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 Behaviors of Poly(p-dioxanone) in Different Environment Media

This work was aimed at researching the aerobic biodegradation of poly(p-dioxanone) (PPDO), a novel kind of degradable polymer material, by simulating real-life conditions in a laboratory-scale test, specified by the standard methods based on two biodegradation environments, composting and aqueous media. To measure and describe the biodegradability of PPDO, not only had carbon dioxide produced by respiratory metabolism of microorganism been measured, which determines the ultimate aerobic biodegradability of chemical compounds, but also the detailed results of biodegradation were further characterized by monitoring physical, chemical and thermal properties changes of test materials at different incubation times in the two media, confirmed by using the appropriate analytical techniques. Scanning electron microscopy was used to observe the surface morphology, and the thermal performance of PPDO was characterized by differential scanning calorimetry. The changes of molecular weight were detected by intrinsic viscosity ([η]) and gel permeation chromatography, and the variations of the molecular structure were monitored by the nuclear magnetic resonance and FT-IR. The results show that PPDO has outstanding character of biodegradation and may be more adapted for biodegrading in liquid medium than in composting.     

Biodegradation of Polycaprolactone Powders Proposed as Reference Test Materials for International Standard of Biodegradation Evaluation Method

Polycaprolactone (PCL) powders were prepared from PCL pellets using a rotation mechanical mixer. PCL powders were separated by sieves with 60 and 120 meshes into four classes; 0–125 μm, 125–250 μm, 0–250 μm and 250–500 μm. Biodegradation tests of PCL powders and cellulose powders in an aqueous solution at 25°C were performed using the coulometer according to ISO 14851. Biodegradation tests of PCL powders and cellulose powders in controlled compost at 58°C were performed by the Mitsui Chemical Analysis and Consulting Service, Inc. according to ISO 14855-1 and by using the Microbial Oxidative Degradation Analyzer (MODA) instrument according to ISO/DIS 14855-2. PCL powders were faster biodegraded than cellulose powders. The reproducibility of biodegradation of PCL powders is excellent. Differences in the biodegradation of PCL powders with different class were not observed by the ISO 14851 and ISO/DIS 14855-2. An enzymatic degradation test of PCL powders with different class was studied using an enzyme of Amano Lipase PS. PCL with smaller particle size was faster degraded by the enzyme. PCL powders with regulated sizes from 125 μm to 250 μm are proposed as a reference material for the biodegradation test.     

Aerobic biometer analysis of glucose and starch biodegradation

The ASTM D5210-91 protocol for evaluating the biodegradability of a polymer was examined. The reactor design was modified not only to account for the total CO₂ evolved but also to allow for the simultaneous carbon assessment in microbes, soluble products, and solid samples. Improvements in the test procedure were implemented such as (1) refining the CO₂ pretrap and posttrap design, (2) optimizing the carbon dioxide removal efficiency, (3) accounting for the total polymeric carbon, (4) standardizing the inoculum, and (5) revising the nutrient medium. By growing the sludge on a suitable substrate prior to polymeric exposure, a constant microbial density was obtained. The modified ASTM method provides an assessment of the polymeric carbon degradation at any given time. The results of this work have specific significance to the behavior of polymers in a sewage waste treatment plant, where sludge is continuously being acrated, and also for aerobic biodegradation in general.     

Microbial biomass yield and turnover in soil biodegradation tests: carbon substrate effects

Most of the standardized biodegradation tests used to assess the ultimate biodegradation of environmentally degradable polymers are based solely on the determination of net evolved carbon dioxide. However, under aerobic conditions, it has to be considered that heterotrophic microbial consortia metabolize carbon substrates both to carbon dioxide and in the production of new cell biomass. It is generally accepted that in the relatively short term, 50% of the carbon content of most organic substrates is converted to CO₂, with the remaining carbon being assimilated as biomass or incorporated into humus. The latter is particularly important when the metabolism of the organic matter occurs in a soil environment. A straightforward relationship between the free-energy content of a carbon substrate (expressed as the standard free-energy of combustion) and its propensity for conversion to new microbial biomass rather than mineralization to CO₂ has been established. This can potentially lead to underestimation of biodegradation levels of test compounds, especially when they consist of carbon in a fairly low formal oxidation state and relatively high free-energy content. In the present work, the metabolism of different kind of carbon substrates, especially in soil, is reviewed and compared with our own experimental results from respirometric tests. The results show that conversion of highly oxidized materials, such as the commonly used reference materials, cellulose or starch, to CO₂ may be significantly overestimated. The addition of glucosidic material to soil leads to greatly increased respiration and is accompanied by a very low conversion to biomass or humic substances. In contrast, relatively less oxidized substrates metabolize more slowly to give both CO₂ and biomass to an extent which may be significantly underestimated if glucosidic materials are used as the reference. The need for an overall carbon balance taking into account both the carbon immobilized as biomass and that volatized as CO₂ must be considered in standard respirometric procedures for assessing the biodegradability of slowly degrading macromolecules.     

