Biodegradation of Poly(ε-caprolactone) (PCL) Film by <Emphasis Type="Italic">Alcaligenes faecalis</Emphasis>

The biodegradation behavior of PCL film with high molecular weight (80,000 Da) in presence of bacterium Alcaligenes faecalis and the analysis of degraded polymer film have been carried out. Thin Films of PCL were prepared by means of solution casting method and the bacterial degradation behavior was carried in basal medium, in presence of bacteria with time variation after UV treatment. It was observed that after UV treatment the degradation of polymer film was increased and the degradation rate followed a three steps degradation mechanism. The degraded polymer film was analyzed by means of Differential Scanning Calorimeter (DSC), Thermo Gravimetric Analyzer (TGA) and Fourier Transform Infrared Spectroscope (FTIR). DSC results revealed that at the initial stages of the degradation up to 15–20 days, the bacterium preferentially degrades the amorphous parts of the polymer film over the crystalline zone. Thermo gravimetric analysis highlighted the low temperature stability of degraded films with extent of degradation. FTIR results showed the chain scission mechanism of the polymer chains and also supported the preferential degradation of amorphous phase over crystalline phase in the initial stages of the degradation.     

Morphology of <Emphasis Type="Italic">Penicillium funiculosum</Emphasis> During Biodegradation of Poly (β-hydroxybutyrate-co-β-hydroxyvalerate) [PHBV] with Poly (ε-Caprolactone) [PCL] Blends

Blends of poly (β-hydroxybutyrate-co-β-hydroxyvalerate) with poly (ε-caprolactone) were produced using melt mixing and solvent casting techniques. The biodegradation of blends was tested based in the ASTM G21-90 using Penicillium funiculosum fungal specie. The CO₂ production during biodegradation was measured and fitted using the Gompertz model. Biodegradation of blends varies according to the mixing technique and the proportion of bacterial polymers in the blends. Although lag phase was larger, solvent-casted blends were easier to degrade due to their porous surface and relative lower crystallinity. P. funiculosum morphology during biodegradation appeared to be related to carbon availability i.e. larger and more complex conidiophores, more phialides per conidiophore and the presence of double-phialides, were found in blends with higher PHAs proportion. P. funiculosum morphology was independent to the blending technique used. Hence, morphology of P. funiculosum could be useful as a reference for carbon bioavailability of the blends.     

Thermal Properties and Crystallization Behavior of Novel Biodegradable Poly(hexamethylene succinate-<Emphasis Type="Italic">co</Emphasis>-6 mol% butylene succinate) and Poly(hexamethylene succinate)

In this research, the thermal properties and crystallization behavior of novel poly(hexamethylene succinate-co-6 mol% butylene succinate) (PHBS) and its homopolymer poly(hexamethylene succinate) (PHS) were extensively studied. With respect to PHS, the introduction of a small content of butylene succinate (BS) unit slightly reduces the melting point and equilibrium melting point but hardly influences the glass transition temperature of PHBS. Despite crystallization temperature, PHS and PHBS crystallize through the same crystallization mechanism. At the same crystallization temperature, PHBS crystallizes more slowly than PHS; furthermore, lowering crystallization temperature enhances the crystallization rates of PHBS and PHS. The spherulites morphologies were observed for both of them, with the spherulites nucleation density of the copolymer being smaller than that of the homopolymer. PHBS and PHS share the same crystal structures, indicative of the location of BS unit in the amorphous region.     

