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.     

Predicting the degradation pattern of organic materials in the composting of a fed-batch operation as inferred from the results of a batch operation

The degradation pattern of organic materials was confirmed by continuously measuring the quantity of CO₂ evolved during the composting process in both batch and fed-batch operations. It was possible to predict the degradation pattern for organic material during a fed-batch operation from that observed during a batch operation after corrections made on the basis of two suppositions. First, it was assumed that the degradation of dog food (which degrades easily) occurred prior to the degradation of the bulking agent and seeding material that were contained in the raw compost mixture; second, it was assumed that the dog food thrown into the fed-batch operation, where the microorganisms were already proliferating, began to be actively degraded with only a short lag time. Received: June 16, 1998 / Accepted: August 7, 1999     

A respirometric method to measure mineralization of polymeric materials in a matured compost environment

A respirometric method was developed to measure the mineralization of polymeric materials in a matured compost environment. For the purpose of evaluating the method, results obtained for the mineralization of glucose and cellulose are presented. The matured compost, in addition to supplied nutrients, micronutrients, and an inoculum, serves as the matrix which supports the microbial activity. Recovery of the substrate carbon in the form of carbon dioxide from the glucose and cellulose added to test vessels was 68 and 70%, respectively. A statistical evaluation of the results obtained on substrate mineralization was carried out and showed acceptable reproducibility between replicate test vessels and test runs. The testing protocol developed has the following important characteristics: (1) the test reactors are maintained at 53 °C at a high solids loading (60% moisture), which has certain characteristics that are similar to a thermophilic compost environment; (2) the test matrix providing microbial activity is derived from readily available organic materials to facilitate reproducibility of the method in different laboratories; (3) the equipment required to perform this test is relatively inexpensive; and (4) the information obtained on polymer mineralization is vital to the study and development of biodegradable polymeric materials.Guest Editor: Dr. Graham Swift, Rohm & Haas.     

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.     

A spectrophotometric method for detection of enzymatic degradation of thin polymer films

An assay method has been developed for monitoring the enzymatic degradation of thin films of translucent polymers. The method was based on the observation that when a solution-cast film of poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) was exposed to a solution of a depolymerase fromPseudomonas lemoignei, the surface of the film roughened and the film became visibly turbid. This increase in turbidity could be measured spectrophotometrically and was reproducible during the initial stage of degradation. Turbidity correlated very closely with film weight loss early in the degradation but reached a maximum value before extensive degradation had taken place. For a given set of films, this correlation was independent of the concentration of the enzyme used, although it did vary with the mode of enzyme exposure. The turbidity was associated with the exposure of crystalline domains due to the removal of amorphous material from the film surface. The increase in crystallinity at the surface was verified by attenuated total reflectance infrared spectroscopy (ATRIR). In conjunction with SEM, weight loss, and ATRIR, the film turbidity assay provided much semiquantitative insight into the mechanism of the enzymatic degradation reaction. This assay was used to study the enzymatic degradation of films of PHBV solution blended with cellulose acetate esters (CAE). The presence of only 25% of CAE of degree of substitution 2.9 severely hampered the enzymatic degradability of PHBV, a result which is consistent with the environmental degradation of these same samples exposed to activated sludge.     

Novel synthesis blends between bacterial polyesters and acrylic rubber: A study on enzymatic biodegradation

The biodegradability of a multicomponent system based on biotechnological occurring polyester (poly(-hydroxybutyrate-co--hydroxyvalerate) (PHBV)) with inclusion of acrylate elastomer (polybutylacrylate) (PBA) was investigated. A bacterium which produced extracellular enzymes that degrades PHBV even when blended with PBA was isolated and tentatively designated asAureobacterium saperdae. It was observed, by morphological investigation, that, while the bacterial degradation was permitted for PBA content of 20% by weight, it was inhibited for PBA content of 30%, owing to the occurrence of a rubbery layer that prevents to the bacteria an easy accessibility in the PHBV-rich regions. In fact, owing the bacterial growth, only PHBV was metabolized, whereas no degradation of PBA was detected for blend samples. It was confirmed that the degradation proceeded via surface erosion of PHBV also in the blends. Finally, mechanical tests on PHBV/PBA specimens as a function of degradation extent have shown different behavior of the blends at different the PBA content. Thermal analysis of blends and PHBV has been reported, too     