Biodegradability and compostability of polymers—test methods and criteria for evaluation

The treatment of solid waste in controlled composting facilities is an important possibility for reducing garbage. Natural and synthetic polymeric materials can be used for many purposes, for example, as packaging materials, where compostability is required. A prerequisite for official regulations and the decision as to which materials may be composted is investigations on their biodegradability and the quality of the compost produced. Several standardization groups at the ISO, CEN, and DIN are developing definitions, test methods, and classification systems for differentiating compostable from noncompostable materials. The concept which will be standardized and used in Germany is described in detail. It includes characterization of the test material, determination of the biodegradability using laboratory tests such as simple aquatic batch tests and a controlled aerobic composting test, investigation of the disintegration of the test material in industrial or bench-scale composting facilities, and finally, chemical and ecotoxicological analysis of the compost produced.     

A New Respirometric Test Simulating Soil Burial Conditions for the Evaluation of Polymer Biodegradation

A new convenient and reliable method is described for assessing the biodegradation properties of polymeric materials under simulated soil burial conditions, which makes it possible to test with nutrient-rich soils. This method consists of the utilization of a minimum amount of a soil layer, in which the samples to be tested are set in close contact, sandwiched between two layers of perlite, a natural porous aluminosilicate. The biodegradation level is monitored by determining the carbon dioxide evolution derived from the test samples. The limited amount of soil used limits carbon dioxide evolution from the blanks, due to the corresponding limited overall amount of soil carbon. This experimental setup allows for an extremely satisfactory level of confidence in the analytical results, permitting a wider variety of soil types to be tested.     

“二级厌氧-微氧-好氧”组合工艺处理模拟碳纤维生产废水

对模拟碳纤维生产废水进行“厌氧-好氧”静态小试,根据COD的去除效果确定该碳纤维废水的可生化性。采用“二级厌氧-微氧-好氧”组合工艺进行动态中试,考察废水的处理效果及系统的抗冲击性能。试验结果表明：该工艺对碳纤维生产废水的处理效果较好;系统具有厌氧池出水pH增大的特点,且抗冲击能力较强;在厌氧池水温为28~38 ℃、好氧池水温不低于15 ℃、废水流量为100 L/h、进水COD为660 mg/L、进水ρ（氨氮）为4.9 mg/L的条件下,出水COD稳定在50 mg/L以下,ρ（氨氮）稳定在5 mg/L以下,能够满足GB 8978-1996《污水综合排放标准》的要求。     

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.     

Photodegradation and Biodegradation Study of a Starch and Poly(Lactic Acid) Coextruded Material

To simulate the behavior of agricultural mulch coextruded poly(lactic acid)(PLA)/starch films, two stages were carried out. The first was an ultraviolet treatment (UV) at 315 nm, during which glass transition temperature T_g, weight, and molecular weight (MW) decreased and a separation between PLA and starch phase was observed. For the second stage, the mineralization of the carbon of the material was followed using the ASTM (D 5209–92 and 5338–92) and ISO/CEN (14852 and 14855) standard procedures. To measure the biodegradability of polymer material, the assessment of the carbon balance allowed determination of the distribution between the carbon rate used to the biomass synthesis or the respiration process (released CO₂), as well as the dissolved organic carbon into the culture medium and the carbon in the residual insoluble material. The influence of the nature of the medium and the standardized procedures on the final rate of biodegradation was investigated. Whatever the standardized method, the biodegradation percentage was significantly stronger in liquid medium (92.4–93.4) than on inert medium (80–83%). In the case of the compost process, only released CO₂ was measured and corresponded to 79.1–80.3%.     

Evaluation of the Biodegradation of Starch and Cellulose Under Controlled Composting Conditions

In order to verify the response of the controlled composting test method (i.e., the ISO/DIS 14855:1997, the ASTM D 5338-92, or the CEN counterpart) to starch at different concentrations, the maximum amount prescribed by the test method (100 g) and lower amounts (60 and 30 g), as if starch were a coingredient in a blend, were tested. After 44 days of incubation (at a constant temperature of 58°C) the biodegradation curves were in a plateau phase, displaying the following final values (referred to a nominal starch initial amount of 100 g): starch 100 g, 97.5%; starch 60 g, 63.7%; and starch 30 g, 32.5%. The data show a CO₂ evolution roughly equal, in each case, to the theoretical maximum, indicating a complete starch mineralization. We cannot discern whether the deviations found at lower concentrations are caused by a priming effect. In any case, the extent of the deviations is not high and is acceptable in biodegradation studies. The average biodegradation of cellulose, obtained gathering four independent experiments with 11 biodegradation curves, turned out to be 96.8 ± 6.7% (SD) after 47 ± 1 days. The data indicate that the controlled composting is a reliable test method also for starch and cellulose and, consequently, for starch-based and cellulose-based materials.     