Study of Trace and Heavy Metals in Rural and Urban Aerosols of Uludağ and Bursa (Turkey)

The concentrations of heavy, trace elements and major ions measuredin the Uluda and Bursa aerosols were investigated to assess size distributions, spatial and temporal variability, sources and source regions affecting the composition of aerosols in Uluda and Bursa. A total of 81 samples were collected in two sites, one in Bursa city and another in the Uluda Mountain during two sampling campaigns. Daily samples were collected using a high volume sampler on Whatman 41 cellulose filters in Uluda, while three days interval samples were collected in Bursa using an automatic dichotomous sampler on PTFE Teflon filters. Samples were analysed for 15 trace and heavy metals (Al, Fe, Ba, Na, Mg, K, Mn, Ca, Cu), (V, Pb, Cd, Cr, Ni, Zn), and 4 major ions (SO₄ ^2-, NO₃ ^-, Cl^-), (NH₄ ⁺) using ICP-AES, GFAAS, HPLC and UV/VIS Spectrophotometer,respectively. In general, concentrations of the metals measured inUluda aerosols were lower than those in Bursa. The concentrations of crustal elements were higher in summer than winter, while anthropogenic elements had higher concentrations in winter than summer. Most of the mass of crustal elements was concentrated in the coarse mode while the mass of the heavy metals was concentrated in the fine mode. Factor analysis revealed four factors with sources including crustal, industrial and combustion. Back trajectory calculations were used to determine long range contributions. These calculations showed that contributions were mostly from European countries, former Soviet Union countries, Black Sea and North Africa.     

Potential of <Emphasis Type="Italic">pinhão</Emphasis> Coat as Constituents of Starch Based Films Using Modification Techniques

The potential of lignocellulosic fibers obtained by dry grinding of pinhão coat as fillers in starch filmogenic solutions for packaging applications was evaluated in this work. To improve the incorporation of this waste into the starch solutions different physical and chemical treatments were conducted. Thereafter, morphology, chemical structure, crystallinity and water absorption of the pinhão coat powders were determined. The composites were also characterized regarding their morphology, chemical structure, crystallinity, mechanical properties, water vapor permeability and hydrophilicity. Poor fiber/matrix adhesion and high water absorption of the fibers were evidenced. Consequently, water vapor permeability of composites was increased by incorporating the fibers. Moreover, mechanical properties were improved and the morphological results were used to support the water absorption differences among the powders. Regarding the food packaging applications, starch/pinhão coat composites appeared as promising materials to reach the requirements of respiring food products.     

Air–Soil Exchange of NO,NO2 and O3 in Forests

The exchange of NO, NO₂ and O₃ at the soil surface wasmeasured with automatic dynamic chambers in a spruce forest and in abeech forest during periods of several months.NO was emitted from the soil at a rate of0–8 ng N m^-2 s^-1(spruce) and 0–15 ng Nm^-2 s^-1(beech), but there was no simple relationship between the flux andeither soil temperature or soil moisture. NO₂ and O₃ weredeposited at the soil surface. Deposition velocities forNO₂were on average 0.3 mm s^-1 (spruce) and 0.1 mms^-1(beech), and the deposition velocities of O₃ were on average 1.6 mm s^-1 (spruce) and 1.4 mm s^-1 (beech). The depositionvelocity of O₃ is fairly constant whereas the deposition velocityof NO₂ varies greatly, but the reasons remain to be investigated.     

Biodegradation of Poly-ε-caprolactones and Poly-<Emphasis Type="SmallCaps">l</Emphasis>-lactides by Fungi

This work assessed biodegradation, by Aspergillus, Fusarium, Penicillium and Parengyodontium fungi, of four samples of poly-ε-caprolactone (PCL), three samples of poly-l-lactide (PLA) and one sample of poly-d,l-lactide (DL-PLA) produced by ring-opening polymerization initiated by aluminium complexes of corresponding lactones. Mesophilic fungal strains actively biodegrading PCL (F. solani) and PLA (Parengyodontium album and A. calidoustus) were selected. The rate of degradation by the selected fungi was found to depend on the physicochemical and mechanical properties of the polymers (molecular weight, polydispersity, crystallinity). The most degradable poly-ε-caprolactone sample was shown to have the lowest molecular weight; the most biodegradable polylactide DL-PLA had the lowest crystallinity. Mass spectral analysis of biodegraded polymer residues showed PCL to be degraded more intensively than PLA. It is established that in the case of Parengyodontium album the colonization of the films of polypropylene composites with DL-PLA is observed, which will undoubtedly contribute to their further destruction under the influence of abiotic factors in the environment.     

