Biodegradability: An assessment of commercial polymers according to the Canadian method for anaerobic conditions

The degradation of several biodegradable polymers was measured as a result of exposure to an anaerobic medium. The polymers investigated included materials based upon polylactic acid, polylactone, and poly(hydroxy butyrate/valerate) as well as those incorporating starch-based materials. The degradation was monitored by methane and carbon dioxide evolution. In addition, the physical and chemical changes were noted as a result of exposure. These measurements included changes in mass, dimension, and molecular weight. FTIR, UV-vis, proton, and¹³C NMR spectra were also recorded prior to and after exposure. The results clearly indicated that several biological and chemical degradation processes were occurring with the biodegradable polymers studied.Paper presented at the Bio/Environmentally Degradable Polymer Society—Second National Meeting, August 19–21, 1993, Chicago, Illinois.Issued as NRCC No. 37549.     

Hydrolysis of Polylactic Acid (PLA) and Polycaprolactone (PCL) in Aqueous Acetonitrile Solutions: Autocatalysis

Polylactic acid (PLA) is a hydrolytically degradable aliphatic polyester. The rate of polymer hydrolysis increases with time, and that has been attributed to the high reactivity of the terminal ester and the kinetics of autocatalysis. Hydrolysis is carried out in an acetonitrile/water solution to eliminate any solid-state contributions such as diffusion and crystallinity to the degradation process. A kinetic equation is derived to describe the autocatalytic effect of the increasing carboxylic acid end-group concentration. The results of solution hydrolysis are examined and found to fit the derived equation. Hydrolysis was also carried out with polycaprolactone (PCL) in acetonitrile, where reaction kinetics were found to differ from those of PLA. The PCL polymer required external acid catalysis by the addition of HCl, whereas hydrolysis of PLA was selfcatalyzed by the carboxylic acid end-groups.     

Decomposition reactions of epoxy resin and polyetheretherketone resin in sub- and supercritical water

Epoxy resin and polyetheretherketone (PEEK) resin were decomposed into their monomers such as phenol, cresols, and their analogues by thermal treatment in sub- and supercritical water in a 10-ml tubing bomb reactor. The addition of basic compounds such as Na₂CO₃ was effective in promoting the decomposition reaction of the resins. In the reaction of epoxy resin, the yield of identified products reached 10% for the reaction at 703K over 1h. In the reaction of PEEK resin, the total yield of phenol and dibenzofuran reached 88% for the reaction at 703K over 3h. Chemical participation of water in the decomposition reaction was confirmed by the reaction of dinaphthylether.     

The contemporary Oceania zinc cycle: one-year stocks and flows

The material flow approach provides a framework from which to address resource management and estimate gross environmental impacts, both spatially and temporally. In this article, the major flows of zinc in Oceania over its entire life-cycle are examined; these include production (mining, milling, and refining), fabrication and manufacturing of semi- and finished products, use, and the waste management system. Comprehensive mass balances were applied to determine the zinc flows, including the quantities of zinc entering stocks in waste and in-use reservoirs. The Oceania cycle shows that substantial amounts of zinc (about 1120Gg/year) are mined on the continent. The total flow of zinc in finished products entering the use stage is about 8.6kg/(capita.year), substantially exceeding the zinc flow in discarded products. This difference, about 7.2kgZn/(capita.year) on average, is added to the in-use reservoir, largely for galvanizing applications in domestic construction and transportation. Less than 60% of all discarded zinc entering the waste management system is recycled. Much of the remaining discarded zinc is diluted into other waste streams, where recovery and recycling are probably not economically feasible.     

Degradation Kinetics of Biodegradable Fiber Composites

In a composite, fast degradable fibers determine the degradation of the slowly degradable matrix. Such biodegradable composites consisting of degummed hemp fibers and a polyester amide matrix were produced with fiber mass fractions between 0 and 0.48. The hot-pressed plates, 1-mm thick, were incubated in a standard soil. The degradation kinetics was quantified by the measurement of CO₂ production. Furthermore, after termination of experiment, the carbon balance was uncovered. The results were fitted to an exponential law taking into account the degradation of fibers. The increased amount of pores realized by high fiber contents induces pronounced degradation. The degradation is fully characterized by the time constant , which is correlated to the fiber mass fraction. The model allows to predict the degradation kinetics of composites with a few well-defined experiments.     

