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.     

Effects of Poly(Ethylene Glycol) on the Production of Poly(β-Hydroxybutyrate) by Azotobacter vinelandii UWD

Azotobacter vinelandii UWD, ATCC 53799, an engineered strain derived from Azotobacter vinelandii UW was used in the poly(ethylene glycol) (PEG)-modulated synthesis of poly(-hydroxybutyrate) (PHB). To the best of our knowledge, this is the first report on modulating the production of PHB by amending the fermentation broth with PEG using A. vinelandii UWD. It was determined that A. vinelandii UWD is prone to back-mutation to the parent strain; hence fermentation experiments require the use of the antibiotic rifampicin. Diethylene glycol (DEG) and PEGs with molecular weights of 400, 2000, and 3400 Da and pentaerythritol ethoxylate (PEE) were used in the modulated fermentation experiments in a concentration of 2% (w/v). The molecular weight of the resulting polymers was reduced by up to 78%. No impact on the productivity of the strain was observed. Spectroscopic evidence showed that PEG-modulated synthesis resulted in the covalent attachment of the ethylene glycol moiety only when a small molecule, DEG, was used. PEGs had the same effects on the polymer formation in terms of molecular weight reduction as DEG, but no spectroscopic evidence was found for the formation of a covalent linkage between PHB and higher molecular weight PEGs.     

The Effect of UV-B Irradiation on the Biodegradability of Poly-β-Hydroxybutyrate (PHB) and Poly-ɛ-Caprolactone (PCL)

The biodegradability of poly--hydroxybutyrate and poly--caprolactone in soil compostage before and after irradiation of the polymers for 192, 425, and 600 h in a Weather-Ometer was examined. The biodegradability tests were done in soil compostage at pH 7.0, 9.0, and 11.0 to assess the influence of this parameter on degradation. The rate of degradation was directly proportional to the soil alkalinity. Poly--hydroxybutyrate showed the greatest weight loss and aging in a Weather-Ometer did not significantly increase the biodegradation, except when the polymer was aged for 425 h and buried in soil compostage of pH 11.0.     

Assessment of the environmental impact of management measures for the biodegradable fraction of municipal solid waste in São Paulo City

There is increasing concern about landfilling of biodegradable wastes. Therefore, biological treatment processes such as composting and biogasification have been considered as alternative strategies for managing those wastes. In this work, life cycle assessment was employed to compare the environmental impacts of landfilling, composting, and biological treatment of municipal solid waste in S?o Paulo City, Brazil. Energy consumption, recovered resources, and emissions to air and water were quantified and analyzed in terms of their potential contribution to global warming, acidification, and nutrient enrichment impact. The results demonstrated that processes that require high levels of energy consumption, such as wastewater treatment, play an important role in the outcome of environmental impact potentials. It was found that the landfilling of all waste is generally the worst strategy from an environmental point of view. However, significant reductions in the resulting impacts can be accomplished through biogasification and composting of the biodegradable fraction. Regarding composting, the application of a biofilter for gas treatment reduced significantly the gaseous emissions.     

Correction: Insight into the Adsorption Properties of Chitosan/Zeolite‑A Hybrid Structure for Effective Decontamination of Toxic Cd (II) and As (V) Ions from the Aqueous Environments

Journal of Polymers and the Environment -     

A method for the isolation of microorganisms producing extracellular long-side-chain poly (β-hydroxyalkanoate) depolymerase

A simple method was developed for the preparation of an autoclavable, long-side-chain poly (-hydroxyalkanoate) (LSC-PHA) colloidal suspension, which was used as a substrate for enzymatic degradation and to prepare agar overlay plates for the isolation of microorganisms producing extracellular LSC-PHA depolymerase. Six cultures producing extracellular LSC-PHA depolymerase were isolated from a composted hydrocarbon-contaminated soil. All were pseudomonads or related bacteria. All (with the possible exception ofXanthomonas maltophilia) could produce LSC PHA. Except forX. maltophilia none could hydrolyze poly (-hydroxybutyrate). Screening of sevenPseudomonas strains known to accumulate LSC PHA showed that all were negative for extracellular LSC-PHA depolymerase production. It was concluded that extracellular LSC-PHA depolymerase producers are found mostly in the genusPseudomonas but that they are relatively uncommon.     

Influence of regulation on the productivity of waste utilities. What can we learn with the Portuguese experience?

