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.     

Enhanced Mineralization of PLA Meltblown Materials Due to Plasticization

Polylactic acid (PLA) is one of the important biodegradable polymers. It is widely used in many industrial applications such as films and fibers. Its biodegradability is based on data derived mostly from composting processes. For a broad application of the PLA material in personal care products, an understanding of anaerobic biodegradability is essential because soiled personal care products are usually disposed of in sanitary landfills, where biodegradability mechanisms are predominately in anaerobic conditions. Extensive laboratory results are acquired to elucidate the effects of the temperature on the PLA anaerobic sludge biodegradation. When the temperature is higher than PLA glass transition temperature (T_g), anaerobic degradation is accelerated. A plausible mechanism to explain this observation is that amorphous part of the polymer is easily accessible by microorganisms. When the degrading temperature is below PLA glass transition temperature, sample mineralization under anaerobic conditions is apparently slowed. The mechanisms elucidated by T_g modification can be utilized to control the rate of PLA biodegradation for sustainable waste management.     

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.     

Assessing the biodegradation potential of polymers in screening- and long-term test systems

This paper presents a test scheme for assessing the biodegradation potential of polymers, starting with aquatic screening systems (aerobic and anaerobic) and continuing to long-term systems. At the end of the scheme the material has to prove its behavior under the relevant disposal conditions. Aerobic screening was performed mainly under aquatic conditions, but also in soil, using BOD-respirometry. Carbon balances were performed to obtain a better evaluation of the biodegradation potential. Under anaerobic conditions, biodegradation in an aquatic medium was followed by measuring CH₄ and CO₂ production. Polymers not fully degraded in the screening systems were tested in aquarium systems for at least 1 year. Biodegradation was followed by monitoring the DOC released in the water, mass loss, and microbial growth on the samples and in the water as well as via FTIR spectroscopy and SEM pictures. Results are presented for the polymers PHB, PHBV, PCL, Mater-Bi AI05H and ZF03U, and Bioceta. By combining the data from the screening with the aquarium system, a good picture of the degradation behavior of the polymers is obtained.Paper presented at the Bio/Environmentally Degradable Polymer Society—Third National Meeting, June 6–8, 1994, Boston, Massachusetts.     

An overview of methods for biodegradability testing of biopolymers and packaging materials

This paper gives an overview of the methods used at the Technical Research Centre of Finland (VTT) for the biodegradability testing of solid polymers and packaging materials. Biodegradability of each polymer included in the packaging material should be separately tested. Aquatic aerobic and anaerobic tests and, in specific cases, enzymatic tests are used for screening purposes. The application of aquatic aerobic tests—an automated Sturm test (OECD 301B; ASTM D5209) and a VTT headspace test as well as an anaerobic test (ASTM D5210)—is discussed. Three composting tests and their applications are summarized. These tests are regarded as important because they can be used to simulate the biodegradability under real-life conditions. Several tests are needed to determine the fate of the polymer under real conditions and to study its biodegradability in different environments. The time needed for complete biodegradation of polymers in nature is impossible to predict with laboratory tests and should be studiedin vivo.According to the lecture given in Sweden at the Royal Institute of Technology, at a workshop on polymers from renewable resources and their degradation, November 10–11, 1994.     

Limits and dynamics of methane oxidation in landfill cover soils

In order to understand the limits and dynamics of methane (CH₄) oxidation in landfill cover soils, we investigated CH₄ oxidation in daily, intermediate, and final cover soils from two California landfills as a function of temperature, soil moisture and CO₂ concentration. The results indicate a significant difference between the observed soil CH₄ oxidation at field sampled conditions compared to optimum conditions achieved through pre-incubation (60 days) in the presence of CH₄ (50 ml l⁻¹) and soil moisture optimization. This pre-incubation period normalized CH₄ oxidation rates to within the same order of magnitude (112-644 μg CH₄ g⁻¹ day⁻¹) for all the cover soils samples examined, as opposed to the four orders of magnitude variation in the soil CH₄ oxidation rates without this pre-incubation (0.9-277 μg CH₄ g⁻¹ day⁻¹).Using pre-incubated soils, a minimum soil moisture potential threshold for CH₄ oxidation activity was estimated at 1500 kPa, which is the soil wilting point. From the laboratory incubations, 50% of the oxidation capacity was inhibited at soil moisture potential drier than 700 kPa and optimum oxidation activity was typical observed at 50 kPa, which is just slightly drier than field capacity (33 kPa). At the extreme temperatures for CH₄ oxidation activity, this minimum moisture potential threshold decreased (300 kPa for temperatures <5 °C and 50 kPa for temperatures >40 °C), indicating the requirement for more easily available soil water. However, oxidation rates at these extreme temperatures were less than 10% of the rate observed at more optimum temperatures (∼30 °C). For temperatures from 5 to 40 °C, the rate of CH₄ oxidation was not limited by moisture potentials between 0 (saturated) and 50 kPa. The use of soil moisture potential normalizes soil variability (e.g. soil texture and organic matter content) with respect to the effect of soil moisture on methanotroph activity. The results of this study indicate that the wilting point is the lower moisture threshold for CH₄ oxidation activity and optimum moisture potential is close to field capacity.No inhibitory effects of elevated CO₂ soil gas concentrations were observed on CH₄ oxidation rates. However, significant differences were observed for diurnal temperature fluctuations compared to thermally equivalent daily isothermal incubations.     