Thermal cracking of oils from waste plastics

Thermal cracking of decomposed waste plastic oil produces a good yield of olefins. The solvent extraction of such waste plastic oil seems to be efficient for increasing gas yields and recycling monomers. To assess the potential of monomer recovery from municipal waste plastics, the oils were cracked using a laboratory-scale quartz-tube reactor. The waste plastic oils were provided by two commercial plants of the Sapporo Plastic Recycle Co. and the Dohoh Recycle Center Co. in Japan. A model waste plastic oil made in a laboratory was also examined. Yields of ethene, propene, and other products were measured at different temperatures. Two-step pyrolysis reduces coking compared with the direct thermal degradation of plastics. The raffinates from waste plastic oils extracted by sulfolane were also cracked. The primary products were almost the same as those from nontreated oils. The maximum total gas yield was 78wt%–85wt% at 750°C, an increase of about 20wt% compared with that of nonextracted oil. Solvent extraction removes stable aromatic hydrocarbons such as styrene, which is more coked than cracked.     

Graft Copolymers, for Erodible Resins, from α-Hydroxyacids Oligomers Macromonomers and Acrylic Monomers

Environmental concerns result in a progressive withdrawal of antifouling paints containing organotin derivatives. The nature of the binders is critical with regard to the erosion of the protecting film through factors such as bond cleavage, dissolution, and diffusion of the degradation products. The versatility of acrylic polymers, due to the possibility of varying their chemical structure had conducted, in the first stage, to combine different types of repeating units in the macromolecular backbone. Formulation and evaluation, in natural sites, of these binders, with a well-defined hydrophobic/hydrophilic balance and with hydrolyzable pendant groups, have shown the possibility to prepare new organotin free resins which can be formulated and which are erodible in seawater over a long period (more than 2 years). A further step has been engaged with the development of graft copolymers containing biocompatible and hydrolyzable oligomers of -hydroxyacids. Their preparation requires the synthesis of -methacryloyloxyoligo--hydroxyacid macromonomers. Copolymers prepared from a mixture of the macromonomer and of an alkyl ester of acrylic acid were formulated with a biocide and deposited on a plate. Their ability to release cuprous oxide, as a model molecule, has been checked and quantified by the inductively coupled plasma analytical method. The uptake of water in the paint, which is enhanced by the hydrolysis of -hydroxyacid oligomers, as determined by the enzymatic measurement of liberated L-lactic acid, conducts to the polymer erosion and to a protecting bioactive surface.     

The degradation of gel-spun poly(β-hydroxybutyrate) “wool”

The apparent biodegradability and biocompatibility of the microbially produced polyester, poly(-hydroxybutyrate) (PHB), has been the focus of much research by a number of authors with regard to its potential for use in packaging and medical implantation devices. PHB has recently been produced by gel-spinning into a novel form, with one possible application being as a wound scaffolding device, designed to support and protect a wound against further damage while promoting healing by encouraging cellular growth on and within the device from the wound surface. This new nonwoven form combines a large volume with a low mass, has an appearance similar to that of cotton wool, and has been called wool because of this similarity. The hydrolytic degradation of this wool was investigated in an accelerated model of pH 10.6 and temperature 70°C. It was determined that the PHB wool gradually collapsed during degradation. The surface area-to-volume ratio was concluded to be a primary influencing factor. Degradation was characterized by a reduction in the glass transition temperatures and melting points and a fusion enthalpy peak of maximum crystallinity, (88%), which coincided with the point of matrix collapse.     

What substances or objects should be recycled? The recycling legislative experience in Taiwan

The legislative framework of waste management in Taiwan has never been efficient, mainly due to unclear definitions and regulations. In 2002, this system was split into two parts by enacting a new law, the Resource Recycling and Re-use Act (RRRA). However, it then became more complicated and recycling effectiveness was impeded. The causes were mainly the unclear definitions, conflicts about the scope, and issues between the RRRA and the Waste Disposal Act (WDA). This article examines the recycling legislation experience in Taiwan, and proposes two modifications for resolving these problems. The first proposal is merging these two acts into one. The second proposed modification maintains a two-system structure but introduces a new subject, discards, into the law. The subject of discards is further categorized as recyclable resources or waste, which correspond to recycling operations and disposal operations, respectively. The new structures, interfaces, prerequisites, properties, and comparisons are also explained.     

