Degradation studies of novel degradable starch-polyethylene plastics containing oxidized polyethylene and prooxidant

Linear low-density polyethylene films were prepared that contained native corn starch (7, 14, or 28%), low or high molecular weight oxidized polyethylene (15%), and a prooxidant mixture (18% POLYCLEAN II) that contains manganese and vegetable oil. For each mixture all components were first mixed at high temperatures in a twin-screw extruder and pelletized. The pellets were cast into films using a single-screw extruder. Oxidized-polyethylene addition did not impair the transparency and thickness of the films and did not reduce the percentage elongation, whereas significant reductions in film mechanical properties were observed. Thermal and photodegradation properties of each film were evaluated by 70°C forced-air oven treatment (20 days), by high-temperature, high-humidity treatment in a steam chamber (20 days), and by exposure to ultraviolet light (365 nm; 4 weeks). Changes in the mechanical properties of the films were determined by an Instron Universal Test Machine; in the carbonyl index, Fourier transform infrared spectroscopy; and in molecular weight, by high-temperature gel-permeation chromatography (HT-GPC). The addition of oxidized polyethylene, especially high molecular weight oxidized polyethylene, and up to 14% starch to the films significantly increased the rate of thermal and photodegradation.Journal Paper No. J-15363 of the Iowa Agriculture and Home Economics Experiment Station, Ames. Project No. 0178 and 2889.     

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.     

Preparation and Characterization of Compatible and Degradable Thermoplastic Starch/Polyethylene Film

The degradability of the compatible thermoplastic starch/polyethylene film was investigated by weight loss percent (WLP), Fourier Transform Infrared (FT-IR) Spectroscopy, and Scanning Electron Microscope (SEM). The compatible film was prepared by using the particles of thermoplastic starch/polyethylene blends that were produced by one-step reactive extrusion. The weight of the film after degradation reduced more than 3% for 30 days and 4% for 60 days. The FTIR results revealed that both starch and polyethylene in the film exhibited varying degrees of degradation. SEM photographs of the films after degradation showed that starch particles in the film disintegrated into smaller particles or separated out of the film surface. Degradation studies demonstrated that the compatible thermoplastic starch/polyethylene film had increased degradability at the given degradable environment. The information implies that this film could be utilized as a degradable plastic.     

Synthesis of3H- polyethylene and its use for fate studies on degradable plastics

Determining the fate of xenobiotic materials in the environment can be aided by the use of radioactive isotope technology. Previous research on the degradation of polymers such as polyethylene (PE) was aided by the utilization of radiotracers. In order to study the environmental fate of degradable (PE/starch) plastics, we synthesized³H-labeled PE. Results of soil incubation studies indicate that only minimal degradation of the PE component, as indicated by the production of water-soluble metabolites, occurred during 2 years of incubation in soil. Despite the minimal degradation, the³H label did not allow for detection of the degradation products. In addition, the³H-PE was particularly useful for tracing the fate of degradable plastics after consumption by terrestrial isopods. The detection of aqueous-soluble radioactivity in isopod frass was used to indicate degradation of the plastic film.     

Degradable polymers: The role of the degradation environment

The degradability of several degradable polymers was examined using three types of degradation environments. These include exposure in a laboratory-scale composting test system containing material representative of the organic fraction of municipal solid waste (MSW), exposure in a thermal hydrolytic environment consisting of water at 60‡C, and exposure in a thermal-oxidative, dry oven environment of 60‡C. The results of the investigation clearly indicate that, in addition to chemical and biological activity which can lead to polymer degradation, physical restructuring and reorganization of the macromolecular structure may also occur at temperatures typically found in a compost environment, resulting in changes in the mechanical properties of the polymer films. In the case of the polyethylene-modified polymers evaluated in this study, all behaved similarly, but differently from the other polymer types. The polyethylene-based films appeared to be susceptible to oxidative degradation and should degrade in a composting environment providing that there is sufficient air in contact with the film for a sufficient period of time. However, when exposed in a laboratory composter, it appears that although ideal temperature-time curves may be obtained, the test time period was insufficient in comparison to the induction period required to achieve the desired thermal oxidative degradation. Issued as NRCC No. 37620.     

