Lignocellulosic polysaccharides and lignin degradation by wood decay fungi: the relevance of nonenzymatic Fenton-based reactions

The brown rot fungus Wolfiporia cocos and the selective white rot fungus Perenniporia medulla-panis produce peptides and phenolate-derivative compounds as low molecular weight Fe(3+)-reductants. Phenolates were the major compounds with Fe(3+)-reducing activity in both fungi and displayed Fe(3+)-reducing activity at pH 2.0 and 4.5 in the absence and presence of oxalic acid. The chemical structures of these compounds were identified. Together with Fe(3+) and H(2)O(2) (mediated Fenton reaction) they produced oxygen radicals that oxidized lignocellulosic polysaccharides and lignin extensively in vitro under conditions similar to those found in vivo. These results indicate that, in addition to the extensively studied Gloeophyllum trabeum-a model brown rot fungus-other brown rot fungi as well as selective white rot fungi, possess the means to promote Fenton chemistry to degrade cellulose and hemicellulose, and to modify lignin. Moreover, new information is provided, particularly regarding how lignin is attacked, and either repolymerized or solubilized depending on the type of fungal attack, and suggests a new pathway for selective white rot degradation of wood. The importance of Fenton reactions mediated by phenolates operating separately or synergistically with carbohydrate-degrading enzymes in brown rot fungi, and lignin-modifying enzymes in white rot fungi is discussed. This research improves our understanding of natural processes in carbon cycling in the environment, which may enable the exploration of novel methods for bioconversion of lignocellulose in the production of biofuels or polymers, in addition to the development of new and better ways to protect wood from degradation by microorganisms.

Linoleic acid peroxidation and lignin degradation by enzymes produced by Ceriporiopsis subvermispora grown on wood or in submerged liquid cultures

Ceriporiopsis subvermispora is a white-rot fungus used in biopulping processes and seems to use the fatty acid peroxidation reactions initiated by manganese-peroxidase (MnP) to start lignin degradation. The present work shows that C. subvermispora was able to peroxidize unsaturated fatty acids during wood biotreatment under biopulping conditions. In vitro assays showed that the extent of linoleic acid peroxidation was positively correlated with the level of MnP recovered from the biotreated wood chips. Milled wood was treated in vitro by partially purified MnP and linoleic acid. UV spectroscopy and size exclusion chromatography (SEC) showed that soluble compounds similar to lignin were released from the milled wood. SEC data showed a broad elution profile compatible with low molar mass lignin fractions. MnP-treated milled wood was analyzed by thioacidolysis. The yield of thioacidolysis monomers recovered from guaiacyl and syringyl units decreased by 33% and 20% in MnP-treated milled wood, respectively. This has suggested that lignin depolymerization reactions have occurred during the MnP/linoleic acid treatment. (C) 2009 Elsevier Inc. All rights reserved.

Biomimetic oxidative treatment of spruce wood studied by pyrolysis-molecular beam mass spectrometry coupled with multivariate analysis and (13)C-labeled tetramethylammonium hydroxide thermochemolysis: implications for fungal degradation of wood

In this work, pyrolysis-molecular beam mass spectrometry analysis coupled with principal components analysis and (13)C-labeled tetramethylammonium hydroxide thermochemolysis were used to study lignin oxidation, depolymerization, and demethylation of spruce wood treated by biomimetic oxidative systems. Neat Fenton and chelator-mediated Fenton reaction (CMFR) systems as well as cellulosic enzyme treatments were used to mimic the nonenzymatic process involved in wood brown-rot biodegradation. The results suggest that compared with enzymatic processes, Fenton-based treatment more readily opens the structure of the lignocellulosic matrix, freeing cellulose fibrils from the matrix. The results demonstrate that, under the current treatment conditions, Fenton and CMFR treatment cause limited demethoxylation of lignin in the insoluble wood residue. However, analysis of a water-extractable fraction revealed considerable soluble lignin residue structures that had undergone side chain oxidation as well as demethoxylation upon CMFR treatment. This research has implications for our understanding of nonenzymatic degradation of wood and the diffusion of CMFR agents in the wood cell wall during fungal degradation processes.

