Biodegradability and Biodegradation of Polyesters

A variety of biodegradable plastics have been developed in order to obtain useful materials that do not cause harm to the environment. Among the biodegradable plastics, aliphatic polyesters such as: poly(3-hydroxybutyrate) (PHB), poly(ε-caprolactone) (PCL), poly(butylene succinate) (PBS), and poly(l-lactide) (PLA) have become the focus of interest because of their inherent biodegradability. However, before their widespread applications, comprehensive studies on the biodegradability and biodegradation mechanisms of these polyesters are necessary. Thus, this paper describes the degradation mechanisms and the effects of various factors on the degradation of polyesters. The distribution of polymer-degrading microorganisms in the environment, different microorganisms and enzymes involved in the degradation of various polyesters are also discussed.     

Crop‐based systems for sustainable risk‐based land management for economically marginal damaged land

The increasing need for biomass for energy and feedstocks, along with the need to divert organic methane generating wastes from landfills, may provide the economic leverage necessary to return this type of marginal land to functional and economic use and is strongly supported by policy at the European Union (EU) level. The use of land to produce biomass for energy production or feedstocks for manufacturing processes (such as plastics and biofuels) has, however, become increasingly contentious, with a number of environmental, economic, and social concerns raised. The REJUVENATE project has developed a decision support framework to help land managers and other decision makers identify potential concerns related to sustainability and what types of biomass reuse for marginal land might be possible, given their particular circumstances. The decision‐making framework takes a holistic approach to decision making rather than viewing biomass production simply as an adjunct of a planned phytoremediation project. The framework is serviceable in Germany, Sweden, and the United Kingdom. These countries have substantive differences in their land and biomass reuse circumstances. However, all can make use of the set of common principles of crop, site, value, and project risk management set out by REJUVENATE. This implies that the framework should have wider applicability across the EU. This article introduces the decision support framework. © 2011 Wiley Periodicals, Inc.     

Critical Review of Norms and Standards for Biodegradable Agricultural Plastics Part II: Composting

The critical review of norms and standards and corresponding tests to determine the compostability of biodegradable plastics, possibly applicable also to biodegradable agricultural plastics, shows that many norms concerning testing and labelling of compostable plastics have been established at the international level. Some of them are about plastic materials, some others are about products like packaging. The media and conditions of testing cover mainly the conditions designed for industrial composting facilities, and only a few concern home composting conditions. Considering that the end of life management of biodegradable agricultural plastic products will be done at the farm to reduce the management of the waste and also its cost, only a few of these norms are considered to be suitable for adaptation to cover also biodegradable agricultural plastic products. The biodegradability validation criteria under composting conditions, such as the threshold percentage of biodegradation and disintegration, the time and temperature, and the ecotoxicity, are presented for the main norms and standard testing methods. Based on these different norms and their content, a list of specs and technical requirements that could be adapted to meet farm composting conditions for agricultural compostable plastics is proposed. These requirements may be used as criteria for the establishment of a new integrative norm for agricultural compostable plastics.     

Bio-Based Polymers and End-of-Life Vehicles

As new materials, such as bio-based plastics and composites, are introduced in vehicles for their improved environmental performance, it is necessary to understand how to efficiently recover these biodegradable materials. This paper provides an overview of the end-of-life phase for automobiles, focusing on the dismantling and shredding processes, and the recovery of materials. Targeted unit operations, such as dismantling of components from vehicles and pretreatment prior to shredding, along with design-for-environment principles, should enable the efficient recovery of materials at the end-of-life phase compared with popularly conceived all-in-one-approaches because of the diverse arrangement of material components.     

Bioabsorbable soy protein plastic composites: Effect of polyphosphate fillers on water absorption and mechanical properties

The use of synthetic and natural bioabsorbable plastics has been severely limited due to their low stiffness and strength properties as well as their strong tendency to absorb moisture. This research focused on the development of bioabsorbable polyphosphate filler/soy protein plastic composites with enhanced stiffness, strength, and water resistance. Bioabsorbable polyphosphate fillers, biodegradable soy protein isolate, plasticizer, and adhesion promoter were homogenized and compression-molded. Physical, mechanical, and water absorption testing was performed on the molded specimens. Results showed improvements in stiffness, strength, and water resistance with increasing polyphosphate filler content up to 20% by weight. Application of a coupling agent produced further mechanical property enhancements and a dramatic improvement in water resistance, interpreted by an interfacial chemical bonding model. Examination of the fracture surfaces of the materials revealed that the addition of the polyphosphate fillers changed the failure mode from brittle to pseudo-ductile. These results suggest that these materials are suitable for many load-bearing applications in both humid and dry environments where current soy protein plastics are not usable.     

