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J Polym Environ (2007) 15:125150 DOI 10.

1007/s10924-007-0053-8

ORIGINAL PAPER

Biodegradation of Agricultural Plastic Films: A Critical Review


Ioanna Kyrikou Demetres Briassoulis

Published online: 12 April 2007 Springer Science+Business Media, LLC 2007

Abstract The growing use of plastics in agriculture has enabled farmers to increase their crop production. One major drawback of most polymers used in agriculture is the problem with their disposal, following their useful lifetime. Non-degradable polymers, being resistive to degradation (depending on the polymer, additives, conditions etc) tend to accumulate as plastic waste, creating a serious problem of plastic waste management. In cases such plastic waste ends-up in landlls or it is buried in soil, questions are raised about their possible effects on the environment, whether they biodegrade at all, and if they do, what is the rate of (bio?)degradation and what effect the products of (bio?)degradation have on the environment, including the effects of the additives used. Possible degradation of agricultural plastic waste should not result in contamination of the soil and pollution of the environment (including aesthetic pollution or problems with the agricultural products safety). Ideally, a degradable polymer should be fully biodegradable leaving no harmful substances in the environment. Most experts and acceptable standards dene a fully biodegradable polymer as a polymer that is completely converted by microorganisms to carbon dioxide, water, mineral and biomass, with no negative environmental impact or ecotoxicity. However, part of the ongoing debate concerns the question of what is an acceptable period of time for the biodegradation to occur and how this is measured. Many polymers that are claimed to be biodegradable are in fact bioerodable, hydrobiodegradable, photodegradable, controlled degradable or just partially biodegradable. This review paper attempts to
I. Kyrikou D. Briassoulis (&) Department of Agricultural Engineering, Agricultural University of Athens, Iera Odos 75, 11855 Athens, Greece e-mail: briassou@aua.gr

delineate the denition of degradability of polymers used in agriculture. Emphasis is placed on the controversial issues regarding biodegradability of some of these polymers. Keywords Degradation Biodegradation Mulching lms Agriculture Polymers

Introduction Polymers are synthetic and natural macromolecules composed of smaller units called monomers that are bonded together. Examples of natural polymers include proteins, polysaccharides, and nucleic acids [1]. Synthetic polymers have been developed for durability and resistance to all forms of degradation [2]. These characteristics and others, such as rigidity, permeability and transparency can be controlled by changing the polymer synthesis, molecular weight and/or by the use of specic additives. The resulting plastics versatility allows them to be used in a very wide range of applications, including agriculture. Because of their wide use, the problems with the disposal of agricultural plastic wastes become more and more severe. Since 1990 the plastics industry, as individual companies and through organizations such as APC (American Plastics Council), has invested more than $1 billion to support increased recycling and educate communities [3]. Despite the continuing growth of recycling, source reduction and energy recovery, some proportion of the waste will always require disposal. The most common method for disposing of municipal solid waste is landlling [4]. A more signicant combination of source reduction, recycling, incineration and composting is being developed in Western Europe, the United States and elsewhere as an alternative to solid waste disposal in landlls.

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Many synthetic polymers are produced and utilized because they are resistant to chemical and physical degradation. On the other hand, polymers resistant to degradation present disposal problems when their usefulness ceases [5]. The degradation of used plastics is not a simple process, when referring to environmental degradation. The detailed mechanisms of how some of the plastics degrade after disposal in specic environments are not thoroughly understood and are the subject of intensive research during the last decades. Degradation under extreme conditions, such as incineration (which is one of various disposal options) is not a physical process, thus is not considered when referring to environmental degradation. Specically for the case of agricultural plastic wastes, one of the alternative ways of disposal is biodegradation. Biodegradation concerns specially designed polymers, the so-called biodegradable polymers. Most experts and acceptable standards [6, 7] dene a fully biodegradable polymer as a polymer that is completely converted by microorganisms to carbon dioxide, water, minerals and biomass (or in the case of anaerobic biodegradation, carbon dioxide, methane and humic material1) without leaving any potentially harmful substances. However, part of the ongoing debate concerns the question of what is an acceptable period of time for the biodegradation to occur and how it is measured. Given enough time (that may be even thousands of years), nearly all carbon-based materials may eventually biodegrade [4]. This does not mean that all carbon-based materials are considered to be biodegradable materials. Only those materials that biodegrade within a limited period of time, as this is dened by international standards (cited later on) and also satisfying a set of additional criteria (e.g. no ecotoxicity or negative environmental impact), shall be considered to be biodegradable. The most acceptable disposal method for biodegradable polymers is composting. However, composting requires an infrastructure, including collection systems and composting facilities [4], while it does not represent a practical solution for most cases of agricultural plastics wastes as compared to biodegradation in soil.

Use of Plastics in Agriculture The Importance of Plasticulture Polymers have been used in agriculture and horticulture since the middle of the last century [8]. The growing use of plastics in agriculture has enabled farmers to increase their crop production. Todays plasticulture (use of plastics in agriculture) [9] results in increased yields, earlier harvests, less reliance on herbicides and pesticides, better protection of food products and more efcient water conservation. Plastic lms are used as coverings of greenhouses or tunnels over crop rows, as silage covers, as bale-wrap lms, and as mulching lms to cover soil [9]. Plastic lms can improve product quality and yield by mitigating extreme weather changes, optimizing growth conditions, extending the growing season and reducing plant diseases. Greenhouses are mainly concentrated in two geographical areas: the Far East (especially China, Japan, and Korea) with almost 80% and the Mediterranean basin with about 15% of the worlds greenhouse covered area. The area covered by greenhouses has been steadily increasing at a rate of 20% per year during the last decade. Development in Europe is very weak but Africa and the Middle East are growing at 1520% annually. Of special interest is the case of China, which has grown from 4200 ha in 1981 to 1,250,000 ha in 2002 (30% per year). The volume of plastic lms used for this application would thus be about 1,000,000 t/year [10, 11]. In general, an estimated 23 million tons of plastics are used each year in agricultural applications [7, 9, 12]. Almost half of this amount is used in protected cultivation (greenhouses, mulching, small tunnels, temporary coverings of structures for fruit trees, etc.). Of extreme importance is the nancial impact of products originating from protected cultivation to the agricultural income in many less favoured regions of southern European Union (EU) countries. The vast majority of the protected cultivations area covered by plastic materials is dominated by the use of plastic made out of polyethylene (PE) [13]. In particular, low-density polyethylene (LDPE) is the most widely used polyethylene grade, due to its relatively good mechanical and optical properties, combined with a competitive market price. Disposal of Agricultural Plastics

