Degradation of Polylactic Acid (PLA) Plastic in Costa Rican Soil and Iowa State University Compost Rows

In this study the degradation of polylactic acid (PLA) plastic films in Costa Rican soil and in a leaf composting environment was investigated. Three types of PLA films were used: Ch-I, (PLA monolayer plastic films from Chronopol, Golden, CO), GII (PLA trilayer plastic films from Cargill Dow Polymers LLC, Minnetonka, MN), and Ca-I (PLA monolayer plastic films from Cargill Dow Polymers LLC). The average soil temperature and moisture content in Costa Rica were 27°C and 80%, respectively. The average degradation rate of PLA plastic films in the soil of the banana field was 7675 M _w/week. Two compost rows were set up at the Iowa State University (ISU) (Ames) compost site. Temperature and relative humidity of the compost rows were kept at 55 ± 5°C and 50 ± 10% RH, respectively. The degradation rates of GII and Ca-I in the compost rows were 113,290 and 71,283 M _w/week, respectively. Therefore, it was estimated that in Costa Rican soil and in compost rows, PLA would be visibly degraded in 6 months and in 3 weeks, respectively.     

Effects of Electron-Beam Irradiation and Ultraviolet Light (365 nm) on Polylactic Acid Plastic Films

Strips of Ca-I [polylactic acid (PLA) monolayer plastic films from Cargill Dow Polymers LLC, Minnetonka, MN] cut in the machine and nonmachine directions were irradiated with an electron beam using a CIRCLE III Linear Accelerator (MeV Industries S.A., Jouy-en-Josas, Cedex, France). The effects of 33-kGy irradiation on the physical properties of the Ca-I strips were studied. In addition, the effects of ultraviolet (UV) light (365-nm) illumination on the degradation of three PLA plastic films, Ch-I (PLA monolayer plastic films from Chronopol, Golden, CO), GII (PLA trilayer plastic films from Cargill Dow Polymers LLC), MN), and Ca-I (PLA monolayer plastic films from Cargill Dow Polymers LLC) were analyzed by a modified ASTM D5208-91 method. Results showed that irradiation had decreased the weight-average molecular weight (M _w), stress at break, percentage of elongation, and strain energy of Ca-I by 35.5, 26.7, 32.3, and 44.8%, respectively (P < 0.01). The shelf life of the irradiated Ca-I strips at 5°C and <20 ± 5% RH was about 6 months. The degradation rate of Ch-I, GII, and Ca-I with no UV light treatment at 55°C and 10% RH was 2512, 5618, and 3785 M _w/week, respectively. Under the UV light illumination (365 nm), the degradation rate of Ch-I, GII, and Ca-I, was 2982, 8722, and 7467 M _w/week, respectively. Hence, the degradation rate of GII and Ca-I was increased 55 and 97% by UV light (P < 0.008), respectively. This trend was not observed in Ch-I because its starting M _w (78,000 g/mol) was close to the tensile strength lost range (50,000 to 75,000 g/mol) of PLA films. To our knowledge, this is the first study to demonstrate that UV light does further enhance the degradation of PLA films.     

Effects of Temperature and Relative Humidity on Polylactic Acid Plastic Degradation

Three high molecular weight (120,000 to 200,000 g mol^–1) polylactic acid (PLA) plastic films from Chronopol (Ch-I) and Cargill Dow Polymers (GII and Ca-I) were analyzed for their degradation under various temperature and relative humidity (RH) conditions. Two sets of plastic films, each containing 11 samples, were randomly hung in a temperature/humidity-controlled chamber by means of plastic-coated paper clips. The tested conditions were 28, 40, and 55°C at 50 and 100% RH, respectively, and 55°C at 10% RH. The three tested PLA films started to lose their tensile properties when their weight-average molecular weight (M _w) was in the range of 50,000 to 75,000 g mol^–1. The average degradation rate of Ch-I, GII, and Ca-I was 28,931, 27,361, and 63,025 M _w/week, respectively. Hence, GII had a faster degradation rate than Ch-I and Ca-I under all tested conditions. The degradation rate of PLA plastics was enhanced by the increase in temperature and relative humidity. This trend was observed in all three PLA plastics (Ca-I, GII, and Ch-I). Of the three tested films, Ch-I was the first to lose its mechanical properties, whereas Ca-I demonstrated the slowest loss, with mechanical properties under all tested conditions.     