Distribution of poly(β-hydroxybutyrate) and poly(ε-caprolactone)aerobic degrading microorganisms in different environments

To assess the capacity of the natural environment for degrading plastics, the populations of poly(-hydroxybutyrate)(PHB)-and poly(-caprolactone)(PCL)-degrading aerobic microorganisms and their ratios to the total number of microorganisms in soil samples were estimated by the plate count method with agar medium containing emulsified PHB or PCL. The numbers of the degrading microorganisms were determined by counting colonies that formed clear zones on the plate. It was found that PHB- and PCL-degrading (depolymerizing) microorganisms are distributed over many kinds of material, including landfill leachate, compost, sewage sludge, forest soil, farm soil, paddy soil, weed field soil, roadside sand, and pond sediment. Of total colony counts, the percentages of PHB and PCL degrading microorganisms were 0.2–11.4 and 0.8–11.0%, respectively. The results suggest that many kinds of degrading microorganisms are present in each environment and that specific consortia differing in biodegradation capacity are constructed.     

Synthesis of Poly(β-hydroxybutyrate) in Simulated Microgravity: An Investigation of Aeration Profiles in Shake Flask and Bioreactor

The microbial strain Azotobacter vinelandii UWD was grown under conditions of simulated microgravity in the National Aeronautics and Space Administration (NASA) Bioreactor. Bacterial growth in simulated microgravity differed significantly from that observed in conventional shake flask experiments: Cells tended to grow in a cluster-like pattern and polymer production started immediately after exposing them to conditions of simulated microgravity, and no lag time was observed. It was imperative to differentiate between the effects derived from microgravity and those imposed by the altered oxygen supply in the bioreactor. Aeration conditions were studied in both reactor types and a gas supply profile was developed for the bioreactor. This supply profile allowed for similar amounts of dissolved oxygen in the bioreactor and the shake flask in the initial stage of the fermentation and, therefore, for an evaluation of the effects of microgravity on biopolyester-producing bacteria. Since the optical density that is conventionally used as a measure for the cell growth could not be used due to the cluster-like growth pattern of the cells, it was determined that bacterial growth behavior in the bioreactor can be monitored through glucose or oxygen consumption.     

Characteristics of NO2 Pollution in the City of Gothenburg, South-West Sweden—Relation to NO x and O3 Levels, Photochemistry and Monitoring Location

Concentrations of NO₂, NO, and O₃ from a rooftop monitoring station in Gothenburg, Sweden (2002–2006) were analysed to characterise NO₂ pollution. [NO₂] was shown to correlate strongly and non-linearly with [NO _x ] (NO _x ?=?NO?+?NO₂), in line with observations in other cities. The [NO₂] to [NO _x ] fraction fell initially with increasing [NO _x ]. At [NO _x ] levels >200 ppb, the decline in [NO₂]/[NO _x ] with increasing [NO _x ] levelled out and [NO₂]/[NO _x ] converged towards approximately 0.15–0.16, independent of [NO _x ]. Data from a traffic route site showed the same pattern. This value of [NO₂]/[NO _x ] at high [NO _x ] can be interpreted as the NO₂ fraction of the NO _x emissions from vehicle exhaust. Situations with high NO _x pollution and minimum [NO₂]/[NO _x ] were always associated with [O₃] close to zero. Plotting [Ox] (Ox?=?NO₂?+?O₃) vs. [NO _x ] provided a strong linear correlation for situations dominated by local pollution ([NO]/[NO₂]>1). The slope of the regression, a measure of the primary NO₂ fraction in NO _x emissions, was 0.13 during the day and 0.14 during the night. With stronger winds, the rooftop monitoring station became more similar, in terms of NO₂ pollution, to a city street site and a traffic route site, although [NO₂] was almost always higher at the street/traffic route locations. The EU standard for the annual average of [NO₂] (40 μg m^?3) was exceeded, while the hourly standard (200 μg m^?3, not to be exceeded more than 18 times per year by 2010) was not exceeded at any of the sites.     