Both humate and humic refer back to organic compounds found in the soil. Humate generally refers to compounds that are generated by the breakdown of plants and animals. Humic generally refers to either one of the organic acids found in soil resulting from the degradation of organic material, or it can refer to the organic layer itself found in many soils. The humic layer in a soil generally appears as a rich, dark earthy layer that is usually found in the upper portions of a soil prole

As the concentration of the plastics used in certain agricultural regions (rather than the overall quantities at national level) is very large and each year the usage is increased, the collection and clearing problems and the nal disposal problems of the accumulated in specic locations agricultural plastic waste is a fact. Therefore, the

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degradation and disposal options, or possibly the biodegradation of the used polymers, represent a very important subject with both economical and environmental aspects. Degradation of Agricultural Plastics Degradation During the Useful Life-time Degradation of a plastic in general, is dened as a detrimental change in its appearance, mechanical, physical properties and chemical structure [1418] (refer to the denitions in Appendix). It is important to make a distinction between the initiation of the degradation process (commencing in the extruder, at temperatures of around 200C, but controlled) and its manifestation during their useful life-time. The degradation process is delayed in actually damaging the plastic by a special balance of inhibitors engineered to the specic application and to the anticipated life expectancy of the plastic. Heat, ultra-violet radiation and stress can accelerate the degradation process of the material [19]. Degradation of agricultural plastics during their useful lifetime is due to a combination of factors (mainly UV radiation) [20] and may be controlled, to some extent, through the use of appropriate additives. Degradation after the Useful Life-time Further degradation of the aged agricultural plastic (i.e. agricultural plastic waste) following their useful lifetime is directly related to the various disposal options. In any case, degradation of agricultural plastic waste should not result in contamination of the soil and pollution of the environment (including aesthetic pollution) and the agricultural products safety. Describing plastics degradation, measuring it, and controlling it are all complicated by three major factors. (i) Mechanisms: Plastics can and do degrade by many routes, consecutively or simultaneously. The plastics can be fragmented through physical forces. Fragmentation often plays an important role in the early stages of degradation and can be brought about by physical forces of mechanical nature. Chemical changes within the plastic can occur and may begin with abiotic degradation. Chemical degradation occurs through reactions of the plastic with agrochemicals or other chemicals. Degradation brought by chemical reactions generally involves chain scissionfragmentation of the polymer chains. Surface erosion can be the result of chain scission resulting from chemical hydrolysis. At some point, some specic plastics may be attacked effectively by microorganismsthe onset of biodegradation. Biodegradation is generally considered as consisting of both enzyme-catalyzed hydrolysis and nonenzymatic hydrolysis [21]. Enzymatic degradation can be

carried out either by extracellular enzymes present in the microorganisms environment or by intracellular enzymes [22]. Both result in chain scission whereby the polymer chains are cleaved into smaller segments. The enzymes may be either endoenzymes, which cleave internal linkages within the chain or exoenzymes, which cleave terminal monomer units sequentially. Endoenzymes cleave the internal chain linkages randomly which results in a rapid decrease in molecular weight; the sequential cleavage of terminal segments leads to less dramatic immediate changes in molecular weight. Under some conditions microorganisms contribute to degradation of polymers through ingestion, mastication and excretion. All of these pathways are potential routes for polymer degradation [23]. (ii) Environmental conditions: How polymers degradation proceeds in a specic case depends on the environment the plastics are exposed to, during their useful lifetime and the environment the polymer wastes are disposed to, afterwards. The kinetics of polymer degradation depend on whether the environment is dry air, humid air, soil, a landll, a composting environment, sewage, freshwater or a marine environment. Each environment has its own characteristic concentration prole of important factors: oxygen, water, other chemicals, daylight and degrading microorganisms [7, 2427]. According to the nature of the environment there may be a relatively more efcient or less efcient mechanism by which degradation can occur. In one environment a very efcient degradation mechanism may be available, whereas in another environment the same mechanism might not be available at all for lack of appropriate conditions. Also according to the nature of the environment, there may be a larger or a smaller concentration of chemicals that react with the plastic during the degradation process. More specically, the environmental factors affecting the rate of degradation that is due to microorganismsthat is the value of biodegradationinclude temperature, moisture level, atmospheric pressure, and pressure of oxygen, concentrations of acids and metals, and the degree of exposure to light. Factors relating to microorganisms include their concentration, whether or not they have enzymes for which the polymer is substrate, the concentration of enzymes, the presence of trace nutrients for the microorganisms and the presence of inhibitors or predators. If any of the required elements is absent, or if it is present at a level that falls below a critical threshold, biodegradation may not only slow down but may stop altogether until proper conditions are once again present [2831]. (iii) Polymer composition: Regardless of the environment, the mechanism and rate of degradation also depends on the chemical composition of the polymer. The rate of possible biodegradation in particular, depends on the polymers characteristics because the polymer is the

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substrate for the enzymes. One factor that determines the degradability or biodegradability of a polymer is the nature of the chemical bonds that are present. The chemical structure of the polyolens contains only carboncarbon single bond in their backbones. That feature makes them particularly resistant to degradation [7, 17, 32]. Also the carbon-carbon single bonds of polyolens make them hydrophobic. Thus they are not susceptible to hydrolytic degradation. They can be degraded through oxidative mechanisms but not very readily while processing increases their resistance [2, 14, 33]. Also, it is well known that antioxidants are added to increase their stability against various degradation mechanisms. Besides the nature of the chemical bonds that are present the details of chain branching and even stereochemistry (the detailed spatial arrangement of atoms and bonds) are also important, because enzymes are often specic to attacking one particular type of chain branching and one particular stereochemistry. The polymers molecular weight and the degree of chain exibility can also be important. The morphology of the polymer is important as well, including the extent of surface and the degree of crystallinity. The degree of crystallinity is important in the case of polyolens because oxygen does not easily enter the crystalline regions; they are impermeable to oxygen. Oxidation of polyolens occurs mainly in the amorphous regions.