Field Exposure Study of Polylactic Acid (PLA) Plastic Films in the Banana Fields of Costa Rica

For use by the banana industry of Costa Rica, polylactic acid (PLA) plastic ropes and banana finger shrouds must remain operational for 14 to 16 weeks, and they also must be able to break down in the soil after serving their purposes. The banana field at La Rebusca Farm (Costa Rica) and the experiment station at University of Costa Rica were selected for a field exposure study of Cargill EcoPla Generation II (GII) and Cargill EcoPla monolayer (Ca-I) PLA films. The average monthly temperature, relative humidity, and cumulative rainfall of the La Rebusca Farm and the University of Costa Rica site were 26 and 22°C, 92 and 84%, and 352 and 177 in., respectively. The PLA plastic films at the La Rebusca Farm lost their mechanical properties earlier than at the University of Costa Rica site because of the higher temperature and relative humidity of the banana farm. The Ca-I film meets the 14-week operational time frame and it is recommended for further studies as ropes and banana shrouds.     

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.     

The Effect of Gamma and Electron Beam Irradiation on the Biodegradability of PLA Films

Biodegradation of poly(lactic) acid (PLA) has been studied extensively, but there is only limited knowledge about the effect of irradiation sterilization on its biodegradability. The aim of this work was to examine the aerobic biodegradation of gamma and electron beam irradiated PLA films along with the effects of aging (3, 6, and 9 months of storage) using a direct measurement respirometric system. Commercial PLA film was exposed to a simulated aerobic compost environment, and its mineralization was 96 % at day 85. Gamma and electron beam irradiation affected the biodegradation of the post-irradiated PLA film. Aging irradiated PLA had some potential to increase the biodegradation rate, as the average value of mineralization after 9 months of storage was higher than for the non-irradiated PLA. Comparison of the effect of storage time on the biodegradability of PLA showed a significant increase in biodegradation of the gamma irradiated PLA after 3 months (70 %) and 9 months of storage (130 %). Similarly, there was a significant difference in the biodegradation of electron beam irradiated PLA between 3 months (68 %) and 9 months of storage (120 %). Due to the priming effect, the percent mineralization of gamma irradiated and E-beam irradiated PLA after 9 months of storage was greater than 100 %. Both non-irradiated and irradiated PLA films can be considered biodegradable plastics since they showed mineralization percentage larger than 90 % of that of the positive control at the end of the test period.     

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.     

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

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

Anaerobic Biodegradation of Poly (Lactic Acid) Film in Anaerobic Sludge

The anaerobic biodegradation rates of four different sizes of poly (lactic acid) (PLA) films (thickness 25???m) in anaerobic sludge at 55?°C were examined. The anaerobic biodegradation rates of small pieces of PLA film were slower than for large pieces of PLA film. We also examined whether PLA film could also be used as a reference material in the anaerobic biodegradation test in addition to PLA powder. The anaerobic biodegradation rate of PLA film became slower with lower activity sludge, but the rate of decrease was gradual, and the anaerobic biodegradation rate of PLA film was faster than the PLA powder (125?C250???m). The anaerobic biodegradation rate of the PLA powder (125?C250???m) reflected the plastic anaerobic biodegradation activity of the sludge more accurately than the thin PLA film (thickness 25???m). Consequently, PLA powder (125?C250???m) is more suitable than thin PLA film (thickness?<?25???m) for use as a reference material to assess the plastic anaerobic biodegradation activity of the sludge in an anaerobic biodegradation test at 55?°C.     

Dialdehyde starch and zein plastic: Mechanical properties and biodegradability

Dialdehyde starch (DAS) and zein, a hydrophobic corn protein, were investigated to produce biodegradable plastics with improved water resistance and mechanical properties. In the study, dialdehyde starch and zein ratio, plasticizers, and degree of starch oxidation were examined. Increased molding temperature and level of starch oxidation decreased water absorption of the plastic. Tensile strength and Young's modulus increased with starch oxidation. The biodegradation of starting materials and ground plastic specimens was studied in aerobic soil reactors maintained at 25°C for 180 days. Biodegradation of corn starch, zein, and dialdehyde starch for 180 days produced CO₂ equivalent to 64, 63, and 10% of theoretical carbon, respectively. Specimens of molded DAS and zein (3 : 1) plastic showed accelerated CO₂ evolution compared to DAS and other raw materials alone. By 180 days, specimens made with starch of low oxidation (1 and 5% oxidized) demonstrated a 60% biodegradation, and specimens with highly oxidized starch (90% oxidized) achieved 37% biodegradation.Paper presented at the Bio/Environmentally Degradable Polymer Society—Third National Meeting, June 6–8, 1994, Boston, Massachusetts.Journal Paper J-15927 of the Iowa Agriculture and Home Economics Experiment Station, Ames, Project No. 3258.     

