Biodegradation and Ecotoxicity of Polyethylene Films Containing Pro-Oxidant Additive

The worldwide accumulation of non-degradable plastic materials, such as plastic bags, is one of the most important environmental concerns nowadays. The use of degradable materials is an option to mitigate the environmental impact generated by the consumption of plastics. One of the technologies used for the manufacture and use of degradable plastics is the use of pro-degradant additives that are incorporated in conventional plastics to promote their degradation under certain conditions. The aim of this study is to evaluate the process of oxidation, biodegradation and potential ecotoxicity of polyethylene films containing an oxo-degradable additive, according to the standard ASTM D-6954. This method establishes a procedure in which the samples are subjected to consecutive steps of accelerated oxidation, biodegradation by composting and ecotoxicity assessment. Furthermore, the effect of the presence of printing ink in the polyethylene samples with oxo-degradable additive was evaluated, and the results were compared with those obtained for samples of conventional polyethylene and polylactic acid. After 180 days of laboratory controlled composting, the samples reached the following percentages of biodegradation: polylactic acid, 41 %; printed oxo-degradable polyethylene, 32.24 %; oxo-degradable polyethylene, 25.84 %; printed polyethylene, 18.23 % and polyethylene, 13.48 %. The cellulose sample used as a control was mineralized in 58.45 %. Ecotoxicity assessment showed that the products of biodegradation of the samples tested, did not generate a negative effect on germination or development of the vegetal species studied. Under proper waste management conditions, these plastics can be used as an option to decrease the environmental impact of plastic films.     

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     

Biodegradability of biodegradable/degradable plastic materials under aerobic and anaerobic conditions

A study was conducted on two types of plastic materials, Mater-Bi Novamont (MB) and Environmental Product Inc. (EPI), to assess their biodegradability under aerobic and anaerobic conditions. For aerobic conditions, organic fractions of municipal solid wastes were composted. For the anaerobic process, anaerobic inoculum from a wastewater treatment plant was used. Cellulose filter papers (CFP) were used as a positive control for both mediums. The composting process was monitored in terms of temperature, moisture and volatile solids and the biodegradation of the samples were monitored in terms of mass loss. Monitoring results showed a biodegradation of 27.1% on a dry basis for MB plastic within a period of 72 days of composting. Biodegradability under an anaerobic environment was monitored in terms of biogas production. A cumulative methane gas production of 245ml was obtained for MB, which showed good degradation as compared to CFP (246.8ml). However, EPI plastic showed a cumulative methane value of 7.6ml for a period of 32 days, which was close to the blank (4.0ml). The EPI plastic did not biodegrade under either condition. The cumulative carbon dioxide evolution after 32 days was as follows: CFP 4.406cm(3), MB 2.198cm(3) and EPI 1.328cm(3). The cumulative level of CO(2) varying with time fitted sigmoid type curves with R(2) values of 0.996, 0.996 and 0.995 for CFP, MB and EPI, respectively.     

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.     

Biodegradability of degradable plastic waste.

Plastic waste constitutes the third largest waste volume in Malaysian municipal solid waste (MSW), next to putrescible waste and paper. The plastic component in MSW from Kuala Lumpur averages 24% (by weight), whereas the national mean is about 15%. The 144 waste dumps in the country receive about 95% of the MSW, including plastic waste. The useful life of the landfills is fast diminishing as the plastic waste stays un-degraded for more than 50 years. In this study the compostability of polyethylene and pro-oxidant additive-based environmentally degradable plastics (EDP) was investigated. Linear low-density polyethylene (LLDPE) samples exposed hydrolytically or oxidatively at 60 degrees C showed that the abiotic degradation path was oxidative rather than hydrolytic. There was a weight loss of 8% and the plastic has been oxidized as shown by the additional carbonyl group exhibited in the Fourier transform infra red (FTIR) Spectrum. Oxidation rate seemed to be influenced by the amount of pro-oxidant additive, the chemical structure and morphology of the plastic samples, and the surface area. Composting studies during a 45-day experiment showed that the percentage elongation (reduction) was 20% for McD samples [high-density polyethylene, (HDPE) with 3% additive] and LL samples (LLDPE with 7% additive) and 18% reduction for totally degradable plastic (TDP) samples (HDPE with 3% additive). Lastly, microbial experiments using Pseudomonas aeroginosa on carbon-free media with degradable plastic samples as the sole carbon source, showed confirmatory results. A positive bacterial growth and a weight loss of 2.2% for degraded polyethylene samples were evident to show that the degradable plastic is biodegradable.     