This paper examines the merits and the perverse effects of quality of service regulation in the performance of urban waste services when implemented alone and compares the performance of different economic regulatory methods. By means of a productivity analysis, we investigate the influence of a five-year period of regulation on the performance of Portuguese urban waste utilities using an unbalanced panel data for the period 2001-2008. Different non-parametric methods were applied to estimate the productivity change, all leading to similar outcomes. We observed a tendency of productivity decline in the urban waste utilities and concluded that in spite of the unequivocal improvements in the quality of service induced by sunshine regulation, more should be done as far as economic regulation is concerned. We also found that the use of sunshine regulation together with low incentive economic regulatory methods is not positive, leading to overinvestment rather than to value for money.     

The introduction of recycled-aggregate concrete specifications in Japan and the research into the freezing–thawing resistance of recycled-aggregate concrete

Journal of Material Cycles and Waste Management - In Japan, recycled concrete aggregate (RCA) and recycled-aggregate concrete (RAC) are standardized in the Japanese Industrial Standards (JIS) A...     

Dioxin emissions: Possible techniques for maintaining the limit of 0.1 ng TE m−3 (as of 1990/91)

Processes which will achieve up to 100-fold reduction of exhaust gas emissions of dioxin as proposed for the new German Standards are reviewed. A combination of processes which remove fly ash, NO_x, SO_x, HCl and other pollutants will also remove dioxins. Reduction of chlorinated compounds fed to the incinerator is not likely to make any significant difference. Good turbulence with elimination of cold spots in the firebox will ensure initial thermal destruction. Dioxins are synthesized on fly ash particles at temperatures between 200 and 400° C. Rapid temperature reduction across this range by water injection will greatly reduce dioxin levels. Catalytic inhibitors can also be used. Since dioxin is adsorbed on fly ash, efficient scrubbing is essential for high removal efficiency. Sorption on active carbon beds is also being evaluated.     

A Methodology to Identify the Releasing of the Amide-Containing β-Glucan from the Usnea Lichen: A Spectroscopic Study

Journal of Polymers and the Environment - Polymer fractions from a biological matrix have been well-characterized by vibrational spectroscopy, XPS, CP/MAS 13C NMR, MALDI-TOF mass...     

The Myth of the “Pristine Environment”: Past Human Impacts in Prince William Sound and the Northern Gulf of Alaska

The coastal region affected by the Exxon Valdez oil spill, although a beautiful and sensitive maritime wilderness with bountiful fish and wildlife, was not a pristine environment in 1989. Prior to the spill, Prince William Sound and the northern Gulf of Alaska region had experienced extensive human impacts from the commercial fur trade, commercial sea-mammal hunting, commercial fishing, logging, mining and introduced exotic species including foxes, Sitka black-tailed deer and hatchery-reared pink salmon. The spill occurred in a scenic area that was (and is) paradoxically both the source of subsistence food for local residents and the scene of extensive natural resource exploitation.Contrary to media sound bites and news headlines, the Exxon Valdez oil spill did not destroy a pristine wilderness. The Russian and American fur traders, commercial whalers and commercial fishermen, miners, loggers, fox farmers and military construction crews had transformed the region long before March 24, 1989. The Exxon Valdez spill was an important chapter in the history of human impacts to the area’s maritime ecosystem, but it was not, as many continue to claim, the mother of all environmental impacts in the region.     

Classification of the sugarcane residues and their characteristics—an environmental assessment of mortar with addition of sugarcane residues

Journal of Material Cycles and Waste Management - The use of agro-residue in resource-limited regions can be a smart way for civil construction to reduce costs, reduce emissions of pollutant gases...     

Purification of Aspergillus fumigatus (Pdf1) Poly(β-hydroxybutyrate) (PHB) Depolymerase Using a New, Single-Step Substrate Affinity Chromatography Method: Characterization of the PHB Depolymerase Exhibiting Novel Self-Aggregation Behavior