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.     

Biodegradation of Low Molecular Weight Organic Acids in a Limed Forest Soil

The effect of liming (3.45 and 8.75 t ha^-1 dolomite; 16 yr after application) on the biodegradation of three low molecular weight organic acids (citrate, oxalate and propionate) in forest soils was investigated. The concentration of organic acids in the soil solution followed the series propionate > citrate > oxalate with liming having no significant impact on soil solution concentrations (mean organic acid concentration = 8.7 ± 2.3 M). Organic acid mineralization by the soil microbial community was rapid in surface organic horizons (mean half-life for citrate = 2–6 h), with biodegradation rate gradually declining with soil depth. Concentration-dependent biodegradation studies (0 to 350 M) showed that the mineralization kinetics generally conformed well to a single Michaelis–Menten equation with V_max values following the series oxalate > citrate > propionate (mean = 9.8 ± 1.0 nmol g^-1 h^-1) and K_M values following the series oxalate = citrate > propionate (mean 168 ± 25 M). The V_max values declined with soil depth, which was consistent with a general reduction in microbial activity down the soil profile. Liming induced a significant increase in V_max for citrate with no change for propionate and reduction in V_max for oxalate. The latter was probably due to adsorption and precipitation of Ca-oxalate making it unavailable for microbial uptake. The higher adsorption/precipitation capacity for oxalate in the limed soils was confirmed by adsorption isotherms. Generally, liming increased soil microbial activity by approximately 10 to 35% with calculations based on soil solution concentrations indicating that organic acid mineralization constituted approximately 3 to 15% of the total soil respiration.     

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.     

Comparative Biodegradation in Soil Behaviour of two Biodegradable Polymers Based on Renewable Resources

This work presents the last phase of long-term experimental studies on the biodegradation in soil behaviour of polymers destined for agricultural applications. The paper focuses on comparative studies between the biodegradation in soil behaviour of two important biodegradable polymers based on renewable resources: poly(lactic acid) (PLA) versus polyhydroxyalkanoates (PHA). Full-scale experiments were carried out during the period June 2008–January 2009. Different methods of exposure were applied in the case of polyhydroxyalkanoates, simulating the agricultural biodegradable mulching films use and their fate in soil after the end of their useful lifetime. The field results were compared with the results of biodegradation under controlled laboratory conditions simulating biodegradation in soil, using soil from the experimental field. Further, the field results were compared against the results of biodegradation under farm composting conditions.     

Modelling Easily Biodegradability of Materials in Liquid Medium-Relationship Between Structure and Biodegradability

In the present project, twenty materials (e.g., polyhydroxybutyrate-hydroxyvalerate, polycaprolactone, cellulose acetate, polyacticacid, polyethylene), representing varied biodegradability levels were studied. An aerobic respirometric test, based on the CEN Draft, was setup. The biodegradability of each plastic film was evaluated by measuring the percentage of carbon converted into CO₂ during 35 days. The values of the CO₂ production were plotted versus days as a cumulative function. In order to reduce its number of points, the cumulative curve was modeled using a sigmoïd function (Hill sigmoïd). This model was compared to one found in the literature. A _i ² test showed that the biodegradation curve was more accurately fitted with the model than the previous one. Three kinetic parameters were determined by this Hill model: one represents the maximal percentage of carbon converted into CO₂, the second the half-life time in days of the degrading part of the material and the third one the curve radius.In addition, the following analyses were carried out on each sample: elemental analysis, thickness, hydrophobicity and surface free energy measurements. In order to compress the information and to keep only relevant pieces, these parameters were submitted to a Principal Component Analysis. PCA found linear combinations of variables that describe major trends in the data. The two principal components which separate groups of materials were closely related to a chemical and a physical axis respectively. Materials showing a high biodegradability were related to high oxygen (and nitrogen) contents and low hydrophobicity: Material thickness did not influence the likeliness to biodegradability described by the maximum biodegradation rate. Finally, this study established the correlation between the biodegradation and the structure of biopolymers.     

