The biodegradation of poly-β-(hydroxybutyrate), poly-β-(hydroxybutyrate-co-β-valerate) and poly(ε-caprolactone) in compost derived from municipal solid waste

Understanding the behavior of polymeric materials, particularly their biodegradation, is fundamental for solving problems in the management of environmental residues. In this work, we used a monitoring system based on an aerobic biodegradation technique known as the Sturm test to investigate the biodegradation of poly-β-(hydroxybutyrate), poly-β-(hydroxybutyrate-co-β-valerate) and poly(ε-caprolactone), in compost derived from municipal solid waste. The thermal analysis of these polymers was done using differential scanning calorimeter. The melting temperature and crystallinity were also determined. The results showed that poly-β-(hydroxybutyrate) degraded faster than the other two polymers, probably because the chemical structure of this polymer made attack by microorganisms easier.     

Oxo-biodegradable full carbon backbone polymers - biodegradation behaviour of thermally oxidized polyethylene in an aqueous medium

Several demonstrations of the effective biodegradation in soil of pro-oxidant activated polyethylene (PE) have been reported recently. Nevertheless a comprehensive understanding of the ultimate fate in the environment of the oxidized fragments of oxo-biodegradable polyethylene materials needs the extension of the studies to other natural environments and in particular to aqueous media (river, lake, brackish and marine waters) where accidental plastic littering and the resulting degraded fragments eventually may end up.In this respect, as part of our continuing activity in the area of oxo-biodegradable polymeric materials, in the present paper we wish to report on the results attained in an ongoing investigation on the biodegradation in a water medium of thermally pre-oxidized low density polyethylene (LDPE) film samples containing pro-oxidant additives.Thermally oxidized LDPE-film samples and corresponding acetone extractable fractions were submitted to the effect of microorganism flora present in river water. The effective biodegradation was assessed by monitoring the amount of CO₂ developed over time in a respirometer apparatus. Levels of biodegradation up to 12 and 48% for the degraded fragments and corresponding fractions extracted with boiling acetone were detected on a 100-day time frame.     

Isolation of strains degrading poly(Vinyl alcohol) at high temperatures and their biodegradation ability

Thermophilic strains were isolated for the first time using activated sludge retrieved from waste water treatment plant of a poly(vinyl alcohol) (PVA) producing factory for biodegradation of PVA at relatively high temperatures. The isolated strains were identified to be Geobacillus tepidamans, Brevibacillus brevis and Brevibacillus limnophilus. The former strain degraded PVA for itself, while the latter 2 strains digested PVA symbiotically. PVA degradation activity of the isolated strains was assessed at first by the halo zone size formed around the colonies and finally by the modified Sturm test. The biodegradation rate of PVA was explored also in the presence of different dyes, because most of the waste water from PVA-consuming factories contains waste dyes.     

Cellulose fiber biodegradation in natural waters: river water,brackish water,and seawater

Cellulose, the main component of plant cell walls, is degradable in nature. However, to the best of our knowledge, this is the first report that compares the biodegradability of cellulose fibers with different structures in natural waters. River water, brackish water, and seawater were collected from the Kamo River and Osaka Bay, Japan. Biodegradation of cellulose fibers with different structures and crystallinities, ramie, mercerized ramie, and regenerated cellulose fibers in the collected natural water was investigated in the dark at 20 °C for 30 days. The primary and aerobic ultimate biodegradability were evaluated by weight loss and biochemical oxygen demand (BOD) tests, respectively. In the weight-loss test, cellulose fibers were found to be degraded by more than 50% in any natural water within 30 days. However, in the BOD test, biodegradation was diminished, with values of 40%, 20–30%, and 2–10% in river water, brackish water, and seawater, respectively. These results indicate that cellulose fibers are easily degraded into fine fragments, but it is difficult to cause their ultimate decomposition into water and carbon dioxide. Existence of such a tendency in the degree of biodegradation among the cellulose fibers remains unclear. The molecular weight of cellulose fibers in natural water was also measured during their degradation. The degradation behavior in river water and seawater was observed to be different from that in brackish water. The results thus obtained indicate that the microorganisms and enzymes that degrade cellulose fibers differ depending on the natural water, which influences the degree and mechanism of biodegradation.