The extracellular poly(-hydroxybutyrate) (PHB) depolymerase of Aspergillus fumigatus Pdf1 was purified by a new, simple, one-step affinity chromatography method using the substrate PHB. The purified enzyme was glycosylated, with the molecular mass of 40 KD, and exhibited a novel self-aggregation behavior by means of hydrophobic interaction that was resolved by Triton X-100 (TX-100) pretreatment of enzyme and also TX-100 incorporation in the native gel. The apparent K _m value of purified enzyme for PHB was 119 g/mL and 3-hydroxybutyrate was detected as the main endproduct of PHB hydrolysis. The depolymerase was insensitive to phenylmethyl sulfonyl fluoride (PMSF), sodium azide, ethylenediaminetetraacetic acid (EDTA), and para-chloromercuric benzoic acid (PCMB), but was inactivated by dithioerythritol (DTT) and showed specificity for short chain-length poly(-hydroxyalkanoates) (PHAs) such as PHB, poly(hydroxyvalerate) (PHV), and copolymers of 3-hydroxybutyrate (3HB) and 3-hydroxyvalerate (3HV). Medium-chain-length PHA failed to get hydrolyzed. The enzyme, however, exhibited strong cross reactivity with the Comamonas sp. PHB depolymerase antibodies, but not with PHV depolymerase antibodies of Pseudomonas lemoignei. Southern hybridization and dot blot analysis of A. fumigatus Pdf1 genomic DNA with alkaline phosphatase labeled probes of P. lemoignei PHB and PHV depolymerase genes revealed no homology, although the enzyme hydrolyzed both PHB and PHV.     

Hydrogeological Basis for Biotechnological Remediation of the Acidic Mining Lake ‘RL 111’, Lusatia (Germany)

The drainage basin of the acidic mining lake RL 111 was characterized by hydrogeological and geochemical models to assess its influence on a planned biotechnological remediation of the lake water and lake sediment. Ground, seepage and lake water, as well as the surrounding sediments, were examined to model the hydrodynamic processes and the geochemical developmentof the lake. The geochemical conditions seem to behave in a stable manner (steady state conditions). A reduction of the high sulphate andacid input has not been observed since the beginning of our investigations. The biotechnological remediation of the whole lake should consider a treatment of the dump sediments to improvethe quality of the inflowing groundwater, as well as to reduce erosion.     

Chronic toxicity of the ‘water-soluble fraction’ of Norman Wells crude oil to juvenile fish

Young rainbow trout were exposed to Norman Wells crude oil for periods as long as 55 d. Mortality was light for the first few days, but it continued throughout exposure with more rapid and increased mortality at the higher exposure levels. The mortality was generally exacerbated by the presence of oil dispersants Corexit 7664 or 9600. Fish surviving the 55-day experiment showed severe fin erosion and apparent ‘flooding’, since mean body water content was increased from about 84% to over 90%. We hypothesize that the oil affected the ability of the fish to regulate their water content.     

Formation of Reactive Gaseous Mercury in the Arctic: Evidence of Oxidation of Hg° to Gas-Phase Hg-II Compounds after Arctic Sunrise

We have measured total gaseous mercury concentrations(Hg°) at Point Barrow, Alaska since September 1998 in aneffort to determine the geographic extent and reaction mechanismof the so-called mercury depletion events (MDE) previouslyreported in the high Arctic at Alert, Canada. Hg° has beensampled now for nearly 2 years at Barrow. In September, 1999, webegan making the first automated measurements of reactive gaseousmercury (RGM) attempted in the Arctic, along with measurements ofHg accumulation in snowpack to determine the fate of the depleted Hg°. During the fall and early winter, Hg°and RGM exhibit only minor variation, Hg° remaining within10% of global background, near 1.6–1.8 ng m^-3. The MDEperiods are quite different, however; within days of Arcticsunrise in January, Hg° exhibits major variations from themean, rapidly dropping as low as 0.05 ng m^-3 and then cyclingback to typical levels, sometimes exceeding global background. These events continue throughout Arctic spring, then end abruptlyfollowing snowmelt, in early June. Prior to Arctic sunrise, RGMremains near detection (<2 pg m^-3), but after sunriseincreases dramatically (to levels as high as 900 pg/m³) insynchrony with the depletion of Hg°. Both phenomenaexhibit a strong diel cycle, in parallel with UV-B. We concludethat MDE's involve rapid in-air oxidation of Hg° to aspecies of RGM by photochemically-driven reactions, probablyinvolving the same reactive bromine and chlorine compoundsinvolved in ozone destruction. Sharp increases in Hg in thesurface snowpack after sunrise coincident with periods of peakRGM suggest surface accumulation of the RGM by dry deposition.     