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.     

Biodegradation of Polyaromatics Synthesized by Peroxidase-Catalyzed Free-Radical Polymerization

Polymers formed from peroxidase-based free-radical polymerization reactions were characterized for rates of mineralization against lignin and humic acid controls. Degradation studies were carried out in soil systems over 202 days and cumulative net CO₂ was determined. Whereas mineralization of the humic acid and alkali lignin controls totaled ca. 20% at the end of the test exposure, there was essentially no net mineralization of the hydrolytic lignin control. Mineralization of the test samples totaled 5% for poly(p-ethylphenol) and 11% for poly(m-cresol). At the same time, mineralization of the poly(p-phenyl phenol) totaled 64%. Conversely, the readily biodegradable polymers cellulose and PHB reached values of 91 to 97% in less than 60 days. Our data suggest that the mineralization kinetics of the enzymatically derived polyaromatics mimic those of the naturally occurring heteropolymers.     

Aging of Toughened Polylactic Acid Nanocomposites: Water Absorption,Hygrothermal Degradation and Soil Burial Analysis

The environmental aging behaviour of montmorillonite (MMT) filled polylactic acid (PLA) nanocomposites (PLA/MMT) and linear low density polyethylene (LLDPE)-toughened PLA (PLA/LLDPE ratio = 90/10) nanocomposites (PLA/LLDPE/MMT) were investigated in this study. The nanocomposites were subjected to water absorption, hygrothermal degradation and soil burial analysis. Both PLA/MMT and PLA/LLDPE/MMT nanocomposites were immersed in distilled water at three different temperatures (room temperature, 60, and 90 °C) and the weight difference before and after immersion was calculated. The kinetics of water absorption for both nanocomposites followed the Fick’s second law of diffusion, where a linear relationship exists between the initial moisture absorption at any time t and t ^1/2 (the square root of time), followed by a horizontal plateau (saturation). The equilibrium moisture content (M _m ) and diffusion coefficient (D) of PLA nanocomposites increased with the addition of MMT (2 phr) and LLDPE. However, the D values of both nanocomposites decreased by increasing MMT (4 phr). The M _m for PLA/MMT and PLA/LLDPE/MMT nanocomposites increased by increasing immersion temperature (60 °C) and prolonged immersion resulted in hygrothermal degradation of both nanocomposites. The hygrothermal degradation studies showed that PLA degrades much faster at 90 °C as compared to 60 °C in both the nanocomposites. The addition of MMT and LLDPE improved the hygrothermal stability of PLA in both nanocomposites. Soil burial test revealed deterioration of impact strength in all samples while the rate of biodegradation was retarded in the presence of MMT and LLDPE.     

Feasibility of greenhouse gas emissions offsets for natural source zone depletion of petroleum hydrocarbons

Hydrocarbon biodegradation is an important process for remediating petroleum hydrocarbons and managing large sites. However, this biodegradation results in what are essentially unavoidable CO₂ emissions to the atmosphere. A feasibility assessment was conducted to quantitatively consider reuse options for petroleum brownfields that would offset contaminant respiration emissions rates in the 2 to 10 micromoles CO₂ per meters squared per second (μmol CO₂ m^?2 s^?1) typically observed. Under a wide range of solar resource scenarios, placement of solar panels over only a fraction (no more than 35%) of the site footprint is estimated as necessary to achieve an emissions offset. Similarly, placement of one 30‐meter tall wind turbine of moderate rating (approximately 30 to 50 kW) is sufficient to provide an offset for a nominal 1,000 square meters site. For spreading of spent calcium‐rich construction materials, under even a high emissions scenario, the required footprint for the offset is less than the site footprint. While these approaches appear feasible, revegetation as forestland is estimated as sufficient only at contaminant respiration rates up to 2 μmol CO₂ m^?2 s^?1. Revegetation as rangeland and cropland, which sequesters CO₂ mainly in soil organic carbon, is estimated as requiring more than the site footprint under many contaminant respiration rates. Revegetation as a wetland fares slightly better from a carbon storage perspective, but it also has the potential for N₂O and CH₄ emissions that may largely undo the benefit from sequestration in soil organic matter. Overall, the results indicate several methods that are viable for achieving emissions offsets and a quantitation method that can be honed with site‐specific input parameters as appropriate.