Recent Advances in the Production, Recovery and Applications of Polyhydroxyalkanoates

Polyhydroxyalkanoates (PHAs) are biodegradable and biocompatible polyesters that can potentially replace certain plastics derived from petroleum. PHAs can be produced using a combination of renewable feedstocks and biological methods. Native and recombinant microorganisms have been generally used for making PHAs via fermentation processes. As much as 90 % of the microbial dry mass may accumulate as PHAs. A range of PHAs has been produced using fermentation methods, including copolymers and block copolymers. Alternative production schemes based on genetically modified plants are becoming established and may become the preferred route for producing certain PHAs. Production in plants is likely to be inexpensive compared to production by fermentation, but it does not appear to be as versatile as microbial synthesis in terms of the range of products that may be generated. Cell-free enzymatic production of PHAs in vitro is receiving increasing attention and may become the preferred route to some specialty products. This review discusses the recent advances in production of polyhydroxyalkanoates by the various methods. Methods of recovering the polymer from microbial biomass are reviewed. Established and emerging applications of PHAs are discussed.     

Synthesis and Characterization of Lactic Acid Oligomers: Evaluation of Performance as Poly(Lactic Acid) Plasticizers

The use of fully bio-based and biodegradable materials for massive applications, such as food packaging, is an emerging tendency in polymer research. But the formulations proposed in this way should preserve or even increase the functional properties of conventional polymers, such as transparency, homogeneity, mechanical properties and low migration of their components to foodstuff. This is not always trivial, in particular when brittle biopolymers, such as poly(lactic acid) (PLA), are considered. In this work the formulation of innovative materials based on PLA modified with highly compatible plasticizers, i.e. oligomers of lactic acid (OLAs) is proposed. Three different synthesis conditions for OLAs were tested and the resulting additives were further blended with commercial PLA obtaining transparent and ductile materials, able for films manufacturing. These materials were tested in their structural, thermal and tensile properties and the best formulation among the three materials was selected. OLA with molar mass (M_n) around 1,000 Da is proposed as an innovative and fully compatible and biodegradable plasticizer for PLA, able to replace conventional plasticizers (phthalates, adipates or citrates) currently used for films manufacturing in food packaging applications.     

An Overview on the Mechanical Behaviour of Biodegradable Agricultural Films

The mechanical behavior of various types of biodegradable materials depends, mainly, on their chemical composition and the application conditions. Various additives are added into the bioblends to improve their properties, which sometimes even reach the levels of the conventional plastics. It is well known that the environmental conditions during production, storage, and usage of these materials influence their mechanical properties. Ageing during the useful lifetime also causes great losses in the elongation. In the present paper, the overall mechanical behavior of biodegradable films, which may be considered suitable for agricultural applications, but also of partially biodegradable films, is reviewed and analyzed. Selected critical mechanical properties of films before their exposure to biodegradation are investigated and compared against those of conventional agricultural films.     

Processing and mechanical properties of biodegradable Poly(hydroxybutyrate-co-valerate)-starch compositions

Poly(hydroxybutyrate-co-valerate) (PHBV) is a completely biodegradable thermoplastic polyester produced by microbial fermentation. The current market price of PHBV is significantly higher than that of commodity plastics such as polyethylene and polystyrene. It is therefore desirable to develop low-cost PHBV based materials to improve market opportunities for PHBV. We have produced low-cost environmentally compatible materials by blending PHBV with granular starch and environmentally benign CaCO₃. Such materials can be used for specific applications where product biodegradability is a key factor and where certain mechanical properties can be compromised at the expense of lower cost. The inclusion of granular starch (25 wt%) and CaCO₃ (10 wt%) in a PHBV matrix (8% HV, 5% plasticizer) reduces the cost by approximately 40% and has a tensile strength of 16 MPa and flexural modulus of 2.0 Gpa, while the unfilled PHBV/plasticizer matrix has a tensile strength of 27 MPa and a flexural modulus of 1.6 GPa.Paper presented at the Bio/Environmentally Degradable Polymer Society—Third National Meeting, June 6–8, 1994, Boston, Massachusetts.The mention of firm names or trade products does not imply that they are endorsed or recommended by the U.S. Department of Agriculture over other firms or similar products not mentioned.     