Controlling the Behaviors of Biodegradable/Bioabsorbable Polymers with Cyclodextrins

The cyclic six, seven, and eight-membered oligosaccharides -, -, and -cyclodextrins (CDs) can serve as hosts for a variety of polymer guests to form crystalline inclusion compounds (ICs), wherein the guest polymers are included in the continuous narrow channels (0.5–1.0 nm in diameter) formed by the host CD stacks. Polymers included as guests in CD-ICs are highly extended and segregated from neighboring chains by the walls of the host CD bracelets. As a consequence, when polymer-CD-ICs are treated with solvents for CDs that are non-solvents for the included polymers or with amylase enzymes, the CDs are removed and the guest polymers are coalesced into bulk samples whose structures, morphologies, and even chain conformations are different from those achieved by consolidation from their randomly coiling, entangled solutions and melts. Often these CD-IC coalesced and consequently reorganized polymer samples exhibit properties that are distinct from their normally processed bulk samples. Here we describe the CD-IC processing of several biodegradable/bioabsorbable homopolymers, copolymers, and blends made from poly (L-lactic acid), poly (-caprolactone), and poly (-hydroxybutyrate)s, with special emphasis placed on their improved and controllable properties. For example, the phase segregation and consequent crystallinities of their normally incompatible homopolymer blends and their block copolymers may be controlled and thus improved. In addition, co-inclusion of small molecule guests, such as drugs or anti-bacterials, in their common CD-ICs, and subsequent coalescence, yields well-mixed blends of these biodegradable/bioabsorbable polymers and the small molecule co-guests, which may lead, for example, to the improved delivery of drugs.     

Enzymatic degradation of poly([R,S] β-hydroxybutyrate)

The synthetic analogue of a bacterially produced polyester, poly(-hydroxybutyrate) (PHB) was synthesized from racemic -butyrolactone using anin situ trimethyl aluminum-water catalyst. The polymer was fractionated into samples differing in molecular weight and isotactic diad content. The latter was closely related to degree of crystallinity. The biodegradation of these fractions were examined by monitoring mass loss over time in the presence of anAlcaligenes faecalis T1 extracellular bacterial poly(-hydroxybutyrate) depolymerase. The fraction with high isotactic diad tacticity content showed little or no degradation over a 50 hour incubation period, whereas the fraction of intermediate isotactic diad content degraded in a continuous steady fashion at a rate that was less than that for bacterial PHB. The low isotactic diad fraction underwent a rapid initial degradation, followed by no further mass loss. The presence of stereoblocks in the polymer structure of the various fractions was an influence on the degree of susceptibility towards degradation and is related to sample crystallinity.     

Distribution of Poly(β-propiolactone) Aerobic Degrading Microorganisms in Different Environments

The distribution of degading microorganisms of high molecular weight poly(-propiolactone) (PPL), whose individual structural units are similar to those of poly(-hydroxybutyrate) (PHB) and poly(€-caprolactone) (PCL), was examined. Despite the fact that PPL is a chemosynthetic polymer, many kinds of PPL-degrading microorganisms were found to be distributed as resident populations widely in natural environments. A total of 77 strains of PPL-degrading microorganisms was isolated. From standard physiological and biochemical tests, at least 41 strains were referred to as Bacillus species. Microbial degradation of fibrous PPL proceeded rapidly in some enrichment cultures but was not as complete as that of PHB. Most of the isolated PPL-degrading microorganisms were determined to be PCL degraders and/or PHB degraders. Therefore, it can be assumed that mostly PPL is recognized by the microorganisms as PHB or another natural substrate of the same type as which PCL is regarded. Microbial degradation of PPL was confirmed by some Bacillus strains from type culture collections. The similarity of microbial degradation between PPL and PCL was found to be very close.     

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.     

Development of a catalytic cracking process for converting waste plastics to petrochemicals

The catalytic degradation of polyolefin using H-gallosilicates was examined using a bench-scale reactor (0.8kg/h) with semicontinuous feeding and the following plastics: (1) low-density polyethylene (LDPE) pellets; (2) linear low-density polyethylene (L-LDPE) pellets; (3) high-density polyethylene (HDPE) pellets; (4) polypropylene (PP) pellets; (5) polyolefin obtained from pulverized industrial waste plastics. The yields of liquid compounds from these materials, which were aromatics in most cases, ranged from 55wt% to 68wt%. With an increase in the ratio of total reactant to catalyst, the liquid yield remained the same. Yields of benzene, toluene, and xylenes (BTXs) decreased rapidly to below 50wt% at a ratio of more than 30. Differences in this ratio for BTXs were always small and were independent of the material. Only about half of the gas product was propane with a fresh catalyst. When the experiments were repeated, propylene, isobutane, and isobutene were found to increase.     