Novel Biodegradable Thermoplastic Elastomer Based on Poly(butylene succinate) and Epoxidized Natural Rubber Simple Blends

Novel biodegradable thermoplastic elastomer based on epoxidized natural rubber (ENR) and poly(butylene succinate) (PBS) blend was prepared by a simple blend technique. Influence of blend ratios of ENR and PBS on morphological, mechanical, thermal and biodegradable properties were investigated. In addition, chemical interaction between ENR and PBS molecules was evaluated by means of the rheological properties and infrared spectroscopy. Furthermore, the phase inversion behavior of ENR/PBS blend was predicted by different empirical and semi-empirical models including Utracki, Paul and Barlow, Steinmann and Gergen models. It was found that the co-continuous phase morphology was observed in the blend with ENR/PBS about 58/42 wt% which is in good agreement with the model of Steinmann. This correlates well to morphological and mechanical properties together with degree of crystallinity of PBS in the blends. In addition, the biodegradability was characterized by soil burial test after 1, 3 and 9 months and found that the biodegradable ENR/PBS blends with optimum mechanical and biodegradability were successfully prepared.     

Parameters affecting the stability of the digestate from a two-stage anaerobic process treating the organic fraction of municipal solid waste

This paper focused on the factors affecting the respiration rate of the digestate taken from a continuous anaerobic two-stage process treating the organic fraction of municipal solid waste (OFMSW). The process involved a hydrolytic reactor (HR) that produced a leachate fed to a submerged anaerobic membrane bioreactor (SAMBR). It was found that a volatile solids (VS) removal in the range 40-75% and an operating temperature in the HR between 21 and 35 °C resulted in digestates with similar respiration rates, with all digestates requiring 17 days of aeration before satisfying the British Standard Institution stability threshold of 16 mg CO₂ g VS⁻¹ day⁻¹. Sanitization of the digestate at 65 °C for 7 days allowed a mature digestate to be obtained. At 4 g VS L⁻¹ d⁻¹ and Solid Retention Times (SRT) greater than 70 days, all the digestates emitted CO₂ at a rate lower than 25 mg CO₂ g VS⁻¹ d⁻¹ after 3 days of aeration, while at SRT lower than 20 days all the digestates displayed a respiration rate greater than 25 mg CO₂ g VS⁻¹ d⁻¹. The compliance criteria for Class I digestate set by the European Commission (EC) and British Standard Institution (BSI) could not be met because of nickel and chromium contamination, which was probably due to attrition of the stainless steel stirrer in the HR.     

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.     

Influence of aeration on CH4, N2O and NH3 emissions during aerobic composting of a chicken manure and high C/N waste mixture

Co-composting of chicken manure, straw and dry grasses was investigated in a forced aeration system to estimate the effect of aeration rates on NH₃, CH₄ and N₂O emissions and compost quality. Continuous measurements of gas emissions were carried out and detailed gas emission patterns were obtained using an intermittent-aeration of 30 min on/30 min off at rates of 0.01 (A1), 0.1 (A2) and 0.2 (A3) m³ min⁻¹ m⁻³. Concentrations of CH₄ and N₂O at the low aeration rate (A1) were significantly greater than those at the other two rates, but there was no significant difference between the A2 and A3 treatments. CH₄ and N₂O emissions for this mixture could be controlled when the composting process was aerobic and ammonia emissions were reduced at a lower aeration rate. Comparison of CH₄, N₂O, NH₃ emissions and compost quality showed that the aeration rate of the A2 treatment was superior to the other two aeration rates.     