Modelling of organic matter dynamics during the composting process

Composting urban organic wastes enables the recycling of their organic fraction in agriculture. The objective of this new composting model was to gain a clearer understanding of the dynamics of organic fractions during composting and to predict the final quality of composts. Organic matter was split into different compartments according to its degradability. The nature and size of these compartments were studied using a biochemical fractionation method. The evolution of each compartment and the microbial biomass were simulated, as was the total organic carbon loss corresponding to organic carbon mineralisation into CO₂. Twelve composting experiments from different feedstocks were used to calibrate and validate our model. We obtained a unique set of estimated parameters. Good agreement was achieved between the simulated and experimental results that described the evolution of different organic fractions, with the exception of some compost because of a poor simulation of the cellulosic and soluble pools. The degradation rate of the cellulosic fraction appeared to be highly variable and dependent on the origin of the feedstocks. The initial soluble fraction could contain some degradable and recalcitrant elements that are not easily accessible experimentally.     

Pure-culture and enzymatic assay for starch-polyethylene degradable plastic biodegradation withStreptomyces species

Eleven starch-polyethylene degradable plastic films were prepared from masterbatches from Archer Daniels Midland Inc. (ADM), EcoStar Inc. (SLS), and Fully Compounded Plastic Inc. The biodegradability of initial and 70°C heat-treated materials was determined using a pure-culture assay withStreptomyces badius 252,S. setonii 75Vi2, orS. viridosporus T7A or without bacterial culture (control). Films were treated with 10-foldS. setonii culture concentrates and compared with inactive enzyme controls. Changes in each films mechanical property, molecular weight distribution, and Fourier-transformed infrared spectrum (FT-IR) were determined, and results were evaluated for significant differences by analysis of variance. Cell mass accumulation on each film was quite pronounced. In pure-culture studies, biodegradation was demonstrated for ADM-7 and SLS-2 initial films and for ADM-6 heat-treated films, whereas after 3-week treatment with activeS. setonii culture concentrates (enzyme assay), reductions in mechanical properties and changes in FT-IR spectrum were illustrated by all the films except SLS-2. Thus the absence of biofilm formation on the film surface permitted enzymatic attack of the materials. Furthermore, inhibition of chemical oxidative degradation in the pure-culture assay was demonstrated for ADM-11, SLS-5, and SLS-10 initial materials and for ADM-4, ADM-7, SLS-8, and SLS-10 heat-treated films. These data suggest that biological and chemical degradation were directly affected by the reduction in oxygen tension on the plastic film surface due to cell mass accumulation. This same phenomenon could be the cause for slow degradation rates in nature.Journal Paper No. J-15061 of the Iowa Agriculture and Home Economics Experiment Station, Ames, Iowa. Project Nos. 0178 and 2889.     

Increased biodegradation of a low-density polyethylene (LDPE) matrix in starch-filled LDPE materials

Preheated¹⁴C-labeled LDPE-films with 15% corn starch and a proxidant formulation [masterbatch (MB)] incubated in aqueous solutions with fungi at ambient temperature are about three times more susceptible to biodegradation than the corresponding preheated pure LDPE as observed by liquid scintillation counting (LSC). The inbuilt induction time before autoxidation commences can be shortened by initial heating. Preheated LDPE-MB materials biodegrade about five times faster than nonheated ones. After 1 year of biodegradation of nonheated LDPE-MB, sporadic increases in the evolution of¹⁴CO₂ have been noted, showing that the induction time may be running toward and end.     

