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.     

Home composting versus industrial composting: Influence of composting system on compost quality with focus on compost stability

Stability is one of the most important properties of compost obtained from the organic fraction of municipal solid wastes. This property is essential for the application of compost to land to avoid further field degradation and emissions of odors, among others. In this study, a massive characterization of compost samples from both home producers and industrial facilities is presented. Results are analyzed in terms of chemical and respiration characterizations, the latter representing the stability of the compost. Results are also analyzed in terms of statistical validation. The main conclusion from this work is that home composting, when properly conducted, can achieve excellent levels of stability, whereas industrial compost produced in the studied facilities can also present a high stability, although an important dispersion is found in these composts. The study also highlights the importance of respiration techniques to have a reliable characterization of compost quality, while the chemical characterization does not provide enough information to have a complete picture of a compost sample.     

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.     

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.     

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.     

高级氧化法处理光引发剂生产废水

分别采用臭氧氧化、微电解—Fenton氧化和电化学降解的方法处理COD为6 000~8 000 mg/L、BOD₅/ COD为 0.12~0.17的光引发剂生产废水,比较了3种方法对废水中COD的去除效果。实验结果表明：臭氧氧化反应2 h时废水COD去除率达35.9%,BOD₅/COD 为0.20;微电解反应4 h再Fenton氧化4 h后,废水COD去除率为38.2%,BOD₅/COD 为0.28;电化学降解2 h后废水COD去除率达83.9%,BOD₅/COD 为0.46,降解反应遵循零级反应动力学,反应速率常数为2.6 kg/（m³·h）。3种方法对光引发剂生产废水的处理效果顺序为：电化学降解>微电解—Fenton氧化>臭氧氧化。     

Dynamic of functional microbial groups during mesophilic composting of agro-industrial wastes and free-living (N2)-fixing bacteria application

Although several reports are available concerning the composition and dynamics of the microflora during the composting of municipal solid wastes, little is known about the microbial diversity during the composting of agro-industrial refuse. For this reason, the first parts of this study included the quantification of microbial generic groups and of the main functional groups of C and N cycle during composting of agro-industrial refuse. After a generalized decrease observed during the initial phases, a new bacterial growth was observed in the final phase of the process. Ammonifiers and (N₂)-fixing aerobic groups predominated outside of the piles whereas, nitrate-reducing group increased inside the piles during the first 23 days of composting. Ammonia-oxidizing bacteria (AOB) and nitrite-oxidizing bacteria (NOB), showed an opposite trend of growth since ammonia oxidation decreased with the increase of the nitrite oxidation activity. Pectinolytics, amylolytics and aerobic cellulolytic were present in greater quantities and showed an upward trend in both the internal and external part of the heaps.Several free-living (N₂)-fixing bacteria were molecularly identify as belonging especially to uncommon genera of nitrogen-fixing bacteria as Stenotrophomonas, Xanthomonas, Pseudomonas, Klebsiella, Alcaligenes, Achromobacter and Caulobacter. They were investigated for their ability to fix atmospheric nitrogen to employ as improvers of quality of compost. Some strains of Azotobacter chrococcum and Azotobacter salinestris were also tested. When different diazotrophic bacterial species were added in compost, the increase of total N ranged from 16% to 27% depending on the selected microbial strain being used. Such microorganisms may be used alone or in mixtures to provide an allocation of plant growth promoting rhizobacteria in soil.     

铁碳微电解耦合光-Fenton氧化法降解水中的十溴联苯醚

采用铁碳微电解耦合光-Fenton氧化法降解模拟废水中的十溴联苯醚(BDE-209)。探索了铁碳微电解法降解BDE-209的影响因素,考察了铁碳微电解耦合光-Fenton氧化法对BDE-209的降解效果。实验结果表明:在模拟废水BDE-209质量浓度为1 mg/L、初始废水p H为2.0、铁碳质量比为1∶1、铁粉投加量为12 g/L、微电解温度为40 oC、微电解时间为60 min的条件下,铁碳微电解法的BDE-209降解率达到82.5%;当H2O2溶液投加量为4 m L/L时,铁碳微电解耦合光-Fenton氧化法的BDE-209降解率达到95.7%。说明添加H2O2的Fenton体系对BDE-209的降解有明显促进作用。     