if degraded, remain intact for many years [29, 30, 3841]. Their persistence, for most part, originates in three of their properties that make them so useful for many applications: they are generally strong mechanically, water resistant and micro-organisms do not readily attack them [32] (and if they do, the extent and rate of attack are not practically signicant). Readily Degradable Plastic (gradually degradated) A readily degradable plastic, usually after its useful life has ended simply self-destructs. The degradation of these materials is gradual and cannot be really controlled. The timing of degradation can be predened however empirically to some extent based on the selection of the type and amount of stabilizing additives. Such a material, after the time required for a useful service is over, during which retains more or less all the properties that it was formulated and processed to have, it simply falls apart and it may, or may not be assimilated by the pervasive microorganisms found in nature. If not, it simply becomes very brittle and its fragments pollute the environment. If yes, it returns to the ecosystem in an environmentally harmless manner, provided that this is not associated with any ecotoxicity effects or negative environmental impact [32] (to be veried by performing testing for ecotoxicity following relevant international standards). This brings forward the question on the biodegradability of several polymers, assumed or claimed to be biodegradable. Plastics of Controlled Degradation (Programmed degradable plastics; step degradated) Programmed degradation, or controlled degradation, is an idea that has started 2030 years ago. The goal of programmed degradation is to program plastics to degrade in a predetermined time under specic conditions according to the needs of particular applications. The difference between programmed degradable plastics and the materials of the previous category lies with the degree of the control of degradation in terms of timing and also the shape of the degradation curve. Programmed degradable plastics exhibit, at least theoretically, a step-wise degradation, with the onset of a rather abrupt and so much more severe degradation occurring at a timing that is better predened than that of the gradually degraded polymers. The programmed degradable materials approach aims at the elimination of the litter problem; one such approach is based on exposure to natural sunlight that is common in agricultural applications. The objective in this case is to modify the resin so as to promote photodegradation (degradation that results from the UV radiation) [4245]. The strategy is to attach a photosensitizing group to the polymer

Plastics Categories The main causes of degradation of agricultural plastics during the useful lifetime are photodegradation and oxidation [34]. The plastics may be categorized according to how readily they degrade during their exposure in a specic environment and the nature of degradation to which they are subjected to, into the following categories [14, 16, 17, 32, 3537]: Non-degradable plastics Readily Degradable Plastic Plastics of controlled degradation (Programmed Degradable Plastics) Environmentally Degradable Plastics (plastics of this category may also fall under the two previous categories)

Non-Degradable Plastics Commodity plastics are typically stable for a specic useful life-time, depending on the application and the environment, and they degrade thereafter to some degree (e.g. in terms of retaining their initial mechanical properties). In some environments, objects made from them, even

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chains by chemical means. When this photosensitive group is exposed to natural light, it absorbs radiation, which causes the chain to break and form smaller segments, a process called scission. As photodegradation proceeds, the chains are broken in more and more places, and the plastic litter is destabilized through embrittlement. Eventually it becomes fragile and is fragmented. Erosion by wind and rain completes the breakdown of the embrittled plastic into friable powder [46]. In more general terms, oxidative programmed degradation is a programmed degradation that results from oxidation. Some polyolen additives allow oxidative degradation to be initiated at a pre-dened time (to some extent), either by natural daylight, or by heat or both or even by mechanical stress [19, 4749]. The applications from such programmed resins are plastic products for which disposal might include earth burial, as with compost bags and agricultural mulch covers. Moreover the fragments formed by oxidative degradation may be wettable, leading to increased interactions with water and promoting hydrolysis [50, 51]. Through oxidative and hydrolytic degradation the polyolen undergoes a progressive chain scission. In time, severe embrittlement leads to extensive fragmentation. Fragmentation is not the same as total degradation. A plastic may fragment after being discarded, but may not degrade readily so as to be decomposed for example by microorganisms [32, 5254]. Through embrittlement a large piece of plastic becomes fragile and the many small pieces of plastic eventually turn into a friable powder sometimes even invisible to the naked eye. In theory, fragmentation of the polymer chains in the plastic makes them more susceptible to other modes of degradation, possibly including some kind of biodegradation activity that should be dened however, in terms of rate and the specic conditions under which it is measured, including the measurement methodologies. What is desirable practically for a programmed degradable plastic is adequate performance properties initially and no signicant decrease in performance properties during the planned useful lifetime. On the other hand after a pre-determined (to some extent) period of use degradation is to begin upon disposal, starting with fragmentation or surface erosion. In any case, it should be ensured that the fragmentation will continue with 100% biodegradation without any ecotoxicity effects and that will leave no remains, whether invisible or not, in the soil within a reasonable time period to avoid accumulation in the soil. Such characteristics have not been conrmed yet beyond any doubt with the available programmed degradable plastics. In practice, questions related to the environmental fate and ecological effects of polyolen fragments have not been conclusively resolved. For example, if agricultural

covers made from modied polyethylene resins (e.g. PE with pro-oxidants) are ploughed into the soil at the end of a growing season, it is not yet known what might be the fate of these remains and what degree of accumulation may be experienced with time (note that the remains are in the form of intermediated-length polyethylene chains due to degradation). Most important is the long-term effect of any accumulating residues of such materials in the soil environment, the agricultural product safety for the consumer and the agricultural productivity for the agricultural soil. It has not been veried systematically with scientic justication so far if there are any, or there are no harmful effects or negative environmental impact. The answers to these questions need long term systematic multidisciplinary research work. Environmentally Degradable Plastics Many polymers that are claimed to be biodegradable are in fact bioerodable, hydrobiodegradable or photodegradable [6], or just partially biodegradable. These different polymer classes are grouped by some authors under the broader category of environmentally degradable polymers. Of course the use of the label environmentally may be unjustied and misleading in these cases. Even though this term is widely used in literature [5257 etc], and while it can also be found in the title of ASTM D600296 (Standard Guide for Assessing the Compostability of Environmentally Degradable Plastics) [6], it was not possible to nd an ofcial denition for it. Environmentally degradable plastics (EDP), based on the use of the term rather than on a specic denition, can be considered to include a wide group of natural and synthetic polymeric materials that undergo chemical change under the inuence of environmental factors. The chemical change must be followed by complete microbial assimilation of degradation products resulting in carbon dioxide and water. In particular, according to literature [54, 58] the process of EDP degradation comprises two phases, disintegration and mineralization. During the initial phase, disintegration is signicantly associated with the deterioration in physical properties, such as discoloration, embrittlement and fragmentation. The second phase is assumed to be the ultimate conversion of plastic fragments, after being broken down to molecular sizes, to CO2, water, cell biomass (aerobic conditions), and CH4, CO2 and cell biomass in the case of anaerobic conditions. The EDP degradation and assimilation must be complete and occur at a sufciently rapid rate so as to avoid accumulation of materials in the environment [42, 56]. There are questions however concerning the validity and the conditions of the assumptions about the second phase [7].