Performance of water cut-off and remediation promotion techniques at coastal waste landfill sites

This paper proposes the construction of steel pipe sheet pile (SPSP) cutoff walls for promoting remediation of water-soluble toxic substances and containment of water-soluble toxic substances at landfill sites in order to maintain and ensure the environmental safety of waste landfill sites over time. It investigates environmental safety at coastal waste landfill sites by applying water cut-off and remediation promotion techniques to the joint sections of SPSP water cut-off walls that provide shore protection for waste landfills. Results from the research herein show that the construction of SPSP water cut-off walls with features such as the containment of water-soluble toxic substances and remediation promotion is possible by applying water cut-off and remediation techniques to H–H joints, which are structural joint components of SPSP walls. In addition, they show that the performance of remediation in H–H joints can be controlled by adjusting the water cut-off efficiency of the H–H joint flange.     

Land treatment and the toxicity response of soil contaminated with wood preserving waste

Soils contaminated with wood preserving wastes, including pentachlo-rophenol (PCP) and creosote, are treated at field-scale in an engineered prepared-bed system consisting of two one-acre land treatment units (LTUs). The concentration of selected indicator compounds of treatment performance included PCP, pyrene, and total carcinogenic polycyclic aromatic hydrocarbons (TCPAHs) was monitored in the soil by taking both composited soil samples at multiple points in time, and discrete soil samples at two points in time. The mean concentration of the indicator compounds and the 95-percent confidence interval (CI) of the composite and discrete samples agreed relatively well, and first-order degradation rate kinetics satisfactorily represented the mean chemical concentration loss of indicator compounds in the LTU. Toxicity of the soil, as measured by Microtox^TM assay of the soil extracts, indicated that toxicity reduction corresponded with indicator compound disappearance. No toxicity effects were observed with time in treated layers of soil (lifts) buried beneath highly contaminated lifts of newly applied soil. This indicated that vertical migration of soluble contaminants from such lifts had little effect on the microbial activity in the underlying treated soil.     

Influence of Filler Particle Size on Physical Properties and Biodegradation of Biocomposites Based on Low-Density Polyethylene and Lignocellulosic Fillers

This study examined biocomposites based on low-density polyethylene (LDPE) and lignocellulosic fillers [wood flour (WF) and oil flax straw (FS)] selecting four size fractions of each lignocellulosic material as fillers for the composites. The primary aim was to evaluate the influence of fraction size on the composites’ basic properties; to accomplish this, the composites’ mechanical properties, thermal oxidation, thermophysical characteristics, and water absorption capacity were examined. Then microphotographs of the samples were created and length-to-diameter (L/D) ratio of the fillers was calculated, finding that the L/D ratio increased with increasing particle size. The particle size influenced the oxidative degradation and water absorption processes in composites with oil flax but not in those with WF. Biodegradation tests performed on the recovered soil found that the loss of mass in composites based on LDPE and FS was higher than in the same composites with WF. Moreover, at the initial stage of composting, the biodegradation rate correlated with the size of filler particles (i.e., the larger the particles, the higher the degradation rate of the biocomposite).     

Biodegradation of low-density polyethylene (LDPE) by isolated fungi in solid waste medium

In this study, biodegradation of low-density polyethylene (LDPE) by isolated landfill-source fungi was evaluated in a controlled solid waste medium. The fungi, including Aspergillus fumigatus, Aspergillus terreus and Fusarium solani, were isolated from samples taken from an aerobic aged municipal landfill in Tehran. These fungi could degrade LDPE via the formation of a biofilm in a submerged medium. In the sterilized solid waste medium, LPDE films were buried for 100 days in a 1-L flask containing 400 g sterile solid waste raw materials at 28 °C. Each fungus was added to a separate flask. The moisture content and pH of the media were maintained at the optimal levels for each fungus. Photo-oxidation (25 days under UV-irradiation) was used as a pretreatment of the LDPE samples. The progress of the process was monitored by measurement of total organic carbon (TOC), pH, temperature and moisture. The results obtained from monitoring the process using isolated fungi under sterile conditions indicate that these fungi are able to grow in solid waste medium. The results of FT-IR and SEM analyses show that A. terreus and A. fumigatus, despite the availability of other organic carbon of materials, could utilize LDPE as carbon source. While there has been much research in the field of LDPE biodegradation under solid conditions, this is the first report of degradation of LDPE by A. fumigatus.     