Assessing Aerobic Biodegradability of Plastics in Aqueous Environment by GC-Analyzing Composition of Equilibrium Gaseous Phase

Testing biodegradability of plastics under varied conditions of the environment as well as under laboratory conditions in accordance with valid international standards is very laborious, lengthy and often also economically demanding. For this reason, applicability was verified of gas chromatography to analyze gaseous phase when investigating the biodegradation course of plastics in an aqueous environment as an alternative to customary employed methods. A mathematical model of acid–basic CO₂ equilibrium in a gas–liquid system was worked out, enabling to determine quantity of produced CO₂ through chromatographic analysis of gaseous phase, in dependence on ratio of liquid and gas phase volumes (V _l/V _g) and on actual pH of liquid phase. Experimental conditions for organizing the tests were optimized. A ratio that proved suitable was V _l/V _g ≅ 0.1 at pH ≈ 7.1 of liquid phase. Under these test conditions, biodegradability of model samples, PHB, Gellan gum and Xanthan gum, was explored; course of biodegradation was studied through produced CO₂ (values ) determined by analyzing gaseous phase through gas chromatography on the one hand, and through customary “titration” procedure on the other. With water-soluble polymers, the decrement in dissolved organic carbon (values D _DOC) was also studied. Difference between values does not exceed 5%. The procedures in question are alternative “substituting” procedures for observing course of aerobic biodegradation of substances in an aqueous environment.     

Dry-thermophilic anaerobic digestion of organic fraction of municipal solid waste: methane production modeling

The influence of particle size and organic matter content of organic fraction of municipal solid waste (OFMSW) in the overall kinetics of dry (30% total solids) thermophilic (55 °C) anaerobic digestion have been studied in a semi-continuous stirred tank reactor (SSTR). Two types of wastes were used: synthetic OFMSW (average particle size of 1 mm; 0.71 g Volatile Solids/g waste), and OFMSW coming from a composting full scale plant (average particle size of 30 mm; 0.16 g Volatile Solids/g waste).A modification of a widely-validated product-generation kinetic model has been proposed. Results obtained from the modified-model parameterization at steady-state (that include new kinetic parameters as K, Y_pMAX and θ_MIN) indicate that the features of the feedstock strongly influence the kinetics of the process. The overall specific growth rate of microorganisms (μ_max) with synthetic OFMSW is 43% higher compared to OFMSW coming from a composting full scale plant: 0.238 d⁻¹ (K = 1.391 d⁻¹; Y_pMAX = 1.167 L CH₄/gDOC_c; θ_MIN = 7.924 days) vs. 0.135 d⁻¹ (K = 1.282 d⁻¹; Y_pMAX = 1.150 L CH₄/gDOC_c; θ_MIN = 9.997 days) respectively.Finally, it could be emphasized that the validation of proposed modified-model has been performed successfully by means of the simulation of non-steady state data for the different SRTs tested with each waste.     

Comparison of semi-aerobic and anaerobic degradation of refuse with recirculation after leachate treatment by aged refuse bioreactor

Two fresh refuse bioreactors (F1 and F2) were operated under semi-aerobic and anaerobic conditions, respectively. The leachate from the bioreactors F1 and F2 was introduced into the aged refuse bioreactors (A1 and A2), and the effluent from A1 and A2 was subsequently recirculated into F1 and F2, respectively. The effect of the semi-aerobic recirculation process on refuse degradation was investigated, comparing it with that of the anaerobic recirculation process. Results indicate that the semi-aerobic recirculation process can increase the accumulated net production of leachate and promote evaporation. The accumulated net production of refuse in F1 is 320 mL/kg and that of F2 is 248 mL/kg, with leachate reduction amounting to 315 and 244 mL/kg refuse, respectively. The leachate quantity reduction of semi-aerobic and anaerobic leachate recirculation process accounted for 98.4% and 98.3% of the accumulated net production of leachate, respectively. The semi-aerobic leachate recirculation process can improve the biodegradation of organic matter from fresh refuse and the reduction rate of the pollutant concentration in leachate. This should shorten considerably the time required to meet the discharge standard and the time of stabilization of the refuse as observed in the anaerobic recirculation process. It was predicted that the COD concentration of leachate from the anaerobic recirculation process would reach 1000 mg/L in the anaerobic recirculation process after 2.2 years, as for semi-aerobic leachate recirculation process it is about 100 days. Compared with anaerobic recirculation process, the semi-aerobic recirculation process is more effective on NH₃-N transformation and TN removal. The NH₃-N and TN concentration of F1 is far below those of F2 at the end of our experiment. Refuse settlement in the semi-aerobic recirculation process was faster than that in the anaerobic recirculation process. At the end of the experiment, refuse settlement ratios in the semi-aerobic and anaerobic bioreactors were 33.5% and 18%, respectively.     