Effects of Storage Time on Properties of Soybean Protein-Based Plastics

Soybean protein has been considered as a potential biodegradable polymer in the manufacture of plastics. The purpose of this investigation was to characterize the effect of storage time on thermal and mechanical properties of soybean protein isolate (SPI) plastics. SPI was separated from defatted soy flour, modified with 1M or 2M urea, or plasticized with glycerol, and compression molded into plastics. Plastic made from SPI alone was used as a control. For all SPI plastics, glass transition temperatures and dynamic storage modulus increased and loss tangent decreased during storage. Excess enthalpy of relaxation of all SPI plastics had an exponential relationship with storage time, indicating a fast aging rate at the beginning of storage. All SPI plastics tended to be stiff and brittle during storage. The plastics with glycerol had the slowest aging rate and were fairly stable after 60 days, with about 8.8 MPa tensile strength and 168% strain at break. Plastics with the 2M urea-modification SPI also had a slow aging rate and became relative stable after 60 days, with about 10 MPa tensile strength and 72% elongation.     

Biodegradation of Whey Protein-Based Edible Films

The biodegradability of the edible films made of whey proteins by disulfide cross-linking was investigated. Whey protein concentrate (WPC) and whey protein isolate (WPI) films were subjected to microbial degradation using Pseudomonas aeruginosa and composting burial degradation. Results from the microbial degradation showed that whey protein films could support the growth of P. aeruginosa. The bacterial growth characteristics were well described using the Gompertz model. WPC films degraded faster than WPI films, suggesting that the biodegradability of protein films is associated with the film composition and the extent of covalent cross-linking. WPI films buried in a compost pile began to degrade in two days and became darker over time. More than 80% of total solids were lost in 7 days.     

Thermal degradation of PMMA in fluidised beds

In recent years, the production and consumption of plastics have increased significantly and wastes are commonly incinerated or dumped in a landfill. Plastics pyrolysis, on the other hand, may provide an alternative means for disposal of plastic wastes with recovery of valuable gasoline-range hydrocarbons or the monomer. Pyrolysis of polymethyl methacrylate (PMMA) may result in very high recycling rates (90-98%) of the monomer methylmethacrylate (MMA) since the cracking of MMA to lighter molecules (CO2, CO and light hydrocarbons) is limited. The MMA-yield is mainly dependent on the residence time of the gas in the reactor and to a lesser extent on the operating temperature. The paper presents experimental work performed in a lead bath and in a fluidised bed. At low temperatures, the reaction is kinetically controlled, whereas at high temperatures, heat transfer restricts the overall reaction rate. It was demonstrated that the heat transfer in the fluid bed could be estimated by the equation of Kothari. A design procedure for a fluid bed PMMA-depolymerisation reactor is outlined and illustrated for a process of 1 tpd PMMA.     

An accelerated laboratory study evaluating the disintegration rates of plastic films in simulated aquatic environments

Six plastic films were exposed to accelerated sunlight while in simulated aquatic environments to determine the effects of chemical composition and environment on the disintegration rates. An environment of UV light/no water was used as a control to determine if the microorganisms in the aquatic systems enhanced the breakdown of the plastic films. The disintegration rate of the plastics was determined by monitoring changes in selected physical properties. The plastics included two conventional plastics commonly used in packaging (LDPE and polystyrene) and four plastics enhanced to have more rapid breakdown in the environment (2% ECO, 10% ECO, PE with ketone graft, and PE with starch). The two ECO copolymers had a significantly faster loss of physical properties than the other plastics evaluated in this study. Degradation was influenced by environmental conditions. Those plastics that showed a change in physical properties had a greater change faster in the UV light/no water than in the environments where water was present. Plastics on the surface of the water showed a more rapid loss of properties than those samples partially or completely submerged. This can be attributed to decreased light intensity and the lack of heat buildup.     

Biodegradable kinetics of plastics under controlled composting conditions

This study models and evaluates the kinetics of C-CO₂ evolution during biodegradation of plastic materials including Polyethylene (PE), PE/starch blend (PE/starch), microcrystalline cellulose (MCE), and Polylactic acid (PLA). The aerobic biodegradation under controlled composting conditions was monitorated according to ISO 14855-1, 2004. The kinetics model was based on first order reaction in series with a flat lag phase. A non-linear regression technique was used to analyze the experimental data. SEM studies of the morphology of the samples before and after biodegradation testing were used to confirm the biodegradability of plastics and the accuracy of the model. The work showed that MCE and PLA produced the high amounts of C-CO₂ evolution, which gave readily hydrolysable carbon values of 55.49% and 40.17%, respectively with readily hydrolysis rates of 0.338 day⁻¹ and 0.025 day⁻¹, respectively. Whereas, a lower amount of C-CO₂ evolution was found in PE/starch, which had a high concentration of moderately hydrolysable carbon of 97.74% and a moderate hydrolysis rate of 0.00098 day⁻¹. The mineralization rate of PLA was 0.500 day⁻¹ as a lag phase was observed at the beginning of the biodegradability test. No lag phase was observed in the biodegradability testing of the PE/starch and MCE. The mineralization rates of the PE/starch and MCE were found to be 1.000 day⁻¹, and 1.234 day⁻¹, respectively. No C-CO₂ evolution was observed during biodegradability testing of PE, which was used for reference as a non-biodegradable plastics sample.     