电催化氧化技术处理含盐有机废水研究进展

介绍了电催化氧化技术在实际工业废水处理中的优势,对其反应原理进行了概述。总结了电催化氧化技术在石油、制药、造纸行业废水和含氨氮类有机废水处理中的研究进展,指出：电催化氧化技术未来的主要研究方向为研发新型电催化阳极材料;开发高效电解反应器;探索电催化氧化技术与其他处理工艺组合联用。     

Physical modelling of the composting environment: a review. Part 2: Simulation performance

This paper reviews previously published heat balance data for experimental and full-scale composting reactors, and then presents an evaluation of the simulation performance of laboratory and pilot-scale reactors, using both quantitative and qualitative temperature profile characteristics. The review indicates that laboratory-scale reactors have typically demonstrated markedly different heat balance behaviour in comparison to full-scale systems, with ventilative heat losses of 36-67%, and 70-95% of the total flux, respectively. Similarly, conductive/convective/radiative (CCR) heat losses from laboratory reactors have been reported at 33-62% of the total flux, whereas CCR losses from full-scale composting systems have ranged from 3% to 15% of the total. Full-scale windrow temperature-time profiles from the literature were characterised by the present authors. Areas bounded by the curve and a 40 degrees C baseline (A(40)) exceeded 624 degrees C. days, areas bounded by the curve and a 55 degrees C baseline (A(55)) exceeded 60 degrees C days, and times at 40 and 55 degrees C were >46 days and >24 days, respectively, over periods of 50-74 days. For forced aeration systems at full scale, values of A(40) exceeded 224 degrees C days, values of A(55) exceeded 26 degrees C days, and times at 40 and 55 degrees C were >14 days and >10 days, respectively, over periods of 15-35 days. Values of these four parameters for laboratory-scale reactors were typically considerably lower than for the full-scale systems, although temperature shape characteristics were often similar to those in full-scale profiles. Evaluation of laboratory-, pilot- and full-scale profiles from systems treating the same substrate showed that a laboratory-scale reactor and two pilot-scale reactors operated at comparatively high aeration rates poorly simulated full-scale temperature profiles. However, the curves from two moderately insulated, self-heating, pilot-scale reactors operated at relatively low aeration rates appeared to closely replicate full-scale temperature profiles. The importance of controlling aeration rates and CCR losses is discussed and further work suggested in order to investigate the links between simulation of the composting environment and process performance.     

Enhanced degradable yard waste collection bag behavior in a field-scale composting environment

The degradation of four formulations of yard waste-filled collection bags was evaluated in a field-scale test of 15.5- or 31-m-long windrows at a community yard waste composting site. Variables of bag contents, bag chemical composition, and length of exposure were evaluated. Chemical compositions of the bags included (1) low-density polyethylene (LDPE) + 6% cornstarch + 2 levels of prooxidant, (2) LDPE + 9% cornstarch + prooxidants, and (3) LDPE without cornstarch but with photooxidation enhancers. Results showed that all products weakened and/or disintegrated to some extent. However, the bags with 6% starch disintegrated too slowly to allow timely processing of the compost. The bags with 9% starch and other additives to promote multiple degradation mechanisms degraded at the fastest rate of those evaluated here. The photodegradable bags with solar exposure during composting disintegrated rapidly, but when turned to expose new surfaces to light, further strength losses occurred slowly.Paper presented at the Biodegradable Materials and Packaging Conference, September 22–23, 1993, Natick, Massachusetts.     

Physical modelling of the composting environment: a review. Part 1: Reactor systems

In this paper, laboratory- and pilot-scale reactors used for investigation of the composting process are described and their characteristics and application reviewed. Reactor types were categorised by the present authors as fixed-temperature, self-heating, controlled temperature difference and controlled heat flux, depending upon the means of management of heat flux through vessel walls. The review indicated that fixed-temperature reactors have significant applications in studying reaction rates and other phenomena, but may self-heat to higher temperatures during the process. Self-heating laboratory-scale reactors, although inexpensive and uncomplicated, were shown to typically suffer from disproportionately large losses through the walls, even with substantial insulation present. At pilot scale, however, even moderately insulated self-heating reactors are able to reproduce wall losses similar to those reported for full-scale systems, and a simple technique for estimation of insulation requirements for self-heating reactors is presented. In contrast, controlled temperature difference and controlled heat flux laboratory reactors can provide spatial temperature differentials similar to those in full-scale systems, and can simulate full-scale wall losses. Surface area to volume ratios, a significant factor in terms of heat loss through vessel walls, were estimated by the present authors at 5.0-88.0m(2)/m(3) for experimental composting reactors and 0.4-3.8m(2)/m(3) for full-scale systems. Non-thermodynamic factors such as compression, sidewall airflow effects, channelling and mixing may affect simulation performance and are discussed. Further work to investigate wall effects in composting reactors, to obtain more data on horizontal temperature profiles and rates of biological heat production, to incorporate compressive effects into experimental reactors and to investigate experimental systems employing natural ventilation is suggested.     