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EDPs can be synthesized on renewable or non-renewable feedstocks. Examples of EDP from renewable feedstocks are cellulose, starch, starch esters, collagen, viscose, cellulose acetate (DS < 2), polyhydroxy alkanoates, polylactic acid etc, and from non-renewable feedstocks are polyvinyl alcohol, polycaprolactone, aliphatic-aromatic copolyesters, blends of starch and biodegradable polyesters etc. Renewable feedstocks used for EDP production can be simple natural compounds (such as amino acids, sugar, sesources of vegetal, aquatic, and animal origins) or can be derivatives of natural compounds that have undergone chemical transformation to give an appropriate building block for EDP. EDP can also be produced from nonrenewable feedstocks, most commonly from natural oil and gas. EDP are often used as blends or composites in which two or more biodegradable materials are combined to provide optimal performance while maintaining or enhancing complete biodegradability [54, 56, 58]. Regardless of feedstock source according to the ICS EDP guideline2003 (International Centre for Science and High Technology of the United Nations Industrial Development Organization (ICS-UNIDO)) [56], an EDP material must have the following properties: Rapid degradation and/or biodegradation Bioassimable degradation products (leading to CO2 and water via biological pathways) Ease of processing High versatility Acceptable performance An acceptable price for intended use.

degradation that occurs is aerobic degradation and carbon dioxide is produced. If there is no oxygen available, the biotic degradation is anaerobic degradation, and methane is produced instead of carbon dioxide. Under some circumstances both gases are produced. Mineralization is dened as the conversion of biodegradable materials or biomass to gases (like carbon dioxide, methane, and nitrogen compounds), water, salts and minerals, and residual biomass. Mineralization is complete when all the biodegradable materials or biomass is consumed and all the carbon in it is converted to carbon dioxide. Complete mineralization represents the rendering of all chemical elements into natural biogeochemical cycles [32, 61]. Usually, there are two steps involved in the biodegradation of the polymer [61]: Mechanical (grinding), chemical (irradiations by ultraviolet rays; e.g. photodegradation), or thermic degradation. During this stage, microscopic fungi and bacteria, or other biological agents (earthworms, insects, roots of plants, even rodents), can also fragment the product (biofragmentation). This rst phase is very useful, because it leads to the increase of the surface of the material exposed to the microbodies occurring in the second phase. The second phase corresponds to the biodegradation Sensu Stricto. Microbodies attack and digest the product, which is transformed in by-products which are assimilated by the microbodies, the nal result being CO2 or CH4, water and biomass production. This second phase is often concomitant of the rst one.

According the Australian Department of Environment and Heritage2 the classes of Environmentally Degradable Plastics are [55]: Biodegradable polyesters Biodegradable starchbased polymers Watersoluble polymers Photodegradable polymers Controlled degradation masterbatches

Factors Affecting Biodegradation Biodegradation is fundamentally an electron transfer process [32]. Biological energy is obtained through the oxidation of reduced materials. Microbial enzymes catalyze the electron transfer. Electrons are removed from organic substrates to capture the energy that is available through the oxidation process. The electrons are moved through respiratory or electron transfer chains (metabolic pathways) composed of a series of compounds to terminal electron acceptors [32]. A large proportion of the microbial population in soil depends upon oxygen as the terminal electron acceptor for metabolism. Loss of oxygen induces a change in the activity and composition of the soil microbial population. Facultative anaerobic organisms (which can use oxygen when it is present or can switch to alternative electron acceptors, such as nitrate and sulphate, in the absence of oxygen) and obligate anaerobic organisms become dominant when oxygen is not available [32], but aerobic biodegradation is typically more efcient.

Biodegradation Biodegradation or biotic degradation is chemical degradation of materials (e.g. polymers) brought about by the action of naturally occurring microorganisms such as bacteria, fungi and algae (chemical degradation that does not involve biological activity is dened as abiotic degradation) [32, 59, 60]. As biodegradation proceeds it produces carbon dioxide and/or methane and water. If oxygen is present the biotic
2

Classication based on work performed for the Australian Department of Environment and Heritage by Nolan-ITU.