Theoretical and experimental study of the thermal degradation of Eucalyptus timber

Thermal action on timber causes it to degrade through combustion of its chemical components, which leads to the release of vapors, combustible gases and surface char. This diminishes its load capacity, due to the reduction of its cross section by charring and to changes in its mechanical properties of strength and stiffness as a function of its exposure to high temperatures. This paper reports the charring rates observed on Eucalyptus structural beams and presents a numerical and experimental study of the behavior of these beams when exposed to fire, in which the properties of strength and stiffness were evaluated as a function of rising temperatures, allowing an analysis of the effect of the section factor on the internal rise in temperature of structural Eucalyptus beams.

Anaerobic degradation of linear alkylbenzene sulfonate (LAS) in fluidized bed reactor by microbial consortia in different support materials

Four anaerobic fluidized bed reactors filled with activated carbon (R1), expanded clay (R2), glass beads (R3) and sand (R4) were tested for anaerobic degradation of LAS. All reactors were inoculated with sludge from a UASB reactor treating swine wastewater and were fed with a synthetic substrate supplemented with approximately 20 mg l(-1) of LAS, on average. To 560 mg l(-1) COD influent, the maximum COD and LAS removal efficiencies were mean values of 97 +/- 2% and 99 +/- 2%, respectively, to all reactors demonstrating the potential applicability of this reactor configuration for treating LAS. The reactors were kept at 30 degrees C and operated with a hydraulic retention time (HRT) of 18 h. The use of glass beads and sand appear attractive because they favor the development of biofilms capable of supporting LAS degradation. Subsequent 16S rRNA gene sequencing and phylogenetic analysis of samples from reactors R3 and R4 revealed that these reactors gave rise to broad microbial diversity, with microorganisms belonging to the phyla Bacteroidetes, Firmicutes, Actinobacteria and Proteobacteria, indicating the role of microbial consortia in degrading the surfactant LAS. (C) 2010 Elsevier Ltd. All rights reserved.

Degradation of formaldehyde in anaerobic sequencing batch biofilm reactor (ASBBR)

The present study evaluated the degradation of formaldehyde in a bench-scale anaerobic sequencing batch reactor, which contained biomass immobilized in polyurethane foam matrices. The reactor was operated for 212 days at 35 C with 8 h sequential cycles, under different affluent formaldehyde concentrations ranging from 31.6 to 1104.4 mg/L (formaldehyde loading rates from 0.08 to 2.78 kg/m(3) day). The results indicate excellent reactor stability and over 99% efficiency in formaldehyde removal, with average effluent formaldehyde concentration of 3.6 + 1.7 mg/L. Formaldehyde degradation rates increased from 204.9 to 698.3 mg/L h as the initial concentration of formaldehyde was increased from around 100 to around 1100 mg/L. However, accumulation of organic matter was observed in the effluent (chemical oxygen demand (COD) values above 500 mg/L) due to the presence of non-degraded organic acids, especially acetic and propionic acids, This observation poses an important question regarding the anaerobic route of formaldehyde degradation, which might differ Substantially from that reported in the literature. The anaerobic degradation pathway can be associated with the formation of long-chain oligomers from formaldehyde. Such long- or short-chain polymers are probably the precursors of organic acid formation by means of acidogenic anaerobic microorganisms. (C) 2008 Elsevier B.V. All rights reserved.

Influence of support material on the immobilization of biomass for the degradation of linear alkylbenzene sulfonate in anaerobic reactors

Two horizontal-flow anaerobic immobilized biomass reactors (HAIB) were used to study the degradation of the LAS surfactant: one filled with charcoal (HAIB1) and the other with a mixed bed of expanded clay and polyurethane foam (HAIB2). The reactors were fed with synthetic substrate supplemented with 14 mg l(-1) of LAS, kept at 30 +/- 2 degrees C and operated with a hydraulic retention time (HRT) of 12 h. The surfactant was quantified by HPLC. Spatial variation analyses were done to quantify organic matter and LAS consumption along the reactor length. The presence of the surfactant in the load did not affect the removal of organic matter (COD), which was close to 90% in both reactors for an influent COD of 550 ring l(-1). The results of a mass balance indicated that 28% of all LAS added to HAIB1 was removed by degradation. HAIB2 presented 27% degradation. Molecular biology techniques revealed microorgan isms belonging the uncultured Holophaga sp., uncultured delta Proteobacterium, uncultured Verrucomicrobium sp., Bacteroides sp. and uncultured gamma Proteobacterium sp. The reactor with biomass immobilized on charcoal presented lower adsorption and a higher kinetic degradation coefficient. So, it was the most suitable support for LAS anaerobic treatment. (c) 2008 Elsevier Ltd. All rights reserved.