Effect of composting on the Cd,Zn and Mn content and fractionation in feedstock mixtures with wood chips from a short-rotation coppice and bark

Micronutrient content and availability in composts may be affected by the addition of wood chips or tree bark as a bulking agent in the compost feedstock. In the first part of this study, micronutrient levels were assessed in bark and wood of poplar and willow clones in a short-rotation coppice. Large differences between species were observed in bark concentrations for Cd, Zn and Mn. In the second part of the study, we aimed to determine the effect of feedstock composition and composting on Cd, Zn and Mn concentrations and availability. By means of three composting experiments we examined the effect of (a) bark of different tree species, (b) the amount of bark, and (c) the use of bark versus wood chips. In general, compost characteristics such as pH, organic matter and nutrient content varied due to differences in feedstock mixture and composting process. During the composting process, the availability of Cd, Zn and Mn decreased, although the use of willow and poplar bark or wood chips resulted in elevated total Cd, Zn or Mn concentrations in the compost. Cd concentrations in some composts even exceeded legal criteria. Cd and Zn were mainly bound in the reducible fraction extracted with 0.5 M NH₂OH?HCl. A higher acid-extractable fraction for Mn than for Cd and Zn was found. Higher Cd concentrations in the compost due to the use of bark or wood chips did not result in higher risk of Cd leaching. The results of the pH-stat experiment with gradual acidification of composts illustrated that only a strong pH decline in the compost results in higher availability of Cd, Zn and Mn.     

苏里格气田压裂返排液的处理及循环利用技术

针对苏里格气田压裂返排液的特点,形成一套以"微生物降解—化学氧化"、"屏蔽-沉淀"、"混凝-沉降"、"交联抑制"为特色的返排液处理技术,处理后水质清澈透明、无异味,满足重复配液需求。开发了一套模块化多功能处理装置,可满足不同的返排液处理需求,灵活方便、可靠性强、效率高,处理能力最高达300m~3/d。该技术已在苏里格区域全面推广应用,取得了良好的社会经济效益。     

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.     

Coffee husk composting: An investigation of the process using molecular and non-molecular tools

Various parameters were measured during a 90-day composting process of coffee husk with cow dung (Pile 1), with fruit/vegetable wastes (Pile 2) and coffee husk alone (Pile 3). Samples were collected on days 0, 32 and 90 for chemical and microbiological analyses. C/N ratios of Piles 1 and 2 decreased significantly over the 90 days. The highest bacterial counts at the start of the process and highest actinobacterial counts at the end of the process (Piles 1 and 2) indicated microbial succession with concomitant production of compost relevant enzymes. Denaturing gradient gel electrophoresis of rDNA and COMPOCHIP microarray analysis indicated distinctive community shifts during the composting process, with day 0 samples clustering separately from the 32 and 90-day samples. This study, using a multi-parameter approach, has revealed differences in quality and species diversity of the three composts.     

废水中难降解有机物的高级氧化技术

综述了近年来废水难降解有机污染物的高级氧化处理技术,主要包括化学氧化、电化学氧化、湿空气氧化、超临界水氧化及光催化氧化技术等。介绍了各种处理技术的基本原理及研究进展,并对其特点进行了评述。     

Use of Oxidation Onset Temperature Measurements for Evaluating the Oxidative Degradation of Isotatic Polypropylene

The widespread use of polymeric materials in many applications requires polymers that are weather resistant. The aim of this study is to examine the usefulness of oxidation onset temperature measurements as a tool for evaluating oxidative degradation of isotatic polypropylene. Differential scanning calorimetry was used to measure the oxidation onset temperature in formulations of isotatic polypropylene containing different concentrations of light and thermal stabilizers after aging in a Weather-Ometer. Oxidation onset temperature gave better results than oxidation induction time for evaluating the degradation of isotatic polypropylene during aging in a Weather-Ometer. However, both tests showed a poor correlation with the appearance of cracks seen by optical microscopy.     

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