Behaviour of biodegradable plastics in composting facilities

Composting is a preferred treatment strategy for biodegradable plastics (BDPs). In this sense, the collection of BDPs together with organic household wastes is a highly discussed possibility. Under the aspect of the behaviour of BDPs in composting facilities, a telephone survey was carried out with selected composting facility operators. They were interviewed with respect to treated wastes, content of impurities, processes for impurity separation, experiences with biodegradable plastics and assumptions to the behaviour of biodegradable plastics in their facility. Forty percent of the facilities had some experiences with BDPs due to test runs, and also since the occurrence of BDPs in their waste was known. The majority of the operators expressed apprehension regarding an increase of impurities resulting from a combined collection of biowaste and BDPs. In the facilities, measures for the impurity separation from the biowaste were used in common practice - in 33% of the cases, separation of disturbing plastics was done before composting, in 33% after composting, and in 13% before and after composting. The most important separation processes for conventional plastics were sieving and manual sorting. In two cases air classification was also used. When asked about the separation possibility of the conventional but not of the biodegradable plastics in their facilities, the majority of operators were not in a position to comment or they replied that it was not an option. No problems were seen in most cases if the impurity separation follows composting. If impurity separation takes place before composting it was often assumed that the BDPs are mainly separated by sieving. In conclusion, in more than half of the cases, BDPs would not be composted if delivered to a composting facility. Under the actual conditions regarding the collection and the treatment/disposal possibilities, an application of BDPs seems to only be reasonable for clean (i.e., source separated on their own) fractions of BDPs.     

Biodegradable Polymers- A Review on Recent Trends and Emerging Perspectives

Recent trends in biodegradable polymers indicate significant developments in terms of novel design strategies and engineering to provide advanced polymers with comparably good performance. However, there are several inadequacies in terms of either technology or cost of production especially in the case of applications in environmental pollution. So, there is a need to have a fresh perspective on the design, properties and functions of these polymers with a view to developing strategies for future developments. The paper reviews the present state-of-art on biodegradable polymers and discusses the salient features of the design and properties of biodegradable polymers. Special emphasis is given to the problems and prospects of (1) approaches adopted to make non-biodegradable synthetic polymers such as polyethylene biodegradable and (2) biodegradable polymers and copolymers made from renewable resources especially poly(lactic acid) based polymers and copolymers which are emerging as the candidate biodegradable materials for the future.     

Critical Review of Norms and Standards for Biodegradable Agricultural Plastics Part Ι. Biodegradation in Soil

A critical review of norms and standards and corresponding tests to determine the biodegradability in soil for biodegradable plastics, possibly applicable also to biodegradable agricultural plastics, is presented. There are only a few norms available at the international level about biodegradable plastics in soil. The criteria, parameters and testing methodologies for the characterization, labelling and validation of the agricultural plastic waste streams with respect to possible biodegradation in soil according to existing international standards are analysed while the relevant controversies are identified. To derive the best suited for agricultural plastics specs and testing methods, the possible developments or adaptation of available specs, is investigated. Considering the existing types of biodegradable plastic products in agriculture and their effective life management at the agricultural field, only a few norms appear to provide suitable tests that could be adapted, following appropriate research work, for testing biodegradability in soil under real field conditions. It is shown that some major revisions are needed, with the support of systematic research work, before a new universal norm and standard testing methods become available for testing agricultural plastics for biodegradation under real, and highly variable, soil conditions. Based on the analysis of the different norms and their content it appears necessary to incorporate provisions for transferability of results to different soils and climates, validation of tests through a positive reference and also, set prerequisites for soil media. Long term biodegradation in soil prediction is another open issue.     

Poly(hydroxyalkanoates) from fluorescent pseudomonads in retrospect and prospect

Poly[(R)-3-hydroxyalkanoates] (PHAs) are biopolymers stored by bacteria, which are currently receiving much attention because of their potential as renewable and biodegradable plastics. Most well-known representatives are poly[(R)-3-hydroxybutyrate] and its copolymers with 3-hydroxyvalerate, which have been commercialized under the trademark Biopol. In addition to these rigid materials, the elastomeric medium-chain length PHAs (mcl-PHAs) produced by fluorescent Pseudomonads are now emerging. The present review aims to survey the important developments concerning research and application prospects of mcl-PHAs.     