Aerobic Biodegradation of Polymers in Solid-State Conditions: A Review of Environmental and Physicochemical Parameter Settings in Laboratory Simulations

During the last few years, biodegradable polymers have been developed to replace petrochemical polymers. Until now, research devoted to these polymers essentially focused on their biodegradability. There is now a need to bear out their nontoxicity. To verify this, the biodegradation must be carried out in accelerated laboratory tests which allow the metabolites and residues to be recovered. To reproduce the natural conditions (compost, field) as closely as possible, degradation experiments must be run on solid-state substrates. We review studies of aerobic degradation in solid-state substrates. This article focuses in particular on the environmental, physical, and chemical parameters (such as substrate nature, moisture, temperature, C/N ratio, and pH) that influence biodegradation kinetics. This study also aims at finding the solid substrate most adapted to residues and metabolite recovery. The most significant parameters would appear to be the substrate type, moisture content, and temperature. Inert substrates such as vermiculite are well suited to residue extraction. This review also opens the field to new research aimed at optimizing conditions for aerobic solid-state biodegradation and at recovering the metabolites and residues of this degradation process.     

Biodegradation of Poly(Aspartic Acid-Itaconic Acid) Copolymers by Miscellaneous Microbes from Natural Water

Poly(aspartic acid-itaconic acid) copolymers (PAI) is a new scale inhibitor for water treatment. Thus, it is necessary to investigate its biodegradability. The biodegradability of PAI was investigated through CO₂ evolution tests under different conditions based on determination of carbon dioxide production. The investigation results showed that the degradation rate of PAI on day 10 and day 28 were respectively 38.7 and 79.5%, indicating that PAI was one kind of easily biodegradable scale inhibitors. With the increase in the content of itaconic acid in copolymerization process, the biodegradability of PAI was significantly reduced. In addition, the high biodegradability might be attributed to the existence of C–N bone-structure and more –COO–. Finally, Cu²⁺ could decrease the degradation percentage and the enzyme inhibition effect of Cu²⁺ was not the linear effect, but the “low-dosage effect”.     

Observations on the methane oxidation capacity of landfill soils

The objective of this study was to determine the role of CH₄ loading to a landfill cover in the control of CH₄ oxidation rate (g CH₄ m⁻² d⁻¹) and CH₄ oxidation efficiency (% CH₄ oxidation) in a field setting. Specifically, we wanted to assess how much CH₄ a cover soil could handle. To achieve this objective we conducted synoptic measurements of landfill CH₄ emission and CH₄ oxidation in a single season at two Southeastern USA landfills. We hypothesized that percent oxidation would be greatest at sites of low CH₄ emission and would decrease as CH₄ emission rates increased. The trends in the experimental results were then compared to the predictions of two differing numerical models designed to simulate gas transport in landfill covers, one by modeling transport by diffusion only and the second allowing both advection and diffusion. In both field measurements and in modeling, we found that percent oxidation is a decreasing exponential function of the total CH₄ flux rate (CH₄ loading) into the cover. When CH₄ is supplied, a cover’s rate of CH₄ uptake (g CH₄ m⁻² d⁻²) is linear to a point, after which the system becomes saturated. Both field data and modeling results indicate that percent oxidation should not be considered as a constant value. Percent oxidation is a changing quantity and is a function of cover type, climatic conditions and CH₄ loading to the bottom of the cover. The data indicate that an effective way to increase the % oxidation of a landfill cover is to limit the amount of CH₄ delivered to it.     