Formulation of a Photosensitized Polyethylene Film; Its Structure and Property Variation Under the Weathering Conditions of Tehran

To develop an environmentally degradable polymer material, a masterbatch pro-oxidant system was blended into low-density polyethylene. The polymer film samples were prepared by compression molding. The prepared films were placed under the natural environment of Tehran for weathering studies and accelerated conditions were also performed for UV aging in UV chamber. At different time intervals, the changes in chemical structure of photosensitized polyethylene samples were studied by FTIR and compared to that of the control polyethylene films. Also the mechanical properties of photosensitized polyethylene films were determined in comparison with the control films by measuring the tensile strength and elongation at break after exposure to the natural environment and UV radiation. Results showed that the overall rate of degradation process is clearly dependent on the polyethylene composition, test conditions (natural or accelerated), season of the year, and the duration of the weathering of the samples.     

Maturity assessment of compost from municipal solid waste through the study of enzyme activities and water-soluble fractions

In this work the dynamics of biochemical (enzymatic activities) and chemical (water-soluble fraction) parameters during 100 days of municipal solid wastes composting were studied to evaluate their suitability as tools for compost characterization. The hydrolase (protease, urease, cellulase, beta-glucosidase) and dehydrogenase activities were characterized by significant changes during the first 2 weeks of composting, because of the increase of easily decomposable organic compounds. After the 4th week a "maturation phase" was identified in which the enzymatic activities tended to gently decrease, suggesting the stabilisation of organic matter. Also the water-soluble fractions (water-soluble carbon, nitrogen, carbohydrates and phenols), which are involved in many degradation processes, showed major fluctuations during the first month of composting. The results obtained showed that the hydrolytic activities and the water-soluble fractions did not vary statistically during the last month of composting. Significant correlations between the enzymatic activities, as well as between enzyme activities and water-soluble fractions, were also highlighted. These results highlight the suitability of both enzymatic activities and water soluble fractions as suitable indicators of the state and evolution of the organic matter during composting. However, since in the literature the amount of each activity or fraction at the end of composting depends on the raw material used for composting, single point determinations appear inadequate for compost characterization. This emphasizes the importance of the characterization of the dynamics of enzymatic activities and water-soluble fractions during the process.     

Degradation and environmental risk of surfactants after the application of compost sludge to the soil

In this work, the degradation of anionic and non-ionic surfactants in agricultural soil amended with sewage sludge is reported. The compounds analysed were: linear alkylbenzene sulphonates (LAS) with a 10-13 carbon alkylic chain, and nonylphenolic compounds (NPE), including nonylphenol (NP) and nonylphenol ethoxylates with one and two ethoxy groups (NP1EO and NP2EO). The degradation studies were carried out under winter (12.7°C) and summer (22.4°C) conditions in Andalusia region. The concentration of LAS was reduced to 2% of the initial concentration 100 day after sludge-application to the soil. The half-life time measured for LAS homologues were ranged between 4 and 14days at 12.7°C and between 4 and 7 days at 22.4°C. With regard to NPE compounds, after 8 and 4days from the beginning of the experiment at 12.7 and 22.4°C, respectively, their concentration levels were increased to 6.5 and 13.5mg/kgdm (dry matter) as consequence of the degradation of nonylphenol polyethoxylates. These concentration levels were reduced to 5% after 63 and 70 days for 12.7°C and 22.4°C, respectively. The half-life times measured for NPEs were from 8 to 16 days at 12.7°C and from 8 to 18 days at 22.4°C. Environmental risk assessment revealed that for LAS homologues no environment risk could be expected after 7 and 8 days of sludge application to the soil for 22.4 and 12.7°C, respectively; however, potential toxic effects could be observed for the nonylphenolic compounds during the first 56 days after sludge application to the soil.     

Industrial wastewater analysis: a toxicity-directed approach

Methods of toxicity-directed analysis have been developed for the characterization and identification of toxic organic constituents in industrial wastewater. Sequential solid-phase extraction is followed by high-performance liquid chromatography (HPLC) fractionation or by automated multiple development thin-layer chromatography fractionation (AMD–TLC) of the toxic extracts. Toxic fractions were finally analyzed by gas chromatography–mass spectroscopy (GC–MS). Toxicity was detected before each of the analytical steps by the bioluminescence inhibition of Vibrio fischeri, which was performed on microtiter plates and on the developed TLC plates. While sequential extraction broadens the polarity range of the procedure, the new variants of the luminescence test make the method very versatile and fast. The potential of this kind of toxicity-directed analysis with respect to resolution and polarity of analytes is discussed and applications to partial effluents of a tannery, to molasses wastewater and a spent dyeing bath are presented. A variety of benzothiazoles and more polar organics were identified as major toxic compounds in tannery effluents. It is shown that the procedures are well suited to detect individual toxic components in complex industrial wastewaters. The use of LC-MS is proposed to extend the polarity range of the final identification step. ©     