A carbon-13 method for evaluating degradation of starch-based polymers

A new method for evaluating biodegradability of starch-based and certain other polymer blends uses the pre- and postexposure stable carbon isotope composition of material coupled with weight loss data to determine which components have degraded. The naturally occurring stable isotope of carbon.¹³C, is enriched in corn starch (¹³C, approx. –11) compared to petroleum-derived synthetic polymers (¹³C, approx. –32). Results on starch-synthetic polymer blends indicate that the ¹³C signatures of these blends are near-linear mixtures of their component ¹³C. Values of a ¹³C for starch-synthetic polymer blends exposed to biologically active laboratory soil and artificial seawater conditions are depleted in¹³C compared to unexposed samples, suggesting loss of the starch component. Combined with weight loss data for the exposed samples, the ¹³C values are statistically consistent with models requiring loss of the soluble component glycerin, followed by loss of starch, then petrochemical polymer, or simultaneous loss of starch and petrochemical polymer. Replicate ¹³C analyses of starch-synthetic polymer blends increase the statistical power of this relatively inexpensive, accessible technique to discriminate between degrading components.     

Solid State Reactions of Potato Starch with Urea and Biuret

Reaction of granular potato starch with urea and biuret resulted in the formation of products, which were soluble neither in cold nor boiling water. The net reaction was a monosubstitution of the hydrogen atom in one hydroxyl group in each D-glucose unit of starch with the either CO–NH₂ or CO–NH–CO–NH₂ moiety, respectively. Properties of the products, particularly these with urea, depended on the mode of reaction. Reactions were carried out in the microwave oven as well as with convection heating. The products retained the granular form of starch but a vast majority of granules were damaged. -Amylolysis of those materials revealed that their susceptibility to the enzyme increasing in the order: starch-amylolysis with simultaneous insolubility in water make these products suitable as ruminant fodder and, eventually, biodegradable material.     

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.     

Effects of Lime and Ash Treatments on DOC Fractions and Low Molecular Weight Organic Acids in Soil Solutions of Acidified Podzolic Soils

Dissolved organic carbon (DOC) fractions and different low molecular weight organic acids (LMWOAs) were determined in soil solutions from two lime or ash treated Norway spruce sites in the south of Sweden. At Hasslöv, 3.45 t ha^-1 or 8.75 t ha^-1 dolomite were applied 15 years before sampling. Horröd was treated with 4.28 t ha^-1 ash and 3.25 t ha^-1 dolomite and sampled four years later. Propionate (7–268 M) and malonate (2–34 M) were the LMWOAsfound in the highest concentrations at Hasslöv. Two other LMWOAs dominated at Horröd, namely citrate (18–64 M)and fumarate (5–31 M). The differences in concentration of most of the determined LMWOAs at Hasslöv were significantly increased due to treatment. The LMWOAs comprised between 1.1–6.3% of the DOC at Hasslöv and 4.5–17.6% at Horröd. At Hasslöv normally 3–10% of the total acidity (TA) was due to LMWOAs and the average specific buffer capacity was 74 ± 22 mmol mol^-1C.The total DOC concentration in the mor layer solution was 16 mM for the dolomite treated plots compared to 10 mM at the untreated plot. A major part of the increase in DOC at the treated plots apparently had a hydrophobic character and was of high molecular weight corresponding to 3–10 kDa. The concentration of DOC < 1 kDa in the control and treated plots was similar.     

Miscibility and Biodegradability of Poly(Butylene Succinate)/Poly(Butylene Terephthalate) Blends

As one of the biodegradable polymers, the blend of poly(butylene succinate) and poly(butylene terephthalate) is dealt with in this study. In our previous work, it was demonstrated that PBS and PBT are immiscible not only from the changes of T _g but also from logG–log G plots. It is expected that the biodegradability of the blends could be improved by enhancing the miscibility. We tried to induce the transesterification reaction between two polyesters with various time intervals to enhance the miscibility of the blends. The extent of transesterification reaction was examined by ¹H-NMR. We utilized a dynamic mechanical thermal analyzer and a rotational rheometer to investigate the changes in miscibility. We also verified the biodegradability of PBS/PBT blends after the transesterification reaction by the composting method.     

In situ bioremediation of a hydrocarbon polluted site with cyclodextrin as a coadjuvant to increase bioavailability

Bioavailability is one main factor that influences the extent of biodegradation of hydrocarbons. They are very poorly soluble in water and easily adsorbed to clay or humus fractions, so they pass very slowly to the aqueous phase where they are metabolised by microorganisms. Cyclodextrins are natural compounds that form soluble inclusion complexes with hydrophobic molecules and increase degradation rate of hydrocarbons in vitro. In the perspective of an in situ application, we previously checked that -cyclodextrin does not increase eluviation of hydrocarbons through the soil and consequently does not increase the risk of groundwater pollution. The results of an in situ application of -cyclodextrin for bioremediation of a hydrocarbon polluted site are presented. We stated that the combination of bioaugmentation and enhanced bioavailability due to -cyclodextrin was effective for a full degradation.