemistry of the manufactured composites. The spectra showed that the surface of planed samples had more wood component than extruded and injection molded samples, respectively. After weathering, the samples were analyzed for color fade, and loss of flexural properties. The final lightness of the composites was not dependent upon the manufacturing method. However the mechanical property loss was dependent upon manufacturing method. The samples with more wood component at the surface (planed samples) experienced a larger percentage of total loss in flexural properties after weathering due to a greater effect of moisture on the samples. The change in surface chemistry of HDPE and WF/HDPE composites after weathering was studied using spectroscopic techniques. X-ray photoelectron spectroscopy (XPS) was used to characterize the occurrence of surface oxidation whereas FTIR spectroscopy was used to monitor the development of degradation products, such as carbonyl groups and vinyl groups, and to determine changes in HDPE crystallinity. Surface oxidation occurred immediately after exposure for both the neat HDPE and WF/HDPE composites. After weathering, the surface of the WF/HDPE composites was oxidized to a greater extent than the neat HDPE after weathering. This suggests that photodegradation is exacerbated by the addition of the carbonyl functional groups of the wood fibers within the HDPE atrix during composite manufacturing. While neat HDPE may undergo cross-linking in the initial stages of accelerated weathering, the WF may physically hinder the ability of the HDPE to cross-link resulting in the potential for HDPE chain scission to dominate in the initial weathering stages of the WF/HDPE composites. To determine which photostabilizers are most effective for WF/HDPE composites, factorial experimental designes were used to determine the effects of adding two hindered amine light stabilizers, an ultraviolet absorber, and a pigment on the color made and mechanical properties of both unweathered and UV weathered samples. Both the pigment and ultraviolet absorber were more effective photostabilizers for WF/HDPE composites than hinder amine light stabilizers. The ineffectiveness of hindered amine light stabilizers in protecting WPCs against UV radiation was attribuated to the acid/base reactions occurring between the WF and hindered amine light stabilizer. The efficiency of an ultraviolet absorber and/or pigment was also examined by incorporating different concentration of an ultraviolet absorber and/or pigment into WF/HDPE composites. Color change and flexural properties were determined after accelerated UV weathering. The lightness of the composite after weathering was influenced by the concentration of both the ultraviolet absorber by masking the bleaching wood component as well as blocking UV light. Flexural MOE loss was influenced by an increase in ultraviolet absorber concentration, but increasing pigment concentration from 1 to 2% had little influence on MOE loss. However, increasing both ultraviolet absorber and pigment concentration resulted in improved strength properties over the unstabilized composites after 3000 h of weather. Finally, the change in surface chemistry due to weathering of WF/HDPE composites that were either unstabilized or stabilized with an ultraviolet absorber and/or pigment was analyzed using FTIR spectroscopy. The samples were tested for loss in modulus of elasticity, carbonyl and vinyl group formation at the surface, and change in HDPE crystallinity. It was concluded that structural changes in the samples; carbonyl group formation, terminal vinyl group formation, and crystallinity changes cannot reliably be used to predict changes in modulus of elasticity using a simple linear relationship. The effect of cross-linking, chain scission, and crystallinity changes due to ultraviolet exposure as well as the interfacial degradation due to moisture exposure are inter-related factors when weathering HDPE and WF/HDPE composites.

Sources and contributions of wood smoke during winter in London: assessing local and regional influences

Determining the contribution of wood smoke to air pollution in large cities such as London is becoming increasingly important due to the changing nature of domestic heating in urban areas. During winter, biomass burning emissions have been identified as a major cause of exceedances of European air quality limits. The aim of this work was to quantify the contribution of biomass burning in London to concentrations of PM2:5 and determine whether local emissions or regional contributions were the main source of biomass smoke. To achieve this, a number of biomass burning chemical tracers were analysed at a site within central London and two sites in surrounding rural areas. Concentrations of levoglucosan, elemental carbon (EC), organic carbon (OC) and K+ were generally well correlated across the three sites. At all the sites, biomass burning was found to be a source of OC and EC, with the largest contribution of EC from traffic emissions, while for OC the dominant fraction included contributions from secondary organic aerosols, primary biogenic and cooking sources. Source apportionment of the EC and OC was found to give reasonable estimation of the total carbon from non-fossil and fossil fuel sources based upon comparison with estimates derived from 14C analysis. Aethalometer-derived black carbon data were also apportioned into the contributions frombiomass burning and traffic and showed trends similar to those observed for EC. Mean wood smoke mass at the sites was estimated to range from 0.78 to 1.0 μgm-3 during the campaign in January–February 2012. Measurements on a 160m tower in London suggested a similar ratio of brown to black carbon (reflecting wood burning and traffic respectively) in regional and London air. Peaks in the levoglucosan and K+ concentrations were observed to coincide with low ambient temperature, consistent with domestic heating as a major contributing local source in London. Overall, the source of biomass smoke in London was concluded to be a background regional source overlaid by contributions from local domestic burning emissions. This could have implications when considering future emission control strategies during winter and may be the focus of future work in order to better determine the contributing local sources.