Temperature Effects on Soil Mineralization of Polylactic Acid Plastic in Laboratory Respirometers

A respirometric system was used to analyze the biodegradation of high molecular weight (120,000 to 200,000 g mol^–1) polylactic acid (PLA) plastic films in soil under laboratory conditions. The respirometric system consisted of air-conditioning pretraps, a soil reactor, and a carbon dioxide (CO₂) posttrap. A 200-g homogeneous soil mixture of all-purpose potting soil : manure soil : sand [1 : 1 : 1 (w/w)] and 1.5 g of PLA plastic films in 1 × 1-cm² squares was added to each bottle. The respirometers were placed in a 28, 40, or 55°C water bath for 182 days. Treatments (three replicates) included native corn starch (positive control), polyethylene (Glad Cling Wrap; negative control), and three PLA films: Ca-I (Cargill Dow Polymers LLC, monolayer), GII (Cargill Dow Polymers LLC, Generation II), and Ch-I (Chronopol; monolayer). The degree of polymer mineralization was indicated by the cumulative CO₂ liberated from each respirometer. The initial average mineralization rate and total percentage mineralized of the PLA plastic films at 28, 40, and 55°C was 24.3, 41.5, and 76.9 mg/day with a 27, 45, and 70% carbon loss, respectively. No decrease in soil pH was observed after 182 days of mineralization. Hence, increase in soil temperature drastically enhanced the biodegradation of PLA plastic films in soil under laboratory conditions (P < 0.0001).     

Biodegradation of pretreated polyethylene film by Pseudomonas aeruginosa AMB-CD-1

A comparative study evaluated the acid, alkali, and heat-treated polyethylene biodegradation efficiency of Pseudomonas aeruginosa AMB-CD-1. The polyethylene (PE) pieces were separately treated with heat (50°C), acid (1N HCl), and alkali (1N NaOH) and then washed with water before use. All the treated samples were analyzed through thermogravimetric analysis. In addition, weight and temperature changes during the decomposition reactions were also measured and determined. In these treatments, the PE films of heat-treated and acid-treated low-density polyethylene (LDPE) indicated more significant weight loss at 120°C (48.99% and 40.75%, respectively) as compared to their control or untreated PE and alkali-treated LDPE (21.84% and 24.68%, respectively). A biodegradation assay was then conducted with treated and untreated LDPE films with P. aeruginosa AMB-CD-1 strain. Fourier transform infrared spectroscopy analysis revealed that the heat or acid-pretreated samples with isolate AMB-CD-1 displayed peaks at 2922.84, 2923.97, and 1450.31, 874.22 cm⁻¹ for C–H stretching deformation vibration, CH₂ scissoring vibration, –CHO stretching, and strong alkyl structure, respectively. Furthermore, the new peaks with a significant difference at 2500–2000 cm⁻¹ (O═C═O, O–H stretching vibration: carboxylic acid) and 1500–1000 cm⁻¹ (–CHO and C═O stretching) were noticed in the infrared spectral range of LDPE degradation. Modifications in the functional group provided evidence that biodegradation had impacted the chemical structure of the LDPE film. Additionally, it was demonstrated that pretreating LDPE films with heat or acid could speed up their biodegradation.     

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”.     

Iron‐mediated abiotic degradation of RDX in a contaminated aquifer

The influence of aqueous‐ and mineral‐phase iron on royal demolition explosive (RDX) destruction has been previously investigated in theoretical settings and bench‐scale tests by various practitioners. The feasible use of in situ redox manipulation to create reactive Fe(II) is contingent upon the aquifer containing enough iron oxides and iron‐bearing clay minerals for the treated zone to remain effective. The following is a summary of a bench‐scale assessment of this relationship using aquifer material from an ongoing groundwater remediation effort at the Iowa Army Ammunition Plant (IAAP). A bench‐scale study was designed to determine the relative contributions of the biotic and iron‐mediated abiotic degradation processes to the net decrease in RDX observed at the site using saturated aquifer samples collected from within the RDX plume. Sterilized samples with a sufficient stoichiometric excess of both soluble and mineral‐phase iron reduced concentrations of RDX in both the soil and water fractions to the same extent as the samples containing native biota. These results indicate that in situ, abiotic degradation of RDX is feasible in areas unsuitable to biotic degradation processes, yielding an additional alternative for in situ RDX remediation. © 2012 Wiley Periodicals, Inc.     

