A New Test Method for Determining Biodegradation of Plastic Material Under Controlled Aerobic Conditions in a Soil-Simulation Solid Environment

A new test method is described for assessing biodegradation of plastic material under simulated soil conditions. An inert substrate can be activated with soil extract and nutrient and used in place of soil in biodegradation tests. The biodegradation level is evaluated by determining the carbon dioxide (CO₂) production released by the test reactors. Effects of substrate nature, solution pH, nutrient composition, soil extract concentration, and activation duration on CO₂ production were investigated, and the experimental conditions were optimized. Results obtained with cellulose showed a biodegradation rate of 80% within 28 days. Moreover, with this kind of substrate, reaction products and residues can be easily extracted and analysed.     

Mineralization of Poly(ɛ-caprolactone)/Adipate Modified Starch Blend in Agricultural Soil

The biodegradability properties of poly(ɛ-caprolactone) (PCL) and modified adipate-starch (AS) blends, using Edenol-3203 (E) as a starch plasticizer, were investigated in laboratory by burial tests of the samples in previously analyzed agricultural soil. The biodegradation process was carried out using the respirometric test according to ASTM D 5988-96, and the mineralization was followed by both variables such as carbon dioxide evolution and mass loss. The results indicated that the presence of AS-E accelerated the biodegradation rate as expected.     

Biodegradability of Quaternized, Crosslinked Sugarcane Bagasse

Quaternized, crosslinked sugarcane bagasse can adsorb anionic dyes from textile wastewater. Disposal of dye-saturated adsorbent by composting or land application would require that modifications made to the bagasse do not interfere with its decomposition. The impact of quaternization and crosslinking on bagasse biodegradability was examined. Bagasse in varying states of modification was mixed with soil and monitored for carbon dioxide evolution for four weeks at 27°C. After subtracting the amount of carbon evolved from control soil samples, the net carbon evolved from the bagasse samples was determined and used as a measure of their extent of biodegradation. Biodegradability decreased in the order: bagasse (approx. 60% degraded after four weeks) > quaternized bagasse > quaternized, epichlorohydrin-crosslinked bagasse > quaternized, methylene-bis-acrylamide-crosslinked bagasse > epichlorohydrin-crosslinked bagasse (less than 5% degraded). Crosslinking severely impacted biodegration, probably by preventing the penetration of (hemi)cellulytic and lignolytic enzymes into the interior of the modified bagasse particles. It is concluded that the biodegradability of quaternized, crosslinked bagasse is too low for composting or land application.     

Kinetic Study of Naphthalene Biodegradation in Aerobic Slurry Phase Microcosms for the Optimisation of the Process

The research was focused on the slurry-phase biodegradation of naphthalene. The biodegradation process was optimised with preliminary experiments in slurry aerobic microcosms. From soil samples collected on a contaminated site, a Pseudomonas putida strain, called M8, capable to degrade naphthalene was selected. Microcosms were prepared with M8 strain by mixing non-contaminated soil and mineral M9 medium. Different experimental conditions were tested varying naphthalene concentration, soil:water ratio and inoculum density. The disappearance of hydrocarbon, the production of carbon dioxide, and the ratio of total heterotrophic and naphthalene-degrading bacteria were monitored at different incubation times. The kinetic equation that best fitted the disappearance of contaminant with time was determined. The results showed that the isolated strain enhanced the biodegradation rate with respect to the natural biodegradation.     

Effects of Weathering on Mechanical,Antimicrobial Properties and Biodegradation Process of Silver Loaded TPE Compounds