Effect of environmental parameters on the degradability of polymer films in laboratory-scale composting reactors

Previous research in our laboratory reported a convenient laboratory-scale composting test method to study the weight loss of polymer films in aerobic thermophilic (53°C) reactors maintained at a 60% moisture content. The laboratory-scale compost reactors contained the following synthetic compost mixture (percentage on dry-weight basis): tree leaves (45.0), shredded paper (16.5), food (6.7), meat (5.8), cow manure (17.5), sawdust (1.9), aluminum and steel shavings (2.4), glass beads (1.3), urea (1.9), and a compost seed (1.0) which is designated Mix-1 in this work. To simplify the laboratory-scale compost weight loss test method and better understand how compost mixture compositions and environmental parameters affect the rate of plastic degradation, a systematic variation of the synthetic mixture composition as well as the moisture content was carried out. Cellulose acetate (CA) with a degree of substitution (DS) value of 1.7 and cellophane films were chosen as test polymer substrates for this work. The extent of CA DS-1.7 and cellophane weight loss as a function of the exposure time remained unchanged when the metal and glass components of the mixture were excluded in Mix-2. Further study showed that large variations in the mixture composition such as the replacement of tree leaves, food, meat, and sawdust with steam-exploded wood and alfalfa (forming Mix-C) could be made with little or no change in the time dependence of CA DS-1.7 film weight loss. In contrast, substituting tree leaves, food, meat, cow manure, and sawdust with steam-exploded wood in combination with either Rabbit Choice (Mix-D) or starch and urea (Mix-E) resulted in a significant time increase (from 7 to 12 days) for the complete disappearance of CA DS-1.7 films. Interestingly, in this work no direct correlation was observed between the C/N ratio (which ranged from 13.9 to 61.4) and the CA DS-1.7 film weight loss. Decreasing moisture contents of the compost Mix-2 from 60 and 50 and 40% resulted in dramatic changes in polymer degradation such that CA DS-1.7 showed an increase in the time period for a complete disappearance of polymer films from 6 to 16 and 30 days, respectively.Guest Editor: Dr. Graham Swift, Rohm & Haas.Paper presented at the Bio/Environmentally Degradable Polymer Society—Second National Meeting, August 19–21, 1993, Chicago, Illinois.     

Cellulose acetate biodegradability upon exposure to simulated aerobic composting and anaerobic bioreactor environments

Cellulose acetate (CA) films with degree of substitution (d.s.) values of 1.7 and 2.5 were exposed to biologically active in-laboratory composting test vessels maintained at approximately 53 °C. The CA 1.7- and 2.5-d.s. films (thickness values of 0.5–1.0 and 2.0 mil, respectively) had completely disappeared by the end of 7- and 18-day exposure time periods in the biologically active bioreactors, respectively. The relatively small CA film weight loss observed in the poisoned control test vessels allows the conclusion that CA film erosion during the composting exposures resulted, at least in part, from biologically mediated processes. Under strictly anaerobic conditions, an active methanogenic inoculum was developed by acclimation of a sewage sludge to a synthetic municipal solid waste (SMSW) mixture at 42°C. The CA 1.7-d.s. film samples (0.5- to 1.0-mil thickness) were exposed in anaerobic serum bottles containing a 25% solids loading of SMSW in which methanogenic activity was rapidly established after introducing of the developed inoculum. For exposures of 30 days only small visually distinguishable fragments of the CA 1.7-d.s. films were recovered. In contrast, exposure of the CA 1.7-d.s. film to a poisoned control test vessel resulted in negligible weight loss. Therefore, degradation of the CA 1.7-d.s. films upon exposure to the anaerobic bioreactors was due, at least in part, to biologically mediated processes.Guest Editor: Dr. Graham Swift, Rohm & Haas.     