Synthesis and biodegradation of poly(γ-butyrolactone-co-l-lactide)

Biodegradable polyesters were synthesized by ring-opening copolymerization of -butyrolactone (BL) and its derivatives withl-lactide (LLA). Although tetraphenyl tin was the main catalyst used, other organometallic catalysts were used as well.¹H and¹³C NMR spectra showed that poly(BL-co-LLA)s were statistical and that their number-average molecular weights were as high as 7×10⁴. The maximum BL content obtained from copolymerization BL/LLA was around 17%. TheT _m andT _g values of the copolymers showed a gradual depression with an increase in BL content. NoT _m was obtained for the copolymers containing more than 13 mol% BL. The biodegradability of the copolyesters was evaluated by enzymatic hydrolysis and nonenzymatic hydrolysis tests. The enzymatic hydrolysis was carried out at 37°C for 24 h using lipases fromRhizopus arrhizus andR. delemar. Hydrolyses by both lipases showed that an increase in BL content of the copolymer resulted in enhanced biodegradability. Nonenzymatic accelerated hydrolysis of copolymers at 70°C was found to increase proportionally to their exposure time. The hydrolysis rate of these copolymers was considerably faster than that of PLLA. The higher hydrolyzability was recorded for the BL-rich copolymers. The copolymerization of -methyl--butyrolactone (MBL) or -ethyl--butyrolactone (EBL) with LLA resulted in relatively LA-rich copolymers.     

Degradation of poly(β-hydroxyalkanoates) and polyolefin blends in a municipal wastewater treatment facility

Six types of plastics and plastic blends, the latter composed at least partially of biodegradable material, were exposed to aerobically treated wastewater (activated sludge) to ascertain their biodegradability. In one study, duplicate samples of 6% starch in polypropylene, 12% starch in linear low-density polyethylene, 30% polycaprolactone in linear low-density polyethylene, and poly(-hydroxybutyrate-co-hydroxyvalerate) (PHB/V), a microbially produced polyester, were exposed to activated sludge for 5 months, and changes in mass, molecular weight average, and tensile properties were measured. None of the blended material showed any sign of degradation. PHB/V, however, showed a considerable loss of mass and a significant loss of tensile strength. In a second study, PHB/V degraded rapidly, but another type of microbial polymer which forms a thermoplastic elastomer, poly(-hydroxyoctanoate), did not degrade. These results illustrate the potential for disposal and degradation of PHB/V in municipal wastewater.     

Viscoelastic Characterization and Degradation Stability Investigation of Poly(butylene-adipate-co-terephthalate) – Calcium-Phosphate Glass Composites

Journal of Polymers and the Environment - In this work new biodegradable composite materials based on poly(butylene-adipate-co-terephthalate) (PBAT) reinforced with water-soluble calcium-phosphate...     

Hydrolytic and enzymatic degradation of poly(γ-glutamic acid) hydrogels and their application in slow-release systems for proteins

The hydrolytic and enzymatic degradation of newly developed hydrogels, produced by cross-linking purified poly(-glutamic acid) (PGA) with dihaloalkane compounds, was studied and is reported in this paper. Analysis of hydrolysis of the hydrogel as a function of pH indicated that the hydrolysis occurred slowly at neutral pH, but fast in both acidic and alkaline solutions, while the polymer could be hydrolyzed rapidly only in acidic solutions. The ester bonds were more sensitive to hydrolysis than peptide bonds. The biodegradability of the hydrogel and polymer was further confirmed when enzymatic degradation was studied by three enzymes (cathepsin B, pronase E, and trypsin), which were able to cleave both ester and peptide bonds gradually. A slow-release system for porcine somatotropin (pST) formed by using the hydrogel as matrix to entrap the hormone was evaluatedin vitro andin vivo. Results demonstrated that the hydrogel was able to release the hormone for a period of 20–30 days and indicated its potential application in slow-release systems for bioactive materials, especially macromolecules, such as peptides and proteins.     