     

Biodegradation behavior of poly(butylene adipate-co-terephthalate) (PBAT), poly(lactic acid) (PLA), and their blend under soil conditions

Poly(lactic acid) (PLA) and poly(butylene adipate-co-terephthalate) (PBAT) were mixed at a ratio of 40:60, extruded to form granules and cast into film; then, the PLA, PBAT, and PBAT/PLA film samples were buried in real soil environments. The residual degraded samples were taken regularly from the soil and analyzed by SEM, DSC, TGA, IR spectroscopy and elemental analysis. The analyses showed that PBAT and PLA had different biodegradation mechanisms. Further, the melting temperature and the melting point change of the various components in the PBAT/PLA blend before and after the biodegradation essentially followed the process of the changes in the respective single polymers. After biodegradation, the carbon atom content in the molecular structure of the PBAT, PLA, and PBAT/PLA samples decreased, while the oxygen atom content increased, indicating that the samples indeed degraded. The biodegradation rates of PBAT and PLA in the PBAT/PLA blend were not the same as those for the single materials.     

改性淀粉材料生物降解性分析体系的建立及应用

测定了热塑性淀粉(TPS)和热塑性双醛淀粉(TPDAS)在堆肥条件下的生物降解能力。根据ISO 14855建立了一套新的测试体系并且验证了这个体系测定高分子材料生物降解性能的可行性。对热塑性淀粉材料生物降解性的测试结果发现化学改性对于淀粉的降解速率和降解速度都有很大的影响。在可控堆肥条件下TPS比TPDAS降解的要快。TPDAS的降解速度和最终的生物降解百分率和双醛淀粉(DAS)的氧化度有密切的关系。文中讨论了存在这种关系的可能原因。有不同降解速率的TPS和TPDAS的降解过程呈现出三个阶段,即迟滞阶段。降解阶段和平稳阶段。     

Synthesis and biodegradation of poly(ester amide)s containing amino acid residues: The effect of the stereoisomeric composition of L‐ and D‐phenylalanines on the enzymatic degradation of the polymers

Biodegradable poly(ester amide)s that contained phenylalanine residues in the main chains were synthesized by the polycondensation of di‐p‐nitrophenyl sebacate and phenylalanine 2‐aminoethyl ester. The stereoisomeric composition (L /D ratio) of the phenylalanine residue in the monomer did not affect the yield and molecular weight of the polymer much. From the optical rotations of the polymers, it was found that the L /D ratio of the phenylalanine residue in the polymer was almost equal to the L /D ratio of the phenylalanine residue in the monomer. The biodegradability of the poly(ester amide)s was studied in aqueous solutions with proteases as catalysts. The polymer with 100% L ‐phenylalanine residue was effectively degraded by α‐chymotrypsin or subtilisins. However, the replacement of 10% L ‐phenylalanine with D ‐isomer resulted in a dramatic decrease in degradability. The polymers with less than 30% L ‐isomer were hardly degraded by the enzymes. Gel permeation chromatography studies suggested that the solubility of the degradation products in water greatly affected the rate and extent of biodegradation. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 40: 385–392, 2002     

Biodegradation of poly(lactic acid) and its nanocomposites

PLA nanocomposites based on organically modified montmorillonites at 5% w/w loading were prepared by melt blending using an internal mixer and then degraded in a commercial compost. The addition of nanoclays was found to increase the PLA degradation rate, especially for the highest dispersed clay in the polymer matrix. Biodegradation by microorganisms isolated from the compost showed the bacterium Bacillus licheniformis as one of the responsible for PLA biodegradation in compost. It was also found that clays can influence the polymer bacterial degradation depending on their chemical structure and affinity of the bacterium towards the clay.     

Electrochemical Sensors Continuously Monitor Magnesium Biodegradation under Cell Culture Conditions

Magnesium (Mg) and its alloys have increasingly been considered as implant materials for orthopedic, craniofacial, and cardiovascular applications. These materials generally have mechanical properties close to those of human bone and they biodegrade in aqueous environments. The biodegradation properties can be tailored to fit the desired application by changing the alloying elements and/or by addition of surface coatings. To test and compare the biodegradation properties of different materials, immersion tests in solutions ranging from simple salt solutions to complex biological media are commonly done that yield some information about the biodegradation rate and the biodegradation products on the surface after completion of the test. Here we report on a method that allows the continuous real‐time monitoring of the biodegradation process using electrochemical sensors for pH and H₂ during immersion of Mg samples in the cell culture medium DMEM/F12 with different concentrations of fetal bovine serum and in the presence of living cells. The sensors effectively indicated the biodegradation behavior of Mg samples in real‐time. This system could be very useful for immersion tests and even supporting biocompatibility testing of implant materials.     