The incorporation of antimicrobial metals such as silver is an alternative to protect the material against microbial attack. However, loaded polymer can lose its antimicrobial properties after some time of use, and the additive may even leak out into the environment becoming harmful to non-target organisms. This study aims to evaluate the mechanical properties and antimicrobial activity of silver containing thermoplastic elastomer (TPE) samples exposed to weathering and the influence of additive incorporation in material biodegradation in the soil. For this purpose, silver ions (Ag⁺_bentonite, Ag⁺_phosphate) and silver nanoparticles (AgNp_silica) based additives were blended in a formulation of SEBS, polypropylene and mineral oil. The test samples were exposed to natural ageing over nine months, and were then evaluated according to their mechanical properties, antimicrobial activity, and degree of crystallinity and surface characteristics. The biodegradation process before and after natural ageing was evaluated through the generation of carbon dioxide. The results show that the action of natural ageing reduced the mechanical properties of loaded and unloaded TPE, and modified the degree of crystallinity and the chemical characteristic of the TPE surface. The presence or type of additive did not influence material resistance after being exposed to weathering. A decrease in antimicrobial activity in samples after natural ageing was observed. At a variable level and according to the chemical content, generation of carbon dioxide from TPE samples was greater in aged samples than in unexposed ones.     

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.     

Availability and leaching of polycyclic aromatic hydrocarbons: Controlling processes and comparison of testing methods

We have studied the availability and leaching of polycyclic aromatic hydrocarbons (PAHs) from two contaminated materials, a tar-containing asphalt granulate (Sigma16 US-EPA PAHs 3412mg/kg) and gasworks soil (SigmaPAHs 900mg/kg), by comparing results from three typical types of leaching tests: a column, sequential batch, and two different availability tests. The sequential batch test was found to largely resemble the column test. However, the leaching of particularly the larger PAHs (>5 aromatic rings) was found to be enhanced in the batch test by up to an order of magnitude, probably due to their association with large DOC (dissolved organic carbon) molecules generated by the vigorous mixing. The release of PAHs in the two availability tests, in which the leaching is facilitated by either a high concentration of DOC or Tenax resin, was similar, although the latter test was easier to perform and yielded more repeatable results. The availability was much higher than the amount leached in the column and sequential batch tests. However, biodegradation had apparently occurred in the column test and the total amount of PAHs released by either leaching or biodegradation, 9% and 26% for asphalt granulate and gasworks soil, respectively, did equal the amount leached in the availability tests. Therefore, the availability was found to provide a relevant measure of the PAH fraction that can be released from the solid phase. These results stress the importance of using the available instead of the total amount of contaminant in the risk analysis of solid materials in utilization or disposal.     

Bioremediation of Stranded Oil on an Arctic Shoreline

The application of slow-release and soluble fertilizers proved to be an effective and environmentally benign way of stimulating oil biodegradation on an Arctic shoreline. Fertilizer application to the surface of the beach delivered nutrients to the oiled sediment beneath the beach surface. There was no significant run-off of this fertilizer to either the nearshore water or to unfertilized plots, and there were no adverse toxicological effects of the fertilizer application. The fertilizer application was followed by an increase in oxygen consumption and carbon dioxide evolution from the beach, increased microbial biomass, and significantly greater biodegradation of oil on the plots that had received fertilizer. The rate of oil biodegradation was approximately doubled over the course of a year by fertilizer applications in the first two months after the spill.Simple test kits proved adequate to monitor the fertilizer-application process in the field in a time frame that would allow the application process to be fine-tuned during treatment on a real spill. Simple test kits and portable instrumentation were useful in demonstrating the initial success of the bioremediation strategy.     

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.     

Study of the Determination of the Ultimate Aerobic Biodegradability of Plastic Materials Under Controlled Composting Conditions

Several ISO standards for determining the ultimate aerobic/anaerobic biodegradability of plastic materials have been published. In particular, ISO 14855-1 is a common test method that measures evolved carbon dioxide using such methods as continuous infrared analysis, gas chromatography or titration and others (ISO 14855-1(2005.9)). This method is a small-scale test for determining the ultimate aerobic biodegradability of plastic materials, where the amounts of compost inoculum and test sample in one tenth comparing with that of ISO 14855-1. This method is well versed in ISO/DIS 14855-2 which the carbon dioxide evolved from test vessel is determined by gravimetric analysis of carbon dioxide absorbent. The focus of this study is to elucidate statistically the results of round robin test by seven countries used MODA, which were various deviations among the experiments.     