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For microora (fungi, bacteria and the like) to convert and assimilate the carbon in any substrate, a number of criteria must be met. The substrate must be waterwettable, and the constituent molecules must be sufciently small that a very large number of their chain ends are accessible at the surface of the material [27]. Hydrocarbon thermoplastics are bioinert because they are hydrophobic, and because their good mechanical properties require very high molecular weights, leading to very few accessible chain ends. Also are resistant to hydrolysis (and for this reason cannot hydrobiodegrade) and to oxidation and biodegradation due to the presence of anti-oxidants, and stabilizers additives [27]. A wide variety of organic materials are easily degraded under aerobic conditions. In aerobic metabolism, O2 is the terminal electron acceptor. When biodegradation follows this pattern, microbial populations quickly adapt and reach high densities. As a result, the rate of biodegradation quickly becomes limited by rate of supply of oxygen or some nutrient, not the inherent microbial capacity to degrade the polymer or other contaminant [32]. Some organic compounds can also be degraded under anaerobic conditions. When oxygen is absent, nitrate (NO ), sulphate (SO ), 3 4 ferric iron (Fe3+), manganese (Mn3+, Mn4+), and bicarbonate (HCO) can serve as terminal electron acceptors, if the mi3 crobes have the appropriate enzyme systems [32]. Under anaerobic conditions, the rate of degradation is usually limited by the inherent reaction rate of the active microorganisms; adaptation is slow, requiring months or years, and metabolic activity results in the formation of incompletely oxidized, simple organic substances, such as organic acids, and by-products such as methane or hydrogen gas. Microorganisms help decompose organic matter in marine environments as well [52]. Numerous factors affect the potential force and the rate of naturally occurring biodegradation at a given site, such as [32, 52]: soil moisture content, porosity, soil temperature, soil pH, O2 availability, presence of suitable microbes, presence of contaminants and their concentration, availability of nutrients, presence of other electron acceptors, redox potential etc. Especially for biodegradable in soil polymers, the rate at which biodegradation occurs depends on soil conditions such as temperature, water content (a measure of the concentration of water), degree of aeration (a measure of the concentration of oxygen), acidity (a measure of the concentration of acids) and the concentration of the microorganisms themselves. Under extremely unfavourable conditions degradation rates can be reduced to nearly zero [32, 61, 62]. Low temperatures strongly inhibit degradation in soil. Water content of the soil is also important; it supports hydrolytic degradation. Aeration supports oxidative

degradation and the degree of aeration determines whether aerobic or anaerobic biotic degradation or bothtakes place. Although there are many bacteria that thrive on an oxygen-free environment, there are many more that use oxygen. Biotic degradation also requires that the soil may be microbial active. Biotic degradation rates can be reduced to nearly zero in a sterile environment, or when the concentration of microorganisms is very low or even if the material is not really biodegradable. Many harmful metabolites may be generated microbiologically in a variety of environments. These products may represent substantive threats to the health, growth, or vigour of humans and a variety of animals and plants, thus determining the environmental impact of the biodegradation. What microorganisms do to that chemical may be of a great importance to human health, agricultural productivity or populations in natural ecosystems. The biological active metabolite formed from a toxicant may not always be toxic. Sometimes, it may be stimulatory [36]. Biodegradable Polymers Materials It is beyond the scope of this work to present an analytical overview of the various biodegradable materials. Only some general information is offered in the present section in support of the main objectives of this work. Biodegradability represents a complex phenomenon difcult to measure. As stated above, a material may be considered to be biodegradable if it can be shown beyond any doubt that it is fully and environmental safely degraded by microbodies under special conditions. The result is the formation of water, CO2 and/or of CH4, and of minerals and a new biomass, leaving no toxic elements for the environment and any remains or fragments. Biodegradable polymers may be naturally occurring or may be synthesized by chemical means [1, 19]. Biodegradable polymers can be divided in general into three groups [8]: 1. 2. natural polymers such as starch, cellulose, proteins, poly-b-hydroxybutyrate natural polymers biologically or chemically modied (e.g. cellulose acetate, lignocellulose esters, polyalkanoate copolymers...) readily biodegradable synthetic polymers modied (complexed or blended etc.) with added natural biodegradable components (starch, reclaimed cellulose, natural rubber, etc.) [63, 64, 65] (note that blends of non-biodegradable polymers with natural biodegradable materials are not and should not be considered to be biodegradable materials [66]).

3.

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Synthesized polymers may come from the processing of crops grown for this purpose or the by products of other crops (renewable resources) or may come from petrochemical feedstocks (non-renewable resources). Biodegradable polymers form a unique class of materials that created an entirely new concept when originally proposed as biomaterials. That is, for the rst time, a material performing a structural application was designed to be completely absorbed and to become weaker over time [67]. This concept was rst applied successfully with catgut sutures and later with more arguable results, on bone xation plates and pins [68]. Later on, biodegradable materials were also introduced to agricultural applications. Systematic reviews of biodegradable materials and examples of really biodegradable materials used in agriculture, such as mulch lms, owerpots and controlled-release fertilisers, can be found in literature [13, 6973]. One of the prototype biodegradable plastics used in agriculture is Mater-Bi [13, 74, 75]. This is a biodegradable and water-soluble thermoplastic material, based on starch, complexed with biodegradable polyesters. The material satises the biodegradability and compostability requirements of European norm EN 13432, and the national norms UNI 10785 and DIN54900. Furthermore, Mater-Bi does not contain any dangerous substances, as dened by the Community Directive 67/548/CEE, as modied by the Commission Directive 97/69/CE and subsequent modications [73]. Other biodegradable polymers used for producing biodegradable agricultural lms include copolyesters [76], poly(vinyl alcohol) [77] and poly(vinyl chloride) [78], acylated starch-plastic [79], modied starch, vegetable oilbased resins and others [69, 73]. Environmental Impact of Biodegradable Polymers It is reported in literature [67] that polymers that degrade by peroxidation followed by bioassimilation (or by a degradation that is assumed to be bioassimilation) of the oxidation products (oxo-biodegradable polymers) are in general more environmental acceptable (green) than some biologically produced hydro-biodegradable polymers. The claim that the use of renewable sources of feedstocks is better than that of non-renewable ones, is a judgment that cannot be made without carrying out a complete environmental impact analysis on each source. According to an analytical approach [80], in the manufacture of hydrocarbon polymers, carbon is taken from one carbon sink3 (e.g. an oil deposit) to another carbon sink
3 A sink is a reservoir that uptakes a chemical element or compound from another part of its cycle. For example, soil and trees tend to act as natural sinks for carboneach year hundreds of billions of tons of carbon in the form of CO2 are absorbed by oceans, soils, and trees.