Permanganate oxidation of sorbed polycyclic aromatic hydrocarbons

The polycyclic aromatic hydrocarbons (PAH) that contaminate soils at many industrial and government sites are resistant to natural biotic and abiotic degradation processes. The recalcitrant nature of these compounds may require aggressive chemical treatment to effectively remediate these sites. This study was conducted to assess the viability of permanganate oxidative treatment as a method to reduce PAH concentration in contaminated soils. Study results demonstrated a reduction in soil sorbed concentration for a mixture of six PAHs that included anthracene, benzo(a)pyrene, chrysene, fluoranthene, phenanthrene, and pyrene by potassium permanganate (KMnO4) oxidative treatment. The greatest reduction in soil concentration was observed for benzo(a)pyrene, pyrene, phenanthrene, and anthracene at 72.1, 64.2, 56.2, and 53.8%, respectively, in 30 min at a KMnO4 concentration of 160 mM. Minimal reductions in fluoranthene and chrysene concentration were observed at 13.4 and 7.8%, respectively, under the same conditions. A relative chemical reactivity order of benzo(a)pyrene>pyrene>phenanthrene>anthracene>fluoranthene>chrysene towards permanganate ion was observed. Aromatic sextet theory was applied to the degradation results to explain the highly variable and compound-specific chemical reactivity order.     

Water transport in polylactic acid (PLA), PLA/ polycaprolactone copolymers, and PLA/polyethylene glycol blends

Polylactic acid (PLA) is a hydrolytically degradable aliphatic polyester, and water vapor permeability may have a significant influence on the rate of degradation. A method is devised to use bags prepared from PLA films and filled with molecular sieves to determine the water vapor permeability in the polymer, its copolymers with caprolactone, and blends with polyethylene glycol. The “solution-diffusion” model is used to determine the permeability parameters. These include the solubility coefficient,S, a measure of the equilibrium water concentration available for hydrolysis and the diffusion coefficient,D, which characterizes the rate of water vapor diffusion into the film under specific conditions. Values ofS andD at 50‡C and 90% relative humidity ranged from 400 × 10^-6 to 1000 × 10^-6 cm³ (STP)/(cm³ Pa) and 0.20 × 10^-6 to 1.0 × 10^-6 cm²/s, respectively. TheS andD coefficients were also measured at 20 and 40‡C and compared to those of other polymers. The degree of crystallinity was found to have little influence on the measured permeability parameters. The heat of sorption, δH_S, and the activation energy of diffusion, E_D, were used to show that the permeability process is best described by the “water cluster” model for hydrophobic polymers. Finally, the diffusion coefficient is used to compare the rate of water diffusion to the rate of water consumption by ester hydrolysis. Results indicate that hydrolytic degradation of PLA is reaction-controlled.     

Plant and Soil System Responses to Ozone After 3 Years in a Lysimeter Study with Juvenile Beech (Fagus sylvatica L.)

A lysimeter study was performed to monitor effects of elevated ozone on juvenile trees of Fagus sylvatica L. as well as on the plant–soil system. During a fumigation period over almost three growing seasons, parameters related to plant growth, phenological development and physiology as well as soil functions were studied. The data analyses identified elevated ozone to delay leaf phenology at early and to accelerate it at late developmental stages, to reduce growth, some leaf nutrients (Ca, K) as well as some soluble phenolics (hydroxycinnamic acid derivatives, total flavonol glycosides). No or very weak ozone effects were found in mobile carbon pools of leaves (starch, sucrose), and other phenolic compounds (flavans). Altered gene expression related to stress and carbon cycling corresponded well with findings from leaf phenology and chemical composition analyses indicating earlier senescence and oxidative stress in leaves under elevated ozone. Conversely in the soil system, no effects of ozone were detected on soil enzyme activities, rates of litter degradation and lysimeter water balances. Despite the fact that the three reported years 2003–2005 were climatically very contrasting including a hot and dry as well as an extremely wet summer, and also mild as well as cold winters, the influence of ozone on a number of plant parameters is remarkably consistent, further underlining the phytotoxic potential of elevated tropospheric ozone levels.