Environmental Degradation of Biodegradable Polyesters: 3. Effects of Alkali Treatment on Biodegradation of Poly(ε-Caprolactone) and Poly[(R)-3-Hydroxybutyrate) Films in Controled Soil

The poly(-caprolactone) (PCL) and poly[(R)-3-hydroxybutyrate] (R-PHB) films with a hydrophilic surface were prepared by the alkali treatment of their as-cast films in NaOH solutions of different concentrations. The alkali-treated PCL and R-PHB films, as well as the as-cast PCL and R-PHB films, were biodegraded in soil controlled at 25°C and the effects of alkali treatment or surface hydrophilicities on their biodegradation were investigated by the use of gravimetry, gel permeation chromatography (GPC), scanning electron microscopy (SEM), and polarization optical microscopy. It became evident that the alkali treatment enhanced the hydrophilicities and biodegradabilities of the PCL and R-PHB films in soil. The biodegradabilities of the as-cast aliphatic polyester films in controlled soil decreased in the following order: PCL > R-PHB > PLLA, in agreement with that in controlled static seawater.     

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.     

Evaluation of biodegradability of poly(ε-caprolactone)/poly(ethylene terephthalate) blends

The results of an investigation aimed at evaluation of the biodegradability of blends of poly(-caprolactone) (PCL) with poly(ethylene terephthalate) (PET) as the major component are reported. Specimens of the blends, as melt extruded films and/or powders, were submitted to degradation tests under different environmental conditions including full-scale composting, soil burial, bench-scale accelerated aerobic degradation, and exposure to axenic cultures and esterolytic enzymes. Indications have been gained that blending in the melt gives rise to insertion of PCL segments in the PET chain. Copolymers thus attained acted as macromolecular compatibilizers, allowing for a complete miscibility of PCL and PET. The biodegradation detected on the blend samples was, however, well below the values expected from chemical composition and behavior of individual homopolymers under the same environmental conditions. The presence of PET as the major component in PET/PCL blends apparently reduces the propensity of PCL to be degraded, at least in the investigated composition range. The degradation data collected under different environmental conditions indicate that the full-scale composting system is the most efficient among the tested degradation procedures.     

Crystallization behavior of predominantly syndiotactic poly(β-hydroxybutyrate)

Predominantly syndiotactic poly(-hydroxybutyrate), syn-PHB, of variable syndioregularity (syndyad fractions 0.59, 0.62, 0.64, and 0.71) and molecular weight was prepared by the dibutyltin dimethoxide catalyzed ring opening of racemic-butyrolactone (BL). The crystallization behavior of the syn-PHB polymers was investigated by DSC and X-ray diffraction analyses. DSC of films after melting and annealing showed at least one, and often two distinct melting transitions occuring over a broad (often 40°C) temperature range. These results indicate that syn-PHB chain segments of variable syndioregularity form crystalline regions with very different thermodynamic stabilities. Maximum degrees of crystallinity for melt annealed 0.64- and 0.71-syn-PHB was observed at an annealing temperature (T _c ) of 30°C. AtT _c values at 45°C and higher, crystallization of relatively lower syndioregular chain segments was apparently excluded to variable degrees dependent onT _c and sample syndiotactic dyad content. After crystallization of syn-PHB samples at elevated temperatures, ambient temperature annealing resulted in an observed lower temperature melting transition at 50°C. This result showed little to no dependence on syn-PHB syndio-regularity andT _c . Both solution precipitated 0.62-syn-PHB and 0.71-syn-PHB have WAXS patterns with poorly resolved crystalline reflections superimposed on amorphous haloes indicating low levels of crystallinity (17% and 25%, respectively) and poorly formed crystals. Isothermal crystallization monitored by DSC showed that the syn- and natural origin PHB showed fastest crystallization rates at temperatures between 50°C and 70°C and 60°C and 90°C, respectively. From the dependence of the higher melting transition onT _c it was determined that the equilibrium melting temperatures for 0.62-syn-PHB (M _n =83,700 g/mol) and a 0.64-syn-PHB (M _n =11,900 g/mol) were 157 and 154°C, respectively. An Avrami analysis of syn-PHB yielded results similar to that found for natural origin PHB indicating that crystal growth occurs by a two-dimensional mechanism.Guest Editor: Dr. Graham Swift, Rohm & Haas.