The relationship between blend miscibility and biodegradation of cellulose acetate and poly(ethylene Succmate) blends

The miscibility of cellulose acetate (CA; degree of substitution = 2.5) and poly(ethylene succinate) (PES) has been investigated using a variety of thermal techniques and by solid-state carbon13 NMR spectroscopy. The blends containing greater than ca. 70% CA were found to be miscible. In the case of blends containing less than ca. 70% CA, a combination of thermal and NMR analyses suggests that these blends are not fully miscible on a 2.5- to 5-nm scale. On the scale which can be probed by dynamic mechanical thermal analysis (15 nm), the low-percentage CA blends exhibit “significant local concentration fluctuations≓. Investigation of the biodegradation of the blend components and of the blends revealed that PES degraded relatively rapidly and that CA degraded slowly. The blends degraded at a rate essentially identical to that of CA. Miscibility (75% CA blend) or crystallization of PES (30% CA blend) had no significant effect. These data suggest that a significant mode of degradation ófPES during composting involves chemical hydrolysis of the polymer followed by biological assimilation of monomers. Degradation of the blends is initiated in the amorphous phase. Because CA is a significant component of the amorphous phase, a small amount of CA significantly impacts the biodegradation rates of the blends.     

Reducing the environmental impact of methane emissions from dairy farms by anaerobic digestion of cattle waste

Four dairy cattle farms considered representative of Northern Spain milk production were studied. Cattle waste was characterised and energy consumption in the farms was inventoried. Methane emissions due to slurry/manure management and fuel consumption on the farms were calculated. The possibility of applying anaerobic digestion to the slurry to minimise emissions and of using the biogas produced to replace fossil fuels on the farm was considered. Methane emissions due to slurry management (storage and use as fertiliser) ranged from 34 to 66 kg CH₄ cow⁻¹ year⁻¹ for dairy cows and from 13 to 25 kg CH₄ cow⁻¹ year⁻¹ for suckler calves. Cattle on these farms are housed for most of the year, and the contribution from emissions from manure dropped in pastures is insignificant due to the very low methane conversion factors. If anaerobic digestion were implemented on the farms, the potential GHG emissions savings per livestock unit would range from 978 to 1776 kg CO₂ eq year⁻¹, with the main savings due to avoided methane emissions during slurry management. The methane produced would be sufficient to supply digester heating needs (35-55% of the total methane produced) and on-farm fuel energy requirements.     

Biodegradable Polymers from 5-Hydroxylevulinic Acid: 1. Synthesis and Characterization of Poly(5-hydroxylevulinic acid)

As an attempt to synthesize new biodegradable polymers from renewable cellulose resources, melt polycondensation of 5-hydroxylevulinic acid (5-HLA) was reported for the first time. The resulting product, poly(5-hydroxylevulinic acid) (PHLA), was synthesized and characterized with GPC, FTIR, ¹H NMR and DSC. The in vitro degradation behaviors in phosphate-buffered saline (PBS) and in deionized water (DW) were also examined. The molecular weight of PHLA is not high (several 1,000s), but it possesses unordinary high glass transition temperature (as high as 120 °C). This is very different from existing aliphatic polyesters that usually have T _gs lower than 60 °C. The high T _g is attributed to the formation of inter- and/or intramolecular hydrogen bonds due to a characteristic keto–enol tautomerism equilibrium in the polymer structure. PHLA readily degraded hydrolytically in aqueous media.     

Evaluation of respiration in compost landfill biocovers intended for methane oxidation

A low-cost alternative approach to reduce landfill gas (LFG) emissions is to integrate compost into the landfill cover design in order to establish a biocover that is optimized for biological oxidation of methane (CH₄). A laboratory and field investigation was performed to quantify respiration in an experimental compost biocover in terms of oxygen (O₂) consumption and carbon dioxide (CO₂) production and emission rates. O₂ consumption and CO₂ production rates were measured in batch and column experiments containing compost sampled from a landfill biowindow at Fakse landfill in Denmark. Column gas concentration profiles were compared to field measurements. Column studies simulating compost respiration in the biowindow showed average CO₂ production and O₂ consumption rates of 107 ± 14 g m⁻² d⁻¹ and 63 ± 12 g m⁻² d⁻¹, respectively. Gas profiles from the columns showed elevated CO₂ concentrations throughout the compost layer, and CO₂ concentrations exceeded 20% at a depth of 40 cm below the surface of the biowindow. Overall, the results showed that respiration of compost material placed in biowindows might generate significant CO₂ emissions. In landfill compost covers, methanotrophs carrying out CH₄ oxidation will compete for O₂ with other aerobic microorganisms. If the compost is not mature, a significant portion of the O₂ diffusing into the compost layer will be consumed by non-methanotrophs, thereby limiting CH₄ oxidation. The results of this study however also suggest that the consumption of O₂ in the compost due to aerobic respiration might increase over time as a result of the accumulation of biomass in the compost after prolonged exposure to CH₄.