A New Polymer Platform for the Future — Sorona<Superscript>®</Superscript> from Corn Derived 1,3-Propanediol

Responding to environmental, sustainability, business, and market factors, DuPont has commercialized a new polymer platform, Sorona®, based on 1,3-propanediol. The physical and chemical property advantages over other polymers are described. The diol component of this polymer, 1,3-propanediol, has been demonstrated to be manufacturable via biological (fermentation) process from corn sugar. The economic, environmental, and process/product quality advantages of bio-PDO over conventional diols are discussed.     

Influence of Processing Additives on the Degradation of Melt-Pressed Films of Poly(ε-Caprolactone) and Poly(Lactic Acid)

Melt-pressed films of polycaprolactone (PCL) and poly(lactic acid) (PLA) with processing additives, CaCO₃, SiO₂, and erucamide, were subjected to pure fungal cultures Aspergillus fumigatus and Penicillium simplicissimum and to composting. The PCL films showed a rapid weight loss with a minor reduction in the molecular weight after 45 days in A. fumigatus. The addition of SiO₂ to PCL increased the rate of (bio)erosion in A. fumigatus and in compost. The use of a slip additive, erucamide, was shown to modify the properties of the film surface without decreasing the rate of bio(erosion). Both the rate of weight loss and the rate of molecular weight reduction of PCL increased with decreasing film thickness. The addition of CaCO₃ to PLA significantly reduced the thermal degradation during processing, but it also reduced the rate of the subsequent (bio)degradation in the pure fungal cultures. PLA without additives and PLA containing SiO₂ exhibited the fastest (bio)degradation, followed by PLA with CaCO₃. The degradation of the PLA films was initially governed by chemical hydrolysis, followed by an acceleration of the weight change and of the molecular weight reduction. PLA film subjected to composting exhibits a rapid decrease in molecular weight, which then remains unchanged during the measurement period, probably because of crystallization.     

Use of recycling stations in Borlänge, Sweden--volume weights and attitudes

This paper presents a study of recycling stations in the municipality of Borl?nge, Sweden. The main objectives were to measure volume weights of recyclables, to facilitate future planning of collection intervals and bin/container volume, and to investigate the general attitudes among the public towards waste management in general and recycling stations in particular. Volume weights measured in bins/containers were: paper/newsprint: 297 kg/m3, glass packaging: 297 kg/m3, metal packaging: 81.7 kg/m3, paper packaging: 27.8 kg/m3, plastic packaging: 28.1 kg/m3. The recycling stations have been in use since 1994. Most visitors (90%) arrived by car but said the visit to the recycling station was not the main purpose of the trip. The results from the interviews indicated that the people who use the recycling stations have found ways to incorporate waste sorting into their everyday lives, with the help of information, design of the collection system and environmental concerns.     

Sources of Alkylphenols and Alkylphenol Ethoxylates in Wastewater—A Substance Flow Analysis in Stockholm, Sweden

This is a study of the sources of alkylphenol and alkylphenol ethoxylates in wastewater, including the new observation that the main contribution is from textiles. Alkylphenols and alkylphenol ethoxylates are widely used chemicals in various applications that are partly under environmental restrictions within Europe. The study sets out to analyze the most important sources of this large group of organic compounds in an urban wastewater system. A substance flow analysis (SFA) of the technosphere in Stockholm, Sweden in 2004 was conducted, allowing a comparison of 13 groups of goods’ emissions to wastewater. It was found that the groups of textiles and cleaning agents were the major sources to wastewater, while the group’s personal care products and paint and lacquers give smaller contributions. The content of alkylphenol ethoxylates in goods, especially in textiles, is a most significant source and is probably valid for other urban areas as well.