Determination of the carbon content of biomass—A prerequisite to estimate the complete biodegradation of polymers

This article presents a method to determine the carbon content of biomass, which is formed when degrading biodegradable polymers in an aerobic aqueous test system. Existing methods for determining the carbon content of biomass (e.g., fumigazation, protein assays, dry solids) have several disadvantages when applied for polymer degradation tests. In this work a protein assay based on the Lowry method was used. It was shown that the ratio between protein and carbon content is not constant but depends on the composition of the microbial population, the growth phase, and the substrate supply. This effect was used for the method presented in this article. For determining the carbon content of biomass the absorbance obtained by the Lowry test is correlated directly with the carbon content of biomass in dependence on the duration of the degradation test. The calibration curves are obtained by a mixed population of microorganisms during the course of a degradation test.     

A kinetic analysis of solid waste composting at optimal conditions

This discussion explores the possibility of having a measure of the biodegradable organic carbon content in solid wastes. Currently, indirect measures for determining the concentration of biodegradable organic matter are being used and most of them are based on respiration indices (oxygen consumption or carbon dioxide production) or chemical parameters (volatile solids or total organic carbon). The results obtained for the cumulative carbon dioxide production in composting experiments can be expressed as "aerobic biodegradable carbon" for the wastes that were studied. The calculation of a useful biodegradable C/N can also be obtained from the aerobic biodegradable carbon content. A comparison with some results obtained in measuring the concentration of "anaerobic biodegradable carbon" also is presented.     

The Relationship Between the Chemical Structure of Poly(alkylene glycol)s and Their Aerobic Biodegradability in an Aqueous Environment

The relationship between the chemical structure of poly(alkylene glycol)s (PAGs) and their biodegradability was studied using a set of polymeric fluids that included poly(ethylene glycol), poly(propylene glycol) (PPG), random copolymers of ethylene oxide (EO) and propylene oxide (PO) differing in the EO/PO ratio as well as PAGs capped with ether or acyl moieties. The PAGs that were tested had an average molecular weight (MW) in the range of 350–3,600 Da and differed in their polymer backbones by either linear (diol type) or branched (triol type) molecules. The ultimate biodegradability of the PAGs was determined according to ISO 14593 (CO₂ headspace test) with a non-pre-exposed (as in OECD 310 test) and pre-exposed (adapted) inoculum. PAGs with the structure of PPG and copolymers of EO/PO of diol or triol structures with average molecular weights lower than 1,000 Da can be considered as readily biodegradable. Their ultimate biodegradation exceeds the limit of 60 % (according to the criteria of the OECD 310 test). PAGs with a copolymer structure and MW values ranging between 1,000 and 3,600 Da are not readily biodegradable, but they can be considered as those of inherent ultimate biodegradability. The increased EO content in PAG structures and the acylation of the terminal hydroxyl groups with carboxylic acids favourably influenced their biodegradability. Capped PAGs containing terminal ether groups appeared to be resistant to biodegradation.     

Processability and Biodegradability Evaluation of Composites from Poly(butylene succinate) (PBS) Bioplastic and Biofuel Co-products from Ontario

This study investigates the processability and biodegradability of composite bioplastic materials. Biocomposites were processed using twin-screw compounding of the bioplastic poly(butylene succinate) (PBS) with bio-based fillers derived from co-products of biofuel production. An extensive biodegradability evaluation was conducted on each biocomposite material, as well as the base materials, using respirometric testing to analyze the conversion of organic carbon into carbon dioxide. This evaluation revealed that the presence of meal-based fillers in the biocomposites increased the rate of biodegradation of the matrix polymer, degrading at a faster pace than both the pure PBS polymer and the switchgrass (SG) composite. This degradation was further confirmed using FT-IR and thermal analysis of the material structure before and after biodegradation. The increased biodegradation rate is attributed to the high concentration of proteins in the meal-based composites, which enhanced the hydrolytic biodegradation of the material and facilitated micro-organism growth. The SG-based composite degraded slower than the pure polymer due to its lignin content, which degrades via a different mechanism than the polymer, and slowed the biodegradation process.     