(plastic) with no net production of atmospheric carbon other than that generated during energy production for the conversion process. The environmental impact of natural products like biopolymers produced by growing bacteria on an appropriate feedstock or starch based or other biodegradable materials has been analyzed by several researchers [81, 82]. According to other analyses on biopolymers, the production based on fermentation is not a sustainable process [83]. In fact, when considering the energy and material requirements for corn farming and wet milling, fermentation, and polymer recovery, a rather discouraging picture emerges. All major environmental indicators such as carbon emissions, air acidication, eutrophication, and depletion of natural resources show that fermentative production has considerably more negative environmental impact than conventional plastic production [83]. This analytical approach suggests that while the major emissions of greenhouse gases occur during the production and use phases of products, the end-of-life phase should not be neglected. Whether to prevent greenhouse emissions from biodegradable materials or to recover resources as material or energy, it is now accepted that diversion of untreated waste from landlls is an important factor in reducing resource use and associated climate change effects [84, 85]. Along the same line, supporters of the programmed degradable polymers claim [16] that the growing of agricultural crops may involve the application of fertilizers, herbicides and pesticides which may leave a deep environmental footprint. Unless appropriate soil management practices are in place the soil risk severe depletion of nutrients, microorganisms etc. In addition chemical or biochemical processes usually are required to extract and purify the polymer. These processes may require water, energy and chemical or biological additives. They also produce wastes which require treatment and disposal. Such claims however, have to be compared against the corresponding footprint of the programmed degradable polymers that includes the fossil-oil based polymers production and the corresponding plastics wastes problem (heavy environmental impact from oil extraction and oil renery industries, processing with energy, waste management impact etc). On the other hand, another important factor to be taken into account is the fact that care is (or can be) taken recently for promoting sustainable low-input agriculture. Additional environmental considerations for the use of biodegradable over conventional polymers are the declining petrochemical sources (the fact that is also responsible for major international geo-strategic conicts), and also the fact that the biodegradable plastics offer a safe and cheap alternative option to recycling, in terms of waste management (especially for mulching lms) [72]. It is important to take into account the fact that the difcult, in any case,

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waste management of non-biodegradable agricultural lms and other plastic materials used in agriculture is also associated with a signicant negative environmental impact and with the corresponding waste management cost. Concerning the environmental impact of various biodegradable materials, one of the most important issues is the degree of biodegradation of the material. The degree and rate of biodegradation is dependent on the chemical composition of the polymer and its working environment, and so there is no single optimal method for determining biodegradation. When comparing the degree to which different polymers biodegrade, several factors must be taken into consideration. The rst of these factors is the environment. Polymers may be tested for biodegradability in a natural or simulated environment [16] (refer to the section on the standard testing methods later on). Finally, the environmental effects of the polymer must be considered. A polymer that biodegrades is of little value if the products that forms are found to contaminate water supplies or be toxic to living organisms in the environment or to be accumulated in the soil over the years because of very slow degradation rate. Claims and Controversies on Labelling Biodegradable Polymers Various studies have shown that several naturally-occurring polymers biodegrade, and chemically modied natural polymers may biodegrade depending on the extent of modication. It has been reported in literature that synthetic addition polymers, with carbon as the only atom in the backbone do not biodegrade at molecular weights above 500 Daltons [62, 86]. According to other authors it has been reported that when the molecular weight is reduced to around 100,000 Daltons the plastic embrittles and akes. According to them, below 40,000 Daltons the molecular structure becomes bio-degradable [87] (possibly under specic conditions). The structure becomes water wettable and microbes and fungi can attach to it, to convert carbon to cell wall structure. If an addition polymer contains atoms other than carbon in the backbone, it may degrade depending on the attached functionality groups. Synthetic condensation polymers may biodegrade to different (more) extent depending on chain coupling (ester > ether > amide > urethane), morphology (amorphous > crystalline), molecular weight (lower > higher), while biodegradation of hydrophilic materials is faster than hydrophobic. However, if a polymer is water soluble, that does not necessarily mean that it is biodegradable [32]. Another major issue is the environmental conditions under which materials can biodegrade. For example, some materials are biodegradable under composting conditions but not in the soil.

In several cases, readily biodegradable polymers are mixed-up with non-biodegradable polymers or polymers with additives. Blends of non-biodegradable polymers with starch have been used [88], among others. In other cases, degradable mulching lms have been developed that break down into small brittle pieces (disintegrate), which pass through harvesting machinery without difculty, but do not actually biodegrade [89]. Of course, real biodegradable polymers have been developed as well [88]. One of the requirements of the ASTM denition of Compostable Plastic [6] is that it leaves no visible, distinguishable or toxic residue after degradation. Thus to be considered as environmentally degradable a plastic must become brittle rapidly enough to disappear visually, and the degraded material must be susceptible to biological attack giving complete conversion to biomass without release of toxic products within an acceptable time period (dened by relevant Standards). The ASTM Standard species certain tests to determine conformance. The classes of plastics promoted and labelled in the market, in terms of the claimed degradation and/or biodegradation mechanisms, are summarized as follows [35]: Oxo-degradable Polymers The oxo-degradable materials are claimed to be inherently degradable that will degrade through photo, thermic degradation and molecular scission in a time controllable manner [35]. Photodegradable Polymers The breakdown of photodegradable polymers depends on irregularities in them. These irregularities cause them to slowly degrade when exposed to ultraviolet (UV) radiation, typically sunlight. In photodegradable plastics, the rate of degradation is increased by adding photosensitive substances, called promoters, to the plastic material [90]. Two common promoters are carbonyl groups (carbon double bonded to oxygen) and metal complexes (metals blended with many ingredients) [69]. The exposure of a mulching lm to ultra violet radiation, for example, is variable and non-existent when the material is buried or even just covered by the cultivation. Thus there is insufcient ultraviolet radiation, leading to insufcient photo degradation of parts of the material. The fate of these materials in the soil, even if photodegradated to very small fragments is strongly disputed [27, 44]. Carbonyl Group: Ketone Carbonyl Copolymers This type of photodegradable plastic is produced by adding a carbonyl group, vinyl ketone comonomer, to the

