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.     

Degradation of Poly(Ethylene Glycol)-Based Nonionic Surfactants by Different Bacterial Isolates from River Water

Different bacterial strains able to attack polyoxyethylene-type nonionic surfactants were isolated by enrichment procedure from the surface waters of the Arno River. Alkylphenol polyethoxylates and alkyl polyethoxylates, as well as polyethylene glycols, were degraded and assimilated by bacterial strains in axenic cultures. Degradative routes of polyethyleneoxide chains were investigated by matching each bacterial isolate with several types of nonionic surfactants and polyethers and by the identification of their degradation products isolated during aerobic digestion experiments. In accordance with previous reports, the first attack led to the shortening of the poly(oxyethylene) chains of the nonionic surfactants. It was found that the strains able to degrade PEG segments of nonionic surfactants possess enzymatic systems unable to degrade free PEGs, whereas those degrading the latter substrates cannot degrade PEG segments coupled to hydrophobic moieties.     

Adsorption/Desorption of Polyvinyl Alcohol on Solid Substrates and Relevant Biodegradation

The rates and extents of absorption and desorption of polyvinyl alcohol (PVA) samples on different solid substrates comprising montmorillonite, quartz sand, and farm soil, as well as humic acid mixture are reported. The uptake of PVA by the substrates was analyzed as a function of PVA hydrolysis (72–98%), molecular weight, and molecular weight distribution. Higher adsorption was detected on montmorillonite followed by farm soil, whereas the quartz sand did not display any specific adsorption affinity for the PVA. An increase in the hydrolysis degree of PVA increased the adsorption rate and extent whereas this feature was reversed by an increase in PVA molecular weight. The desorption of PVA samples from the different substrates was performed both under various pH conditions and in the presence of concentrated HF that was used to dissolve the silicon derivatives present in the substrates. Biodegradation experiments carried out in liquid cultures of PVA adsorbed on montmorillonite showed that the mineralization of the adsorbed PVA was much lower than that detected for the nonadsorbed PVA. This investigation suggests that irreversible adsorption of PVA on the clay component occurs in soil, thus substantially inhibiting PVA biodegradation.     

生物基聚合物PHBV和PLA复合材料在不同介质中的生物降解及其影响因素

传统工艺的塑料生产不仅依赖石油资源的持续开发利用,同时给环境造成了前所未有的压力,近年来生物基聚合物（聚（3-羟基-3-戊酸酯）-PHBV,聚乳酸-PLA）日渐成为传统石油基塑料的替代产品.本文采用呼吸测试手段,旨在揭示均质复合材料在不同环境介质（土壤、熟化堆肥、水体）条件下及有机添加剂（木质素）,无机添加剂（蒙脱石）和天然有机物链增长剂（Joncryl）作用下的生物降解特征.结果表明：当链增长剂Joncryl添加量为5%时,对所有介质PHBV和PLA复合材料产生显著抑制作用.Joncryl添加量为0.2%时,未对所测样品的生物降解行为产生干扰作用.在熟化堆肥介质中,PLA复合材料比PHBV基质混合物的生物降解速率明显降低.有机木质纤维添加剂（榛子壳粉末）单独在聚合物中添加或者和链增长剂Joncryl以及非有机添加剂（Dellite72T）共同作用下都可促进PLA聚合物中各组分的相容连接性.实验结果表明,新型添加剂在不同介质中以二元或三元添加的方式对生物降解过程产生重要影响,该研究将为新型材料使用后的生物降解效应提供理论依据.     

Bio-based Polyethylene–Lignin Composites Containing a Pro-oxidant/Pro-degradant Additive: Preparation and Characterization

Formulations of low cost bio-based oxo-biodegradable polyethylene (PE)/Lignin hybrid polymeric composites were prepared by using ethylene/vinyl acetate (EVA) copolymer as compatibilizer and a transition metal salt as oxo-biodegradation promoter. The hybrid composites and relevant Lignin-free blends were formulated by following a statistical mixture design. The effect of Lignin, pro-degradant additive, EVA copolymer and their compatibility with the PE continuous matrix, was evaluated by means of structural features by attenuated total reflectance, morphological by scanning electron microscopy, thermal by differential scanning calorimetry and thermo-gravimetric analysis and mechanical properties by an Instron Machine. The results attained in this study, regarding especially the thermal and mechanical properties, suggest that bio-based oxo-biodegradable hybrid composites offer an interesting way to produce low cost bio-based materials with fairly enhanced properties. The moderate-low cost hybrid materials appear to be attractive for their potential in the mercantile area of commodities including: packaging, personal care products, agricultural mulch films and disposable items. This will constitute a novel added-value contribution aimed at mitigating the environmental burden caused by plastic waste items improperly abandoned in the environment.     

Starch-filled polyethylene in a composting environment: Evidence for polyethylene matrix oxidation

Two series of starch-filled polyethylene films, consisting of high-density or low-density polyethylene and 0–20% starch, have been exposed for 60 days to a controlled composting environment. Evidence is reported that the oxidation of the polyethylene matrix is dependent upon the polyethylene type and content of starch.     