Speciation of Cu and Zn during composting of pig manure amended with rock phosphate

Pig manure usually contains a large amount of metals, especially Cu and Zn, which may limit its land application. Rock phosphate has been shown to be effective for immobilizing toxic metals in toxic metals contaminated soils. The aim of this study work was to investigate the effect of rock phosphate on the speciation of Cu and Zn during co-composting of pig manure with rice straw. The results showed that composting process and rock phosphate addition significantly affected the changes of metal species. During co-composting, the exchangeable and reducible fractions of Cu were transformed to organic and residue fractions, thus the bioavailable Cu fractions were decreased. The rock phosphate addition enhanced the metal transformation depending on the level of rock phosphate amendment. Zinc was found in the exchangeable and reducible fractions in the compost. The bioavailable Zn fraction changed a little during the composting process. The composting process converted the exchangeable Zn fraction into reducible fraction. Addition of an appropriate amount (5.0%) of rock phosphate could advance the conversion. Rock phosphate could reduce metal availability through adsorption and complexation of the metal ions on inorganic components. The increase in pH and organic matter degradation could be responsible for the reduction in exchangeable and bioavailable Cu fractions and exchangeable Zn fraction in rock phosphate amended compost.     

Odorous gaseous emissions as influence by process condition for the forced aeration composting of pig slaughterhouse sludge

Compost sustainability requires a better control of its gaseous emissions responsible for several impacts including odours. Indeed, composting odours have stopped the operation of many platforms and prevented the installation of others. Accordingly, present technologies collecting and treating gases emitted from composting are not satisfactory and alternative solutions must be found. Thus, the aim of this paper was to study the influence of composting process conditions on gaseous emissions. Pig slaughterhouse sludge mixed with wood chips was composted under forced aeration in 300 L laboratory reactors. The process conditions studied were: aeration rate of 1.68, 4.03, 6.22, 9.80 and 13.44 L/h/kg of wet sludge; incorporation ratio of 0.55, 0.83 and 1.1 (kg of wet wood chips/kg of wet sludge), and; bulking agent particles size of <10, 10 < 20 and 20 < 30 mm. Out-going gases were sampled every 2 days and their composition was analysed using gas chromatography coupled with mass spectrometry (GC–MS). Fifty-nine compounds were identified and quantified. Dividing the cumulated mass production over 30 days of composting, by odour threshold, 9 compounds were identified as main potential odour contributors: hydrogen sulphide, trimethylamine, ammonia, 2-pentanone, 1-propanol-2-methyl, dimethyl sulphide, dimethyl disulphide, dimethyl trisulphide and acetophenone. Five gaseous compounds were correlated with both aeration rate and bulking agent to waste ratio: hydrogen sulphide, trimethylamine, ammonia, 2-pentanone and 1-propanol-2-methyl. However, dropping the aeration rate and increasing the bulking agent to waste ratio reduced gaseous odour emissions by a factor of 5–10, when the required threshold dilution factor ranged from 10⁵ to 10⁶, to avoid nuisance at peak emission rates. Process influence on emissions of dimethyl sulphide, dimethyl disulphide, dimethyl trisulphide were poorly correlated with both aeration rate and bulking agent to waste ratio as a reaction with hydrogen sulphide was suspected. Acetophenone emissions originated from the wood chips. Olfactory measurements need to be correlated to gaseous emissions for a more accurate odour emission evaluation.     

The effects of apple pomace,bentonite and calcium superphosphate on swine manure aerobic composting

The effects of additives such as apple pomace, bentonite and calcium superphosphate on swine manure composting were investigated in a self-built aerated static box (90 L) by assessing their influences on the transformation of nitrogen, carbon, phosphorous and compost maturity. The results showed that additives all prolonged the thermophilic stage in composting compared to control. Nitrogen losses amounted to 34–58% of the initial nitrogen, in which ammonia volatilization accounted for 0.3–4.6%. Calcium superphosphate was helpful in facilitating composting process as it significantly reduced the ammonia volatilization during thermophilic stage and increased the contents of total nitrogen and phosphorous in compost, but bentonite increased the ammonia volatilization and reduced the total nitrogen concentration. It suggested that calcium superphosphate is an effective additive for keeping nitrogen during swine manure composting.     