Bioabsorbable Soy Protein Plastic Composites: Effect of Polyphosphate Fillers on Biodegradability

The use of biodegradable polymers made from renewable agricultural products such as soy protein isolate has been limited by the tendency of these materials to absorb moisture. A straightforward approach for controlling the inherent water absorbency of the biodegradable polymers involves blending special bioabsorbable polyphosphate fillers, biodegradable soy protein isolate, plasticizer, and adhesion promoter in a high-shear mixer followed by compression molding. The procedure yields a relatively water-resistant, biodegradable soy protein polymer composite, as previously reported. The aim of the present study is to determine the biodegradability of the new polyphosphate filler/soy protein plastic composites by monitoring the carbon dioxide released over a period of 120 days. The results suggest that the composites biodegrade satisfactorily, with the fillers having no significant effect on the depolymerization and mineralization of the soy protein plastic, processes that would otherwise result in nonbiodegradable composites. Further, the results indicate that the biodegradation and useful service life of these biocomposites may be controlled by changing the filler concentration, making the biocomposites useful in applications in which the control of water resistance and biodegradation is critical.     

Assessment of Several Test Methods for the Determination of the Anaerobic Biodegradability of Polymers

Anaerobic degradation of eight commercially available biodegradable polymers was compared in two anaerobic tests using digestion sludge, according to ISO 11734 and ASTM D.5210-91. Cotton, polyhydroxybutyrate/hydroxyvalerate copolymer (PHB/PHV), starch blend, thermoplastic cellulose acetate, and cellulose acetate fibers proved to be anaerobically degradable, but only a low extent of degradation was found for polylactide, polyvinylalcohol, and polycaprolactone. Both test methods gave the same overall results, but with the ISO medium, longer lag phases and greater ranges of variation in the results were observed. These effects are presumably due to low concentrations of carbon dioxide in the ISO medium. Carbon dioxide has been demonstrated to be essential for the growth of various anaerobic bacteria, notably homoacetogenic and methanogenic bacteria.     

Test methods to aid in the evaluation of the diversion of biodegradable municipal waste (BMW) from landfill

This discussion explores one crucial point about the use of biodegradability indicators to monitor biological processes in organic solid waste treatment plants. Today, some different measures are being used for the determination of biodegradable organic matter and most of them are based on respiration indices (oxygen consumption or carbon dioxide production under aerobic conditions) or biogas production tests (under strict anaerobic conditions). However, it is not evident from scientific literature that both tests may be equivalent or comparable. This discussion includes the results obtained when trying to correlate both anaerobic and aerobic tests to complement the recent work published by Wagland et al. [Wagland, S.T., Tyrrel, S.F., Godley, A.R., Smith, R., 2009. Test methods to aid in the evaluation of the diversion of biodegradable municipal waste (BMW) from landfill. Waste Management 29, 1218–1226].     

Enzymatic Degradation of Cellulose-Based Materials

The biodegradability of cellulose-based materials was compared in the standard Sturm test and by enzymatic hydrolysis. Trichoderma reesei culture filtrate, the purified enzymes endoglucanase I and II from T. reesei, and -glucosidase from Aspergillus niger were used in the experiments. The unpurified Trichoderma reesei culture filtrate was found to contain a mixture of enzymes suitable for cellulose degradation. However, when purified enzymes were used the right balance of the individual enzymes was necessary. The addition of -glucosidase enhanced the enzymatic hydrolysis of cellulose materials when both culture filtrate and purified enzymes were used. In the Sturm test the biodegradability of most of the cellulose materials exceeded 70% carbon dioxide generation, but, in contrast, the biodegradability of the highly substituted aminated cellulose and cellulose acetate was below 10%. The results concerning enzymatic hydrolysis and biodegradability were in good agreement for kraft paper, sausage casing, aminated cellulose, and cellulose acetate. However, diverging results were obtained with cotton fabric, probably as a result of its high crystallinity.     

Kinetics of Aerobic Polymer Degradation in Soil by Means of the ASTM D 5988-96 Standard Method

The standard test method ASTM D 5988-96 for determining the degree and rate of aerobic biodegradation of plastic materials in contact with soil was applied to poly(3-hydroxybutyrate) and poly(-caprolactone). The method proved to be reliable and supplied reproducible measurements of CO₂ production, provided potassium (instead of barium) hydroxide was used as a trapping solution. The trends of CO₂ evolution, as a function of time, observed for the degradation of polymer powders in soil are similar to those predicted by simple first order kinetics in solution. The experimental data are described by a Michaelis–Menten type model, which accounts for the heterogeneity of the polymer-soil system. The kinetic equation deduced predicts the degradation rate to the proportional to the exposed polymer surface area.