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.     

Predicting biodegradable volatile solids degradation profiles in the composting process

This paper presents a new method for the prediction of the pattern of biodegradable volatile solids (BVS) degradation in the composting process. The procedure is based on a re-arrangement of the heat balance around a composting system to numerically solve for the rate of BVS carbon (BVS-C) disappearance. Input data for the model was obtained from composting experiments conducted in a laboratory-scale, constant temperature difference (CTD) reactor simulating a section of an aerated static pile, and using a simulated feedstock comprising ostrich feed, shredded paper, finished compost and woodchips. These experiments also provided validation data in the form of exit gas CO(2) carbon (CO(2)-C) profiles. The model successfully predicted the generic shape of experimental substrate degradation profiles obtained from CO(2) measurements, but under the conditions and assumptions of the experiment, the profiles were quantitatively different, giving an over-estimate of BVS-C. Both measured CO(2)-C and predicted BVS-C profiles were moderately to well fitted by a single exponential function, with replicated rate coefficient values of 0.08 and 0.09 d(-1), and 0.06 and 0.07 d(-1), respectively. In order to explore the underlying shape of the profiles, measured and predicted data at varying temperature were corrected to a constant temperature of 40 degrees C, using the temperature correction function of Rosso et al. [Rosso, L., Lobry, J.R., and Flandrois, J.P., 1993. An unexpected correlation between cardinal temperatures of microbial growth highlighted by a new model. Journal of Theoretical Biology, 162, 447-463], with cardinal temperatures of 5, 59 and 85 degrees C. Multi-phase profiles were generated for both the measured CO(2)-C and the predicted BVS-C data in this case. However, when alternative cardinal temperatures of 5, 55 and 80 degrees C, or 5, 50 and 80 degrees C, were used, the predicted profiles assumed an exponential shape, and excellent fits were obtained using a double exponential function. These findings support the argument that a substrate degradation curve generated under laboratory conditions at 40 degrees C, would, given correct cardinal temperatures, generate a correct substrate degradation profile under varying temperature conditions and that this in turn would enable an accurate and precise prediction of the temperature profile, using a heat and mass balance approach. In order to realise this prospect, it is proposed that further work to obtain experimental data under completely mixed conditions, more accurately estimate the overall heat transfer coefficient and obtain correct values for the cardinal temperatures used in the temperature correction function, is required.     

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.     

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.     

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.     

PLA and Organoclays Nanocomposites: Degradation Process and Evaluation of ecotoxicity Using Allium cepa as Test Organism

In this study, nanocomposites of PLA and organoclays Cloisite 20A and Cloisite 30B were prepared by the melt intercalation method and the obtained samples were characterized by transmission electron microscopy (TEM). Since composting is an important proposal to the final disposal of biopolymers, the influence of clays on the hydrolytic degradation process of PLA was evaluated by visual analysis and monitoring of molecular weight after periods of 15 and 30 days of degradation in compost. After degradation of the materials in composting environment, the evaluation of cytotoxic, genotoxic and mutagenic effects of compost aqueous extract was carried out using a bioassay with Allium cepa as test organism. The TEM micrographs permitted the observation of different levels of dispersion, including exfoliated regions. In the evaluation of hydrolytic degradation it was noted that the presence of organoclays can decrease the rate of degradation possibly due to the barrier effect of clay layers and/or the higher degree of crystallinity in the nanocomposite samples. Nevertheless, even in the case of nanocomposites, the molecular weight reduction was significant, indicating that the composting process is favorable to the chain scission of PLA in studied materials. In the analysis performed by the bioassay using A. cepa as test organism, it was found that after degradation of the PLA and its nanocomposites the aqueous extract of compost samples induced a decreasing in the mitotic index and an increasing in the induction of chromosomal abnormalities. These results were statistically significant in relation to the negative control (distilled water). By comparing the results obtained for the nanocomposites in relative to pure polymer, there were no statistically significant differences. The types of the observed chromosomal aberrations indicated a possible genotoxic effect of the materials, which may be related to an aneugenic action of PLA degradation products.     