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     

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.     

GHG emission factors developed for the recycling and composting of municipal waste in South African municipalities

GHG (greenhouse gas) emission factors for waste management are increasingly used, but such factors are very scarce for developing countries. This paper shows how such factors have been developed for the recycling of glass, metals (Al and Fe), plastics and paper from municipal solid waste, as well as for the composting of garden refuse in South Africa. The emission factors developed for the different recyclables in the country show savings varying from ?290 kg CO₂ e (glass) to ?19 111 kg CO₂ e (metals – Al) per tonne of recyclable. They also show that there is variability, with energy intensive materials like metals having higher GHG savings in South Africa as compared to other countries. This underlines the interrelation of the waste management system of a country/region with other systems, in particular with energy generation, which in South Africa, is heavily reliant on coal. This study also shows that composting of garden waste is a net GHG emitter, releasing 172 and 186 kg CO₂ e per tonne of wet garden waste for aerated dome composting and turned windrow composting, respectively. The paper concludes that these emission factors are facilitating GHG emissions modelling for waste management in South Africa and enabling local municipalities to identify best practice in this regard.     

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.     

The influence of degree of substitution on blend miscibility and biodegradation of cellulose acetate blends

In this account, we report our findings on blends of cellulose acetate having a degree of substitution (DS) of 2.49 (CA2.5) with a cellulose acetate having a DS of 2.06 (CA2.0). This blend system was examined over the composition range of 0–100% CA2.0 employing both solvent casting of films (no plasticizer) and thermal processing (melt-compressed films and injection molding) using poly(ethylene glycol) as a common plasticizer. All thermally processed blends were optically clear and showed no loss in optical quality after storage for several months. Thermal analysis and measurement of physical properties indicate that blends in the middle composition range are partially miscible, while those at the ends of the composition range are miscible. We suggest that the miscibility of these cellulose acetate blends is influenced primarily by the monomer composition of the copolymers. Bench-scale simulated municipal composting confirmed the biodestructability of these blends and indicated that incorporation of a plasticizer accelerated the composting rates of the blends.In vitro aerobic biodegradation testing involving radiochemical labeling conclusively demonstrated that both the lower DS CA2.0 and the plasticizer significantly enhanced the biodegradation of the more highly substituted CA2.5.While this work was in progress, Robert Gardner was struck with cancer and died on June 6, 1995. This paper is dedicated to his memory and to his contributions as a friend and colleague.     

Molecular Weight Changes and Polymeric Matrix Changes Correlated with the Formation of Degradation Products in Biodegraded Polyethylene

The molecular weight changes in abiotically and biotically degraded LDPE and LDPE modified with starch and/or prooxidant were compared with the formation of degradation products. The samples were thermooxidized for 6 days at 100°C to initiate degradation and then either inoculated with Arthobacter paraffineus or kept sterile. After 3.5 years homologous series of mono- and dicarboxylic acids and ketoacids were identified by GC-MS in abiotic samples, while complete disappearance of these acids was observed in biotic environments. The molecular weights of the biotically aged samples were slightly higher than the molecular weights of the corresponding abiotically aged samples, which is exemplified by the increase in from 5200 g/mol for a sterile sample with the highest amount of prooxidant to 6000 g/mol for the corresponding biodegraded sample. The higher molecular weight in the biotic environment is explained by the assimilation of carboxylic acids and low molecular weight polyethylene chains by microorganisms. Assimilation of the low molecular weight products is further confirmed by the absence of carboxylic acids in the biotic samples. Fewer carbonyls and more double bonds were seen by FTIR in the biodegraded samples, which is in agreement with the biodegradation mechanism of polyethylene.