Evaluation of the anaerobic degradation of black liquor from a Kraft pulp plant with addition of organic co-substrates

The purpose of this study was to assess the anaerobic degradation of black liquor with and without additional carbon sources. Batch experiments were conducted using black liquor, from an integrated pulp and paper mill adding ethanol, methanol and nutrients. The PCR/DGGE technique was used to characterize the structure of the microbial community. The addition of extra sources of carbon did not significantly influence the degradation of black liquor under the conditions evaluated and the microbial community was similar in all experiments. It was observed an increase in some members of the archaeal in reactors that had the best efficiencies for removal of black liquor (around 7.5%). Either ethanol or methanol can be used as co-substrates because the produce the same quantitative and qualitative effect.

Performance of a horizontal-flow anaerobic immobilized biomass (HAIB) reactor and dynamics of the microbial community during degradation of pentachlorophenol (PCP)

The anaerobic biological treatment of pentachlorophenol (PCP) and methanol as the main carbon source was investigated in a horizontal-flow anaerobic immobilized biomass (HAIB) reactor at 30 +/- 1 degrees C, during a 220-day trial period. The reactor biomass was developed as an attached biofilm on polyurethane foam particles, with 24 h of hydraulic retention time. The PCP concentrations, which ranged from 2.0 to 13.0 mg/L, were controlled by adding synthetic substrate. The HAIB reactor reduced 97% of COD and removed 99% of PCP. The microbial biofilm communities of the HAIB reactor amended with PCP, without previous acclimatization, were characterized by polymerase chain reaction (PCR) and amplified ribosomal DNA restriction analysis (ARDRA) with specific Archaea oligonucleotide primers. The ARDRA technique provided an adequate analysis of the community, revealing the profile of the selected population along the reactor. The biomass activities in the HAIB reactor at the end of the experiments indicated the development of PCP degraders and the maintenance of the population of methanogenic Archaea, ensuring the high efficiency of the system treating PCP with added methanol as the cosubstrate. The use of the simplified ARDRA method enabled us to monitor the microbial population with the addition of high concentrations of toxic compounds and highlighting a selection of microorganisms in the biofilm. (C) 2008 Published by Elsevier Ltd.

Degradation of detergent (linear alkylbenzene sulfonate) in an anaerobic stirred sequencing-batch reactor containing granular biomass

This study aimed to determine the efficiency of an anaerobic stirred sequencing-batch reactor containing granular biomass for the degradation of linear alkylbenzene sulfonate (LAS), a surfactant present in household detergent. The bioreactor was monitored for LAS concentrations in the influent, effluent and sludge, pH, chemical oxygen demand, bicarbonate alkalinity, total solids, and volatile solids. The degradation of LAS was found to be higher in the absence of co-substrates (53%) than in their presence (24-37%). Using the polymerase chain reaction and denaturing gradient gel electrophoresis (PCR/DGGE), we identified populations of microorganisms from the Bacteria and Archaea domains. Among the bacteria, we identified uncultivated populations of Arcanobacterium spp. (94%) and Opitutus spp. (96%). Among the Archaea, we identified Methanospirillum spp. (90%), Methanosaeta spp. (98%), and Methanobacterium spp. (96%). The presence of methanogenic microorganisms shows that LAS did not inhibit anaerobic digestion. Sampling at the last stage of reactor operation recovered 61 clones belonging to the domain bacteria. These represented a variety of phyla: 34% shared significant homology with Bacteroidetes, 18% with Proteobacteria, 11% with Verrucomicrobia, 8% with Fibrobacteres, 2% with Acidobacteria, 3% with Chlorobi and Firmicutes, and 1% with Acidobacteres and Chloroflexi. A small fraction of the clones (13%) were not related to any phylum. Published by Elsevier Ltd.

Stepping-motor-driven constant-shear-rate rotating viscometer

Despite the frequent use of stepping motors in robotics, automation, and a variety of precision instruments, they can hardly be found in rotational viscometers. This paper proposes the use of a stepping motor to drive a conventional constant-shear-rate laboratory rotational viscometer to avoid the use of velocity sensor and gearbox and, thus, simplify the instrument design. To investigate this driving technique, a commercial rotating viscometer has been adapted to be driven by a bipolar stepping motor, which is controlled via a personal computer. Special circuitry has been added to microstep the stepping motor at selectable step sizes and to condition the torque signal. Tests have been carried out using the prototype to produce flow curves for two standard Newtonian fluids (920 and 12 560 mPa (.) s, both at 25 degrees C). The flow curves have been obtained by employing several distinct microstep sizes within the shear rate range of 50-500 s(-1). The results indicate the feasibility of the proposed driving technique.