Biodegradation of a synthetic co-polyester by aerobic mesophilic microorganisms

The aerobic biological degradation of the synthetic aliphatic-aromatic co-polyester Ecoflex™ (BASF) by 29 strains of enzyme-producing soil bacteria, fungi and yeasts was investigated at moderate environmental conditions. Previous studies had shown that these materials could be degraded but these studies were done under thermophilic conditions. In this paper, a screening procedure was developed to assess the biodegradability of the co-polyester at ambient environmental conditions and to investigate the mechanism of biodegradation. Results showed that the aliphatic-aromatic co-polyester could be degraded by a number of different microorganisms. However, after 21 days exposure to even the most promising cultures of pure microorganisms, only partial degradation of the Ecoflex™ was accomplished and only a few samples showed visible signs of degradation as loosely defined by the mechanical weakening of the films. Weight loss was not as obvious as the visual degradation and suggested broader types of microbial attack. The bacteria studied preferentially degraded the bonds between aliphatic components of the copolymer and the rate of biodegradation of oligomers was appreciably faster than that for the polymer chains. Using GC-MS techniques, degradation intermediates were identified to be the monomers of the co-polyester. Gel permeation chromatography results suggested exo-enzyme type degradation, where the microbes hydrolysed the ester bonds at the termini of the polymeric chains preferentially.     

Aerobic and anaerobic microbial degradation of poly-beta-hydroxybutyrate produced by Azotobacter chroococcum

Food industry wastewater served as a carbon source for the synthesis of poly-β-hydroxybutyrate (PHB) by Azotobacter chroococcum. The content of polymer in bacterial cells grown on the raw materials reached 75%. PHB films were degraded under aerobic, microaerobic, and anaerobic conditions in the presence and absence of nitrate by microbial populations of soil, sludges from anaerobic and nitrifying/denitrifying reactors, and sediment from a sludge deposit site. Changes in molecular mass, crystallinity, and mechanical properties of PHB were studied. Anaerobic degradation was accompanied by acetate formation, which was the main intermediate utilized by denitrifying bacteria or methanogenic archaea. On a decrease in temperature from 20 to 5° C in the presence of nitrate, the rate of PHB degradation was 7.3 times lower. Under anaerobic conditions and in the absence of nitrate, no PHB degradation was observed, even at 11°C. The enrichment cultures of denitrifying bacteria obtained from soil and anaerobic sludge degraded PHB films for a short time (3–7 d). The dominant species in the enrichment culture from soil were Pseudomonas fluorescens and Pseudomonas stutzeri. The rate of PHB degradation by the enrichment cultures depended on the polymer molecular weight, which reduced with time during biodegradation.     

Hybrid process for the conversion of lignocellulosic materials

Because of the recalcitrant nature of lignocellulosic materials, it is important to pretreat the biomass in order to obtain a suitable material for the bioconversion. In this study, two different types of pretreatments were performed. The first experiment used a 2-gal Parr reactor operated at 140, 150,160, and 170‡C with sulfuric acid concentrations varying from 0.5 to 2%. A second pretreatment was performed with a two-stage low-temperature process. The first-stage pretreatment was performed at 100 or 120‡C with sulfuric acid concentrations of 0.5, 2, and 5% followed by a secondstage pretreatment at 120‡C with 2% acid concentration. The best residues for enzymatic hydrolysis and simultaneous saccharification and fermentations (SSF) came from the higher temperature pretreatment with the Parr reactor. However, a large portion of the xylose fraction was degraded to furfural and glucose was degraded to HMF. On the contrary, the two-stage low temperature pretreatment resulted in a very low percentage of xylose degradation, and no glucose degradation. The residues from this two-stage pretreatment performed satisfactorily toward the production of ethanol by SSFs. This study discusses the results obtained from these experiments.     