Effect of the composting substrate on biodegradation of solid materials under controlled composting conditions

Biodegradability under composting conditions is assessed by test methods, such as ASTM D 5338-92, based on the measurement of CO₂ released by test materials when mixed with mature compost and maintained in a controlled composting environment. However, in real composting, biodegradation occurs in fresh waste. To clarify this point, the biodegradation of paper and of a starch-based biodegradable thermoplastic material, Mater-Bi ZI01U, was followed by measuring the weight loss of samples introduced either into a mature compost or into a synthetic waste. The weight loss in mature compost was higher at the beginning but tended to decrease; in synthetic waste a first lag phase was followed by an exponential phase. Complete degradation of paper was noticed simultaneously in the two substrates (after 25 days). The bulkier Mater-Bi samples were fully degraded after 20 days in fresh waste, but after 45 days in mature compost. Therefore, the test methods using mature compost as a substrate can possibly underestimate the biodegradation rate occurring in fresh waste, i.e., in real composting plants, and have to be considered as conservative test methods. The test procedure described in this paper seems very suitable as a screening method to verify the compostability of plastic materials in a composting environment.     

Application of a simplified mathematical model to estimate the effect of forced aeration on composting in a closed system

The aeration rate is a key process control parameter in the forced aeration composting process because it greatly affects different physico-chemical parameters such as temperature and moisture content, and indirectly influences the biological degradation rate. In this study, the effect of a constant airflow rate on vertical temperature distribution and organic waste degradation in the composting mass is analyzed using a previously developed mathematical model of the composting process. The model was applied to analyze the effect of two different ambient conditions, namely, hot and cold ambient condition, and four different airflow rates such as 1.5, 3.0, 4.5, and 6.0m(3)m(-2)h(-1), respectively, on the temperature distribution and organic waste degradation in a given waste mixture. The typical waste mixture had 59% moisture content and 96% volatile solids, however, the proportion could be varied as required. The results suggested that the model could be efficiently used to analyze composting under variable ambient and operating conditions. A lower airflow rate around 1.5-3.0m(3)m(-2)h(-1) was found to be suitable for cold ambient condition while a higher airflow rate around 4.5-6.0m(3)m(-2)h(-1) was preferable for hot ambient condition. The engineered way of application of this model is flexible which allows the changes in any input parameters within the realistic range. It can be widely used for conceptual process design, studies on the effect of ambient conditions, optimization studies in existing composting plants, and process control.     

Biodegradation of Bloodmeal-Based Thermoplastics in Green-Waste Composting

Polymers that are compostable and manufactured from renewable resources have gained significant importance in recent years. The objective of this work was to assess the biodegradability of bloodmeal-based thermoplastics in a commercial green-waste composting situation. Materials plasticised with tri-ethylene–glycol lost about 45% of their original mass after 12 weeks composting while unplasticised samples lost 35%. Degradation appeared to have been in two phases; an initial loss of soluble, low molecular compounds in the mesophilic phase followed by degradation of high molecular compounds as the temperature exceeded about 40 °C in the thermophilic phase. It was found that as degradation proceeded materials became more soluble. In addition, plasticised and unplasticized samples contained about 60 wt% moisture after 4 weeks of composting conditioning at 50% relative humidity resulted in approximately 8–10 wt% moisture, unaffected by the extent of degradation. FTIR revealed that proteins underwent hydrolytic cleavage resulting in the formation of primary amines. A significant reduction in combustion temperature was observed, indicative of a reduction in covalent bonding, likely due to shorter chains lengths or less cross-linking.     

Boiling treatment of ABS and PS plastics for flotation separation

A new physical method, namely boiling treatment, was developed to aid flotation separation of acrylonitrile–butadiene–styrene (ABS) and polystyrene (PS) plastics. Boiling treatment was shown to be effective in producing a hydrophilic surface on ABS plastic. Fourier Transform Infrared analysis was conducted to investigate the mechanism of boiling treatment of ABS. Surface rearrangement of polymer may be responsible for surface change of boiling treated ABS, and the selective influence of boiling treatment on the floatability of boiling treated plastics may be attributed to the difference in the molecular mobility of polymer chains. The effects of flotation time, frother concentration and particle size on flotation behavior of simple plastic were investigated. Based on flotation behavior of simple plastic, flotation separation of boiling treatment ABS and PS with different particle sizes was achieved efficiently. The purity of ABS and PS was up to 99.78% and 95.80%, respectively; the recovery of ABS and PS was up to 95.81% and 99.82%, respectively. Boiling treatment promotes the industrial application of plastics flotation and facilitates plastic recycling.