Friction coefficient and abrasive wear modes in ball-cratering tests conducted at constant normal force and constant pressure-Preliminary results

The micro-scale abrasive wear test by rotative ball has gained large acceptance in universities and research centers, being widely used in studies on the abrasive wear of materials. Two wear modes are usually observed in this type of test: ""rolling abrasion"" results when the abrasive particles roll on the surface of the tested specimen, while ""grooving abrasion"" is observed when the abrasive particles slide; the type of wear mode has a significant effect on the overall behaviour of a tribological system. Several works on the friction coefficient during abrasive wear tests are available in the literature, but only a few were dedicated to the friction coefficient in micro-abrasive wear tests conducted with rotating ball. Additionally, recent works have identified that results may also be affected by the change in contact pressure that occurs when tests are conducted with constant applied force. Thus, the purpose of this work is to study the relationship between friction coefficient and abrasive wear modes in ball-cratering wear tests conducted at ""constant normal force"" and ""constant pressure"". Micro-scale abrasive wear tests were conducted with a ball of AISI52100 steel and a specimen of AISIH10 tool steel. The abrasive slurry was prepared with black silicon carbide (SiC) particles (average particle size of 3 mu m) and distilled water. Two constant normal force values and two constant pressure values were selected for the tests. The tangential and normal loads were monitored throughout the tests and their ratio was calculated to provide an indication of the friction coefficient. In all cases, optical microscopy analysis of the worn craters revelated only the presence of grooving abrasion. However, a more detailed analysis conducted by SEM has indicated that different degrees of rolling abrasion have also occurred along the grooves. The results have also shown that: (i) for the selected values of constant normal force and constant pressure, the friction coefficient presents, approximately, the same range of values and (ii) loading conditions play an important role on the occurrence of rolling abrasion or grooving abrasion and, consequently, on the average value and scatter of the friction coefficient in micro-abrasive wear tests. (C) 2009 Elsevier B.V. All rights reserved.

Characterization of the cold ductility degradation after aging in centrifugally cast 20Cr32Ni+Nb alloy tube

The mechanical properties (yield stress, ultimate tensile stress and elongation) of alloy 20Cr32Ni + Nb subject to isochronal aging at temperatures between 670 and 820 degrees C for 200 h were investigated using samples extracted from a centrifugally cast tube. The results confirm the occurrence of embrittlement in the aged samples, with maximum embrittlement observed around 770 degrees C without significant gain in strength. (C) 2008 Elsevier Ltd. All rights reserved.

Batch distillation: Better at constant or variable reflux?

Due to its outstanding flexibility, batch distillation is still widely used in many separation processes. In the present work, a comparison between constant and variable reflux operations is studied. Firstly, a mathematical model is developed and then validated through comparison between predicted and experimental results accomplished in a lab-scale apparatus. Therefore, case studies are performed through mathematical simulations. It is noted that the most economical form of batch distillation is at constant overhead product composition, keeping the flow rate of vapor from the top of the column constant. (C) 2010 Elsevier B.V. All rights reserved.

A mechanistic kinetic model for phenol degradation by the Fenton process

The objective of this paper is to develop and validate a mechanistic model for the degradation of phenol by the Fenton process. Experiments were performed in semi-batch operation, in which phenol, catechol and hydroquinone concentrations were measured. Using the methodology described in Pontes and Pinto [R.F.F. Pontes, J.M. Pinto, Analysis of integrated kinetic and flow models for anaerobic digesters, Chemical Engineering journal 122 (1-2) (2006) 65-80], a stoichiometric model was first developed, with 53 reactions and 26 compounds, followed by the corresponding kinetic model. Sensitivity analysis was performed to determine the most influential kinetic parameters of the model that were estimated with the obtained experimental results. The adjusted model was used to analyze the impact of the initial concentration and flow rate of reactants on the efficiency of the Fenton process to degrade phenol. Moreover, the model was applied to evaluate the treatment cost of wastewater contaminated with phenol in order to meet environmental standards. (C) 2009 Elsevier B.V. All rights reserved.