Effects of biodegradable plastic components on metabolism of an estuarine benthos

We examined the metabolic response of an estuarine benthic community to additions of three materials being considered for use in manufacture of biodegradable substitutes for plastics. Diver-collected cores containing benthos were dosed with 59 g/m² of three test materials, cornstarch, a bacterial polyester (PHBV), and ethylene vinyl alcohol (EVOH), or left undisturbed as controls. Fluxes of dissolved nutrients (ammonia, nitrate + nitrite, phosphate, silica) and dissolved inorganic carbon (DIC) were similar in control cores and cores dosed with EVOH during a 1-month test period at 20°C. Fluxes in cores dosed with starch and PHBV differed significantly from controls but not from each other. After 2 weeks of incubation, production of DIC was higher in cores containing starch and PHBV, while efflux of ammonia, nitrate, and nitrite was reduced. After 4 weeks of incubation, production of DIC was similar among all treatments and controls, while efflux of ammonia was high in the starch- and PHBV-containing cores compared to controls and cores with EVOH. Fluxes of silica and phosphate were similar in all cores during the experiment. These results indicate that both starch and PHBV are carbon-rich substrates readily metabolized by the benthic community but that their presence significantly alters normal nutrient exchange patterns. This response is expected because of the high carbon-to-nitrogen ratio of starch and PHBV and indicates that impacts of these two materials would be similar. However, the high biological oxygen demand of such materials and resulting disturbance of normal nutrient regeneration patterns of the benthos (delayed ammonia efflux and potential stimulation of denitrification) must be considered in developing strategies for their disposal.Paper presented at the Biodegradable Materials and Packaging Conference, September 22–23, 1993, Natick, Massachusetts.     

Biosynthesis of poly-(R)-3-hydroxyalkanoate: An emulsion polymerization

Poly-(R)-3-hydroxyalkanoates (PHAs) are bacterial storage polyesters, which are accumulated by a wide variety of microorganisms as a reserve of carbon and energy. Currently, these biopolymers are receiving much attention because of their potential application as biodegradable and biocompatible plastics. The polymer appears as submicron intracellular granules. The biosynthesis of these granules has been studied extensively but many observations remain inexplicable. This paper draws an analogy between the process of emulsion polymerization and that of granule formation. This analogy may explain many of the unknown features of granule formation and may also lead to useful applications of granules as latex products.     

Biodegradation of Agricultural Plastic Films: A Critical Review

The growing use of plastics in agriculture has enabled farmers to increase their crop production. One major drawback of most polymers used in agriculture is the problem with their disposal, following their useful life-time. Non-degradable polymers, being resistive to degradation (depending on the polymer, additives, conditions etc) tend to accumulate as plastic waste, creating a serious problem of plastic waste management. In cases such plastic waste ends-up in landfills or it is buried in soil, questions are raised about their possible effects on the environment, whether they biodegrade at all, and if they do, what is the rate of (bio?)degradation and what effect the products of (bio?)degradation have on the environment, including the effects of the additives used. Possible degradation of agricultural plastic waste should not result in contamination of the soil and pollution of the environment (including aesthetic pollution or problems with the agricultural products safety). Ideally, a degradable polymer should be fully biodegradable leaving no harmful substances in the environment. Most experts and acceptable standards define a fully biodegradable polymer as a polymer that is completely converted by microorganisms to carbon dioxide, water, mineral and biomass, with no negative environmental impact or ecotoxicity. However, part of the ongoing debate concerns the question of what is an acceptable period of time for the biodegradation to occur and how this is measured. Many polymers that are claimed to be ‘biodegradable’ are in fact ‘bioerodable’, ‘hydrobiodegradable’, ‘photodegradable’, controlled degradable or just partially biodegradable. This review paper attempts to delineate the definition of degradability of polymers used in agriculture. Emphasis is placed on the controversial issues regarding biodegradability of some of these polymers.     