Investigation of the synergy in intumescent polyurethane by 3D computed tomography

The morphology of carbonized materials resulting from an intumescence phenomenon was studied. The investigated material is a polyurethane matrix filled either by 30 wt.-% of ammonium polyphosphate or by a combination of 28 wt.-% of ammonium polyphosphate and 2 wt.-% of nano-magnesium oxide. These fillers were incorporated in the polyurethane directly during the synthesis step. The carbonized materials or char, are obtained in a specific fire scenario. Characterization of their morphology is carried out using X-ray computed tomography. The heat conductivity of the systems is additionally measured as a function of temperature in order to correlate structure and properties of the intumescent residues. The formation of different char structures with incorporation of magnesium oxide (in particular formation of bubbles of different size) is first evidenced. These observations are consistent with the heat conductivity data. Tomography images demonstrate that the intumescence process is a dynamic process since non degraded polymer is left at the beginning of the fire test, which is not the case for longer time. The dispersion of fillers has finally been investigated in the chars and it is evidenced different steps of intumescence's development in the material.     

How the biodegradability of wheat gluten-based agromaterial can be modulated by adding nanoclays

The objective of this work was to investigate the influence of clay nanoparticles on the biodegradability of wheat gluten-based materials through a better understanding of multi-scale relationships between biodegradability, water transfer properties and structure of wheat gluten/clay materials. Wheat gluten/clay (nano)composites materials were prepared via bi-vis extrusion by using an unmodified sodium montmorillonite (MMT) and an organically modified MMT. Respirometric experiments showed that the rate of biodegradation of wheat gluten-based materials could be slowed down by adding unmodified MMT (HPS) without affecting the final biodegradation level whereas the presence of an organically modified MMT (C30B) did not significantly influence the biodegradation pattern. Based on the evaluation of the water sensitivity and a multi-scale characterization of material structure, three hypotheses have been proposed to account for the underlying mechanisms. The molecular/macromolecular affinity between the clay layers and the wheat gluten matrix, i.e. the ability of both components to establish interactions appeared as the key parameter governing the nanostructure, the water sensitivity and, as a result, the overall biodegradation process.     

Degradation of Mater-Bi/wood flour biocomposites in active sewage sludge

The mechanical properties of Mater-Bi^® are, in general, not adequate for certain applications and the addition of a filler is therefore necessary. Among the different fillers, natural fibres are particularly interesting because they potentially allow improving the performance of the material without compromising its biodegradability.In order to improve the basic mechanical properties of a Mater-Bi grade and to obtain a new, fully biodegradable material, wood flour based composites were prepared by different processing methods. To simulate actual and not laboratory bacterial attack on the prepared materials, in this work we studied the biodegradation of the composites in a real active sewage sludge reactor. In particular, the biodegradation rates were investigated with reference to different pre-treatments of the materials and different environmental conditions (summer and winter). The results showed that wood flour enhances the biodegradability of the materials. The results indicated also strong relationships between the surface roughness and the biodegradation rates (in particular, higher roughness leads to wider bacterial attack). The different processing techniques had direct effects on the overall biodegradation rates. In particular, when higher smoothness and packing is achieved, the biodegradation rate is lower. The mechanical analysis indicated that adding wood flour to Mater-Bi has positive effects on the elastic modulus, but when the bacterial attack becomes critical, a general sudden drop of the mechanical properties is observed.     

Abiotic and biotic degradation of oxo-biodegradable polyethylenes

Conventional polymeric materials accumulate in the environment due to their low biodegradability. However, an increase in the biodegradation rate of these polymers may be obtained with the addition of pro-degrading substances. This study aimed to evaluate abiotic and biotic degradation of polyethylenes (PEs) using plastic bags of high-density polyethylene (HDPE) and linear low-density polyethylene (LLDPE) formulated with pro-oxidant additives as test materials. These packaging materials were exposed to natural weathering and periodically analyzed with respect to changes in mechanical and structural properties. After a year of exposure, residue samples of the bags were incubated in substrates (compost of urban solid waste, perlite and soil) at 58 °C and at 50% humidity. The biodegradation of the materials was estimated by their mineralization to CO₂. The molar mass of the pro-oxidant-activated PE decreased and oxygen incorporation into the chains increased significantly during natural weathering. These samples showed a mineralization level of 12.4% after three months of incubation with compost. Higher extents of mineralization were obtained for saturated humidity than for natural humidity. The growth of fungi of the genera Aspergillus and Penicillium was observed on PE films containing pro-oxidant additives exposed to natural weathering for one year or longer. Conventional PE films exposed to natural weathering showed small biodegradation.     