A New Respirometric Test Simulating Soil Burial Conditions for the Evaluation of Polymer Biodegradation

A new convenient and reliable method is described for assessing the biodegradation properties of polymeric materials under simulated soil burial conditions, which makes it possible to test with nutrient-rich soils. This method consists of the utilization of a minimum amount of a soil layer, in which the samples to be tested are set in close contact, sandwiched between two layers of perlite, a natural porous aluminosilicate. The biodegradation level is monitored by determining the carbon dioxide evolution derived from the test samples. The limited amount of soil used limits carbon dioxide evolution from the blanks, due to the corresponding limited overall amount of soil carbon. This experimental setup allows for an extremely satisfactory level of confidence in the analytical results, permitting a wider variety of soil types to be tested.     

Assessment of the Whole Environmental Degradation of Oxo-Biodegradable Linear Low Density Polyethylene (LLDPE) Films Designed for Mulching Applications

The current paper is aimed at understanding the environmental fate of linear low density polyethylenes (LLDPE) films designed for mulching purposes and loaded with different pro-degradant additives. These were analyzed, upon exposure to natural sunlight for a period intended to mimick a general crop season in the mediterranean region. The selected samples underwent a relatively low extent of degradation as monitored by carbonyl index, molecular weight variation, extractability by solvent, changes in the onset of the decomposition temperature and crystallinity. The tendency to biodegradation of outdoor exposed LLDPE was then assessed under different environmental compartments including soil medium, aqueous medium as well as in axenic culture of white-rot fungus Phanerochaete chrysosporium. That fungus is known to be effective in the degradation of recalcitrant organic materials and plastic items. During the soil burial biodegradation test, lasted for 27?months, samples specimen were withdrawn at time intervals and characterized by means of structural and thermal analysis. These analytical assessments allowed to monitor any progress of oxidative degradation as a direct effect of the incubation in an active microbial environment. Analogous characterizations were carried out at the end of the biodegradation tests in aqueous medium and in P. chrysosporium axenic cultures. Data presented here are in keeping with the initial abiotic oxidation via a free radical chain reaction promoted by a pro-degradant additive acting on hydroperoxides and peroxide moieties present initially in the polymer bulk. This step was followed by a free radical cascade reactions leading to degradation once the oxidation started under relatively mild conditions (sunlight exposure). During the incubation step in soil, the abiotically degraded samples underwent significant variation in the level of oxidation and degradation with respect to the detected starting values. Indications were gained on the synergistic effect of a random fashion microbial metabolization coupled to biotically mediated oxidation of the original abiotically fragmented samples. Similar results were obtained in the biodegradation tests carried out in the aqueous media and in presence of P. chrysosporium axenic cultures. These evidences are suggesting the role of natural occurring microorganisms in promoting both partial oxiditation and degradation of LLDPE samples in combination with contextual mineralization process of the oxidized fragments.     

Poly[(R)-3-hydroxy butyrate] Melt Processing: Strategy for Prevention of Degradation Reactions

Poly[(R)-3-hydroxy butyrate] (PHB) as well as all the components of the poly[(R)-3-hydroxy alkanoate]s (PHAs) family tend to degrade during processing at temperatures above their melting point via a hydrolytic mechanism induced by moisture attack and a concerted reaction mechanism induced by temperature. Therefore, the PHAs stabilization in the molten state is particularly important for production of biodegradable ecocompatible plastic items of commercial value. In order to refrain the indicated negative degradation effects, PHB was melt processed in a torque rheometer in the presence of a polymeric carbodiimide agent. Processed specimens were characterized by using FTIR, GPC, DSC, TGA and tensile properties. GPC analysis showed that the increase of the additive content in the formulation resulted in an increase of PHB molecular weight. However, decreasing in PHB thermal stability, glass transition temperature and mechanical properties, was observed with the increase of the additive amount. This behaviour most likely arises from the formation of new chemical structures promoted by the presence of the additive aimed at preventing the onset of hydrolitic processes.     

Characterization of Biodegradable Composite Films Prepared from Blends of Poly(Vinyl Alcohol), Cornstarch,and Lignocellulosic Fiber

Several composite blends of poly(vinyl alcohol) (PVA) and lignocellulosic fibers were prepared and characterized. Cohesive and flexible cast films were obtained by blending lignocellulosic fibers derived from orange waste and PVA with or without cornstarch. Films were evaluated for their thermal stability, water permeability and biodegradation properties. Thermogravimetric analysis (TGA) indicated the suitability of formulations for melt processing, and for application as mulch films in fields at much higher temperatures. Composite films were permeable to water, but at the same time able to maintain consistency and composition upon drying. Chemical crosslinking of starch, fiber and PVA, all hydroxyl functionalized polymers, by hexamethoxymethylmelamine (HMMM) improved water resistance in films. Films generally biodegraded within 30 days in soil, achieving between 50–80% mineralization. Both starch and lignocellulosic fiber degraded much more rapidly than PVA. Interestingly, addition of fiber to formulations enhanced the PVA degradation.