Biomass Carbon Ratio of Polymer Composites Measured by Accelerator Mass Spectrometry

The evaluation method of biomass carbon ratio of polymer composite samples including organic and inorganic carbons individually was investigated. Biodegradable plastics and biobased plastics can have their mechanical properties improved by combining with inorganic fillers. Polymer composites consisting of biodegradable plastics and carbonate were prepared by two different methods. Poly(lactic acid) (PLA) composite was prepared by synthesis from l-lactide with catalyst and calcium carbonate (CaCO₃) powders from lime. Poly(butylene succinate) (PBS) composite was prepared by hot-pressing the mixture of PBS powder and CaCO₃ powders from oyster shells. The mechanical properties of composite samples were investigated by a tensile test and a compression test using an Instron type mechanical tester. Tensile test with a dumbbell shape specimen was performed for PBS composite samples and compression test with a column shape specimen for PLA composite samples. Strength, elastic modulus and fracture strain were obtained from the above tests. Biomass carbon ratio is regulated in the American Standards for Testing and Materials (ASTM). In ASTM standards on biomass carbon ratio, it is required that carbon atoms from carbonates, such as CaCO₃, are omitted. Biomass carbon ratio was evaluated by ratio of ¹⁴C to ¹²C in the samples using Accelerator Mass Spectrometry (AMS). The effect of pretreatment, such as oxidation temperature and reaction by acid, on results of biomass carbon ratio was investigated. Mechanical properties decrease with increasing CaCO₃ content. The possibility of an evaluation method of biomass carbon ratio of materials including organic and inorganic carbons was shown.     

Experimental Processing of Biodegradable Drip Irrigation Systems—Possibilities and Limitations

The increased cost associated with the waste removal and disposal of conventional agricultural plastic in contact with the soil combined with the gradually decreasing cost of the biodegradable plastics allowed the commercialization of biodegradable mulching films. Since the conventional thin wall or tape drip irrigation system lies under the mulching film and is used for one season only, it would be desirable to replace it with a biodegradable one. This paper presents the results of a research work investigating the possibilities and limitations in developing biodegradable drip irrigation thin wall pipes and pipes. The first ever experimental biodegradable drip irrigation thin wall pipes were produced. Rigid pipes were also produced for experimental purposes. Manufacturing problems were encountered in the processing of the biodegradable drippers and irrigation thin wall pipes with the experimental materials due to the complex formulation of the raw materials and the fact that the machinery used was specifically designed for PE processing. Experimental biodegradable thin wall pipes made of Bioflex with embedded drippers made of Mater-Bi were produced. The processing problems encountered with the production of thin wall pipes were surpassed during the experimental production of rigid type irrigation pipes. A biodegradable rigid irrigation pipe made of a grade of Mater-Bi, with embedded cylindrical drippers made of another grade of Mater-Bi was produced successfully. A better understanding of the thermal profile of the biodegradable raw materials and the use of processing equipment adapted to this profile might allow in the future the manufacturing of thin wall drip irrigation pipes for agricultural applications, and the use of alternative biodegradable materials.     

Comparison of the weight-loss degradability of various biodegradable plastics under laboratory composting conditions

Eight kinds of biodegradable plastics were compared for their degradability in controlled laboratory composting conditions. A thin film of each plastic was mixed into the composting material, and weight-loss degradability was calculated from the weight changes of the film during composting. It was found that weight-loss degradability strongly depended on the specific kind of biodegradable plastic; two were very high, four moderate, and the remaining two very slight. The most easily degradable plastic degraded by as much as 81.4% over 8 days of composting. By comparing the weight-loss degradability with ultimate degradability, which is defined as a molar ratio of carbon loss as CO₂ to the carbon contained in the biodegradable plastic, the order of the ease of degradation of the biodegradable plastics differed. Received: February 7, 2000 / Accepted April 14, 2000     

Biodegradation Properties of Poly-ε-caprolactone,Starch and Cellulose Acetate Butyrate Composites

Blending starches with polymers such as poly-ε-caprolactone (PCL) has been used as a route to biodegradable plastics. The addition of starch has a significant effect on all physical properties including toughness, elongation at break. On blending cellulose acetate butyrate (CAB) with starch and PCL, improvements in most physical and mechanical properties were observed. This is may be due to CAB acts as a compatibilizer between PCL and starch due to the presence of both hydroxyl groups (in starch and CAB) and ester carbonyls (in PCL and CAB). The presence of different compounds affects the way in which other components degrade. For example the structure of CAB within a starch and PCL combination might make the degradation rate different to that when starch was only mixed with PCL. To check whether this was the case, three combinations of different blends were used to calculate the rate of degradation of each of them separately. These degradation rate constants were then used to predict the theoretical degradation which was checked against the experimental value for other different combinations.