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polymers such as polyethylene (PE) and polystyrene (PS) [90]. The resulting copolymer degrades when the carbonyl group absorbs sunlight. Because these products require direct sunlight to degrade, this material is ideal for mulch lm (assuming that the lm is exposed to sun-light and not covered by the plants; part of the lm is buried in the soil along the two longitudinal sides of the lm anyway and so it is not exposed to sunlight). In order for the material to be completely consumed by microorganisms a biodegradation process should be activated and completed following the end of the useful lifetime of the material. Such a biodegradation process has not been conrmed for these materials, at least not conrmed beyond any doubt. Carbonyl Group: Carbon Monoxide Copolymers In this category of materials, the carbonyl group carbon monoxide is added to produce a degradable copolymer, called carbon monoxide copolymers. Manufacturers of this materialincluding Dow Chemical, DuPont, and Union Carbideclaim that carbon monoxide copolymers are able to degrade into benign by-products. However, questions remain about the extent of degradation. More research is needed to determine whether carbon monoxide products completely degrade into non-plastic products or whether they simply disintegrate into smaller pieces of plastic [90]. Metal Complexes A relatively new approach to photodegradable plastics is adding metal salts. Degradation of these polymers is invariably activated by a transition metal. The main difference between plastics containing metal salts and other photodegradable materials is its ability to break down also in the absence of solar radiation. In fact, if they receive enough UV radiation before burial, these products may even be able to degrade in landlls. Products being made from polymers with metal complexes include mulching lms and tree shelters. Currently, one of the main concerns with these materials is the heavy toxic metal residues remaining after degradation takes place [90]. More details about the metal complexes used are needed to evaluate the possible applicability and limitations of these materials. In any case, strong concerns on the possible biodegradation of these materials have been expressed in the literature and the relevant scientic questions remain open [7, 47, 48, 68]. Thermodegradable Polymers

proceed by b-H elimination or syn-elimination. This process, known as internal elimination (Ei), is generally believed to be a single step mechanism with a cyclic transition structure, as rst proposed by Hurd and Blunck [89]. Questions are raised however with respect to the possible biodegradation of these materials as well [91]. Compostable Polymers Compostable biodegradable plastics must be demonstrated to biodegrade and disintegrate in a compost system during the composting process (typically within around 12 weeks at temperatures over 50C) [7, 27, 70] (refer to the denitions in the Appendix). The EU Directive on Packaging and Packaging Waste (94/62/EC) [92] denes requirements for packaging to be considered recoverable. The compost must meet quality criteria such as heavy metal content, ecotoxicity, and leave no obvious distinguishable residues caused by the breakdown of the polymers. Compostable biodegradable plastics are a subset of biodegradable plastics. Hydro-biodegradable Polymers Some biodegradable polymer materials experience a rapid dissolution when exposed to particular (chemically based) aqueous solutions [93]. These polymers, the hydro-biodegradable polymers, are claimed to be broken down in a two-step processan initial hydrolysis stage, followed by further biodegradation [87, 94]. Single degradation phase water-soluble polymers also exist. Bioerodable Polymers Many polymers that are claimed to be biodegradable are in fact bioerodable (i.e. biodegradation is limited at the surface level) and may degrade further (i.e. in the bulk material) without the action of micro-organisms. This is also known as abiotic disintegration, and may include processes such as dissolution in water, oxidative embrittlement (heat ageing) or photolytic embrittlement (UV ageing) [2, 46, 47, 69, 87]. Systematic research work is needed to clarify the terminology and the conditions under which the claimed degradation behaviour and rate is ensured and can in fact be measured by standard testing methods (see below). The Question on Possible Biodegradation of Polyolens The Polyethylene Case

Degradation of these polymers initially begins when the product is exposed to heat (refer to the denitions in the Appendix). Usually these polymers contain azo-groups in the main polymer chain. Thermolytic cleavage is known to

There is a very long controversial discussion going on for years now over the possible biodegradation of polyethylene in soil. Many sources clearly indicate that polyethylene

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(PE) is perfectly stable and thus is not directly oxidisable [70], or that PE is inert [8] and not biodegradable [67]. Two preliminary treatments (heat and ultra violet radiation) are essential to modify its chemical structure. These are found to oxidize (introduce oxygen in the form of hydroxyls, carbonyls, peroxides), degrade (reduce the molecular weight or increase it by crosslinking reactions) and destructure (modify the crystalline structure) the PE. Karlsson et al. [34] have estimated PE oxidization to be very slow, namely, in the order of 1 mg per 100 g of the product per week or about 0.001% of the product per week. It has been reported that the molecular weight of degraded polyelythene varies between 200,000 and 600 Daltons [26, 34, 59], and that apparition of the double bonds has been observed at a rate of 0.0035% [70], that is 1 in 30,000. Other contradictory results show notable increases of molar mass during the oxidization of the PE [33, 59]. (Bio?)degradation of low-density polyethylene (LDPE) has been reported, but the rate is very slow. Albertsson [95] found 0.2% weight loss for LDPE lms buried in soil for 10 years. Of course, such a rate cannot justify the use of the term biodegradation, as biodegradation is also related to the rate. In this survey, Albertsson et al. [95] used LDPE lms labelled with 14C, cut them into small pieces, and buried them under soil, which was kept in controlled conditions. The degree of biodegradation was estimated by the yield of 14CO2, which is the possible nal product of the metabolic cycle of the degradation of the LDPE. These phenomena are very slow (300 years to break down a thickness of 60 lm) and affect the outer surface of the material [30], they are limited to a thickness of the order of 1 lm. The UV light accelerates the breaking down [29, 30], as much as doubling the breakdown speed process. In a report published in 2005, Hadad et al. [96] claimed that that polyethyleneconsidered to be inertcan be biodegraded if the right microbial strain is isolated. They used enrichment culture methods which were found to be effective for isolating a thermophilic bacterium (brevibaccillus borstelensis) capable of utilizing polyethylene as the sole carbon and energy source. Incubation of polyethylene with B. borstelensis (30 days, at 50C) reduced its gravimetric and molecular weights by 11 and 30% respectively. Brevibaccillus borstelensis also degraded polyethylene in the presence of mannitol Maximal biodegradation was obtained in combination with photo-oxidation, which showed that carbonyl residues formed by photo-oxidation play a role in biodegradation. They reported that Brevibaccillus borstelensis also degraded the CH2 backbone of nonirradiated polyethylene. Of course such a selective microbial treatment under laboratory conditions has only theoretical interest as it is not possible under real agricultural soil conditions.