Comparison of several wood smoke markers and source apportionment methods for wood burning particulate mass

Residential wood combustion has only recently been recognized as a major contributor to air pollution in Switzerland and in other European countries. A source apportionment method using the aethalometer light absorption parameters was applied to five winter campaigns at three sites in Switzerland: a village with high wood combustion activity in winter, an urban background site and a highway site. The particulate mass from traffic (PMtraffic) and wood burning (PMwb) emissions obtained with this model compared fairly well with results from the 14C source apportionment method. PMwb from the model was also compared to well known wood smoke markers such as anhydrosugars (levoglucosan and mannosan) and fine mode potassium, as well as to a marker recently suggested from the Aerodyne aerosol mass spectrometer (mass fragment m/z 60). Additionally the anhydrosugars were compared to the 14C results and were shown to be comparable to literature values from wood burning emission studies using different types of wood (hardwood, softwood). The levoglucosan to PMwb ratios varied much more strongly between the different campaigns (4–13%) compared to mannosan to PMwb with a range of 1–1.5%. Possible uncertainty aspects for the various methods and markers are discussed.

Canopy gaps promote selective stem-cutting by small mammals of two dominant tree species in an African lowland forest: the importance of seedling chemistry

Small mammals can impede tree regeneration by injuring seedlings and saplings in several ways. One fatal way is by severing their stems, but apparently this type of predation is not well-studied in tropical rain forest. Here, we report on the incidence of 'stem-cutting' to new, wild seedlings of two locally dominant, canopy tree species monitored in 40 paired forest understorey and gap-habitat areas in Korup, Cameroon following a 2007 masting event. In gap areas, which are required for the upward growth and sapling recruitment of both species, 137 seedlings of the long-lived, light-demanding, fast-growing large tropical tree (Microberlinia bisulcata) were highly susceptible to stem-cutting (83% of deaths) - it killed 39% of all seedlings over a c. 2-y period. In stark contrast, seedlings of the more shade-tolerant, slower-growing tree species (Tetraberlinia bifoliolata) were hardly attacked (4.3%). In the understorey, however, stem-cutting was virtually absent. Across the gap areas, the incidence of stem-cutting of M. bisulcata seedlings showed significant spatial variation that could not be explained significantly by either canopy openness or Janzen-Connell type effects (proximity and basal area of conspecific adult trees). To examine physical and chemical traits that might explain the species difference to being cut, bark and wood tissues were collected from a separate sample of seedlings in gaps (i.e. not monitored for stem-cutting). These analyses suggested that, compared with T. bifoliolata, the lower stem density, higher Mg and K and fatty acid concentrations in bark, and fewer phenolic and terpene compounds in M. bisulcata seedlings made them more palatable and attractive to small-mammal predators, likely rodents. We conclude that selective stem-cutting is a potent countervailing force to the current local canopy dominance of the grove-forming M. bisulcata by limiting the recruitment and abundance of its saplings. Given the ubiquity of gaps and ground-dwelling rodents in pantropical forests, it would be surprising if this form of lethal browsing was restricted to Korup.

Seawater carbonate chemistry and nutrient fluxes during experiments with brittlestar Amphiura filiformis, 2009

Rising levels of atmospheric carbon dioxide and the concomitant increased uptake of this by the oceans is resulting in hypercapnia-related reduction of ocean pH. Research focussed on the direct effects of these physicochemical changes on marine invertebrates has begun to improve our understanding of impacts at the level of individual physiologies. However, CO2-related impairment of organisms' contribution to ecological or ecosystem processes has barely been addressed. The burrowing ophiuroid Amphiura filiformis, which has a physiology that makes it susceptible to reduced pH, plays a key role in sediment nutrient cycling by mixing and irrigating the sediment, a process known as bioturbation. Here we investigate the role of A. filiformis in modifying nutrient flux rates across the sediment-water boundary and the impact of CO2- related acidification on this process. A 40 day exposure study was conducted under predicted pH scenarios from the years 2100 (pH 7.7) and 2300 (pH 7.3), plus an additional treatment of pH 6.8. This study demonstrated strong relationships between A. filiformis density and cycling of some nutrients; activity increases the sediment uptake of phosphate and the release of nitrite and nitrate. No relationship between A. filiformis density and the flux of ammonium or silicate were observed. Results also indicated that, within the timescale of this experiment, effects at the individual bioturbator level appear not to translate into reduced ecosystem influence. However, long term survival of key bioturbating species is far from assured and changes in both bioturbation and microbial processes could alter key biogeochemical processes in future, more acidic oceans.