Biodegradation of Chitosan-Gellan and Poly(L-lysine)-Gellan Polyion Complex Fibers by Pure Cultures of Soil Filamentous Fungi

The degradation of two kinds of polyion complex (PIC) fibers, chitosan-gellan (CGF), and poly(L-lysine)-gellan (LGF) fibers, by seven species of soil filamentous fungi has been investigated. All of the pure-line soil filamentous fungi, Aspergillus oryzae, Penicillium caseicolum, P. citrinum, Mucor sp., Rhizopus sp., Curvularia sp., and Cladosporium sp. grew on the two fiber materials. Microscopic observation of the biodegradation processes revealed that P. caseicolum on the CGF and LGF grew, along with the accompanying collapse of the fiber matrices. In the biochemical oxygen-demand (BOD) test, the biodegradation of the LGF by P. caseicolum and Curvularia sp. exceeded 97% carbon dioxide generation and the biodegradation of the CGF by A. oryzae was 59%. These results might offer some clues to the applications of the PIC fibers as environmentally biodegradable materials.     

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.     

Radiation Crosslinking of Poly(Butylene Succinate) in the Presence of Inorganic Material and Its Biodegradability

Three kinds of poly(butylene succinate)s (PBS) with different molecular weight were irradiated with electron beams in the presence of inorganic material. Fourteen kinds of inorganic materials were used in this work. The presence of inorganic material inside cross-linked PBS samples enhances the yield of gel formation. The heat stabilities of PBS samples were checked; it was found that silicon dioxide and carbon black significantly improve these properties. Enzymatic and soil burial tests were performed; the presence of these inorganic materials in cross-linked PBS accelerates the rate of biodegradation.     

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.     

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.     

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.     

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.     

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.     

Treatment of sludge containing nitro-aromatic compounds in reed-bed mesocosms - Water, BOD, carbon and nutrient removal

Since the mid-1970s, Sweden has been depositing 1 million ton d.w sludge/year, produced at waste water treatment plants. Due to recent legislation this practice is no longer a viable method of waste management. It is necessary to improve existing and develop new sludge management techniques and one promising alternative is the dewatering and treatment of sludge in constructed wetlands. The aim of this study was to follow reduction of organic carbon, BOD and nutrients in an industrial sludge containing nitro-aromatic compounds passing through constructed small-scale wetlands, and to investigate any toxic effect such as growth inhibition of the common reed Phragmites australis. The result showed high reduction of all tested parameters in all the outgoing water samples, which shows that constructed wetlands are suitable for carbon and nutrient removal. The results also showed that P. australis is tolerant to xenobiotics and did not appear to be affected by the toxic compounds in the sludge. The sludge residual on the top of the beds contained low levels of organic carbon and is considered non-organic and could therefore be landfilled. Using this type of secondary treatment method, the amount of sludge could be reduced by 50-70%, mainly by dewatering and biodegradation of organic compounds.     

Evaluation of Solvita compost stability and maturity tests for assessment of quality of end-products from mixed latrine style compost toilets

It is challenging and expensive to monitor and test decentralized composting toilet systems, yet critical to prevent the mismanagement of potentially harmful and pathogenic end-product. Recent studies indicate that mixed latrine composting toilets can be inhibited by high ammonia content, a product of urea hydrolysis. Urine-diverting vermicomposting toilets are better able to accomplish the goals of remote site human waste management by facilitating the consumption of fecal matter by earthworms, which are highly sensitive to ammonia. The reliability of Solvita® compost stability and maturity tests were evaluated as a means of determining feedstock suitability for vermicomposting (ammonia) and end-product stability/completeness (carbon dioxide). A significant linear regression between Solvita® ammonia and free ammonia gas was found. Solvita® ranking of maturity did not correspond to ranking assigned by ammonium:nitrate standards. Solvita® ammonia values 4 and 5 contained ammonia levels below earthworm toxicity limits in 80% and 100% of samples respectively indicative of their use in evaluating feedstock suitability for vermicomposting. Solvita® stability tests did not correlate with carbon dioxide evolution tests nor ranking of stability by the same test, presumably due to in situ inhibition of decomposition and microbial respiration by ammonia which were reported by the Solvita® CO₂ test as having high stability values.