Cationic ester-containing gemini surfactants: chemical hydrolysis and biodegradation

Two cationic gemini surfactants having ester bonds between the hydrophobic tail and the cationic moiety have been synthesized. The ester bonds were either with the ester carbonyl group away from the positive charge (esterquat type arrangement) or facing the positive charge (betaine ester type arrangement). The chemical hydrolysis of the surfactants was investigated and compared with the hydrolysis of the corresponding monomeric surfactants. The betaine ester type of surfactants was found to hydrolyze much faster than the esterquat surfactants. It was also seen that above the critical micelle concentration the gemini surfactants were much more susceptible to alkaline hydrolysis than the corresponding monomeric surfactants. The biodegradation of the geminis and the monomeric surfactants were also studied. It was found that whereas the monomeric surfactants were rapidly degraded, the two gemini surfactants were more resistant to biodegradation and could not be classified as readily biodegradable. The 60% biodegradation was reached after 35-40 days. Thus, there was no correlation between rate of chemical hydrolysis and rate of biodegradation.     

Fungal Biodegradation of Lignin Graft Copolymers from Ethene Monomers

Abstract

White rot Basidiomycetes were able to biodegrade styrene (1-phenylethene) or methyl methacrylate (4-methyl-2-oxy-3-oxopent-4-ene) graft copolymers of lignin containing different proportions of lignin and polystyrene [poly(1-phenylethylene)] or polymethyl methacrylate [poly(1-methyl-1-(1-oxo-2-oxypropyl)ethylene)]. The biodegradation tests were run on lignin/styrene copolymerization products which contained 10.3, 32.2, and 50.4 wt% lignin while biodegradation tests were run on lignin/methyl methacrylate copolymerization products which contained 11 to 18 wt% lignin. The styrene polymer samples were incubated with white rot Pleurotus ostreatus, Phanerochaete chrysosporium, Trametes versicolor, and brown rot Gloeophyllum trabeum. The methyl methacrylate polymer samples were incubated with white rot Pleurotus ostreatus, Trametes versicolor, and Phlebia radiata. White rot fungi degraded the plastic samples at a rate which increased with increasing lignin content in the copolymer sample. Both polystyrene and lignin components of the copolymer were readily degraded. Polystyrene pellets and polymethyl methacrylate sheets were not degradable in these tests. Degradation was verified by weight loss, quantitative ultraviolet spectrophotometric analysis of both lignin and styrene residue, and scanning electron microscopy of the plastic surface for both incubated or control samples. Brown rot fungus did not affect any of these plastics.     

Determination of Biodegradation Process of Benzene,Toluene, Ethylbenzene and Xylenes in Seabed Sediment by Purge and Trap Gas Chromatography

Benzene, toluene, ethylbenzene, and xylenes (BTEX) are commonly found in crude oil and are used in geochemical investigations as direct indicators of the presence of oil and gas. BTEX are easily volatile and can be degraded by microorganisms, which affect their precise measurement seriously. A method for determining the biodegradation process of BTEX in seabed sediment using dynamic headspace (purge and trap) gas chromatography with a photoionization detector (PID) was developed, which had a detection limit of 7.3–13.2 ng L⁻¹ and a recovery rate of 91.6–95.0%. The decrease in the concentration of BTEX components was monitored in seabed sediment samples, which was caused by microorganism biodegradation. The results of BTEX biodegradation process were of great significance in the collection, transportation, preservation, and measurement of seabed sediment samples in the geochemical investigations of oil and gas.

     

壳聚糖超声可控降解及降解动力学研究

通过正交实验法考察了壳聚糖溶液浓度、反应温度、超声强度以及醋酸溶液浓度对超声降解反应的影响,确定了最佳反应条件,制备了一系列不同分子量的壳聚糖.研究了壳聚糖溶液浓度、反应温度以及壳聚糖原料分子参数与降解速率常数的关系.通过红外光谱、X-射线衍射和凝胶渗透色谱对降解产物进行了表征.结果表明,超声降解壳聚糖的最佳条件为10℃,壳聚糖溶液浓度2.5g/L.降解速率常数随壳聚糖溶液浓度和反应温度的降低而增大.高分子量和低脱乙酰度的壳聚糖原料有较高的降解速率和降解速率常数,壳聚糖原料的分子量对降解速率和降解速率常数的影响大于脱乙酰度对其的影响.超声波导致了壳聚糖分子量的降低和产物晶体结构的破坏,但没有改变产物的脱乙酰度和糖残基结构.