Fragmentation of the lms can result from the presence of microorganisms [59]. Rain, temperature, light etc. are factors that affect the degradation, which may be accelerated by their synergist activities or inhibited by their adverse effects. As a result of degradation (fragmentation), the condition of the degraded LDPE may encourage attack by microbes (i.e. an afnity of LDPE to microbes is assumed to become so strong that the biodegradationalong with a complex degradation mechanism composed of several factors such as normal oxidization, effects of moisture and metal ions in soilis promoted [30]). The degradation in which microbes may participate, is developed from the surface to the inside of the lm; the rate of degradation progressing to the inside is determined by the diffusion rate of metabolites from microbes, not by that of oxygen, water and metal ions [30]. According to other authors, when the level of oxides formation is increased (and that can be accomplished with the use of special additives), the result could be biodegradation. The assimilation of the order of 60%, of the total carbon after 180 days in an articial soil maintained at 60C has been reported [70]. However this procedure does not simulate real soil conditions and the conclusions reached may be misleading with regard to possible biodegradation of agricultural lms in soil. In another work published by Karlssson et al., it has been reported that after 426 days, 27.8% mineralization is obtained in compost. Some theory has been established to demonstrate the role of additives in the PE degradation mechanism [20]. Ohtake et al. [30, 97] tested LDPE bottles exposed in aerobic soil for over 30 years and observed some evidence of biodegradation using SEM of the degraded parts. These bottles were found buried under bioactive soil. It was estimated that the period that these plastics were buried under the soil was 3237 years, as this was specied by the time at which these plastics were discarded under soil. In another study [29], sampling for buried LDPE lms was carried out in garden soil located in Japan. The samples were collected at about 10 and 50 cm depth from the surface respectively. It has been shown that LDPE lms are gradually degraded, accompanied by a molecular weight reduction caused by microbes in the soil, as opposed to other common plastics such as urea-formaldehyde resin (UF), polyvinyl chloride resin (PVC) and polystyrene resin (PS). Based on the studies of [29], it is estimated that it takes about 300 years to entirely degrade LDPE lms with thickness of 60lm (the estimation of 300 years comes from the rate of weight loss estimated from computed ratios between parts in contact with soil and parts-not-in-contact with soil in weight per unit area of the LDPE lms concealed in soil for more than 30 years [29, 30]). The rate of the weight loss then predicts complete degradation at a period of 300 years provided the rate of weight loss is

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constant. However, this estimation implies an unrealistically high rate of biodegradation for LDPE in contrast to the conventional supposition, justied with many published reports [67, 90, 98, 99 etc.] that it takes several thousand years for the LDPE (a non-degradable polymer) to be completely degraded [29]. But even with this overestimated rate (300 years), if the accumulation rate in the soil is considered, the end result is that the LDPE remains will continue to increase with time, instead of decreasing, with irreversible contamination of the soil. For many years there has been an approach to creating polymers that could eventually function as biodegradable polymers, by the addition of organic starch materials into a petrochemical product (mainly PE). Unfortunately the results obtained, suggest a number of aws to this system: The two materials (i.e. starch and polyethylene) are entirely incompatible. The properties of what was once a highly efcient and minimalist material are highly compromised [88, 100]. b. The starch has to be present in large amounts to be accessible to microorganisms. This in turn, requires the use of thicker lms and thus more PE to ascertain good mechanical properties to the composite material [101]. c. Starch-based technologies and aliphatic polyesters, are hydro-degradable and rely on microbial active environments to degrade. This is not true for polyethylene. So nally only a part of the starch of such polymers, the part that is accessible by the microorganisms can biodegrade. These materials cannot therefore be considered and labelled as biodegradable but only partially biodegradable [88]. These materials accumulate in the environment with time as pollutants and so cannot be characterized as environmental friendly ones either. a.

3. 4.

In another case biodegradation of a LDPE/starch blend is reported under controlled biologically active soil. Biodegradation was measured through the percent conversion of the carbon content from the designed biodegradable plastic to CO2 in aerobic environment.

The condition under which polyethylene is tested for possible biodegradation constitutes the key factor to the interpretation of the results obtained. Thus, in order to estimate the material life of polymers which undergo oxidative degradation, the accelerated test is used [60]. This test is based on the assumption that the oxidative degradation is an activated process (i.e. needs some external factor in order to get started). In general, it requires long extrapolation from high-temperature data to obtain the room temperature based life needed for oxidation. As far as the biodegradation is concerned however, the oxidation proceeds via an enzymatic process with very low activation energy which is the only possibility for mild conditions in the range of room temperature. Thus, it is practically impossible to apply the accelerated test to study biodegradation, especially in soil. It is necessary to carry out longterm degradation tests under model conditions which are similar to those of a real (e.g. soil) system in order to get reliable results concerning biodegradation [60].

Additives Functions of Additives Most conventional plastics contain additives to facilitate their processing and to enhance the physical characteristics of the products manufactured from them. This is also true for the degradable materials appearing in the market [46, 48, 49]. Some of the most common types of additives are process additives, stabilizers, performance additives and plasticizers [18, 32]. Additives are useful to modify polymers for three basic features [101]: They are chemically active and they react with the polymer to lead to a new chemical structure or they slow down the degradation of the polymer. They are physically active and modify the rheology, mechanical properties, optical or electrical characteristics. They may be inexpensive and simple, reduce costs (or sophisticated and expensive; depending on the application), and at the same time alter the polymer properties.

Conditional Polymers (bio?)Degradation Concerning the question of possible (bio?)degradation of polyethylene, many reports have been published claiming that PE is biodegradable. In most cases the samples used in the corresponding research projects are pre-treated or special conditions and inoculums have been used for the experiments. Several characteristic cases are summarized in Table 1 for illustrative purposes. In general it can be pointed out that: 1. In all but two cases, polyethylene was reported as biodegaradable, following however thermal pretreatment to induce thermal oxidation; this pre-treatment does not simulate real soil conditions though. In one case, biodegradation of PAH (polyaromatic hydrocarbons) is reported under extremely acidic environment.

2.

Theoretically, each additive is added into a compound to enhance a single property of the polymer to allow a precise engineering application [46, 48, 49]. They modify: Aesthetics, mechanical, thermal, electrical, optical performances.

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Table 1 Reported (bio?)degradation of polymers in literature Conditions Usage of activated sludge Bioactive soil (rather shallow) Slow rate of oxidative degradation Pre-thermally-oxidized at 55C 800 weeks (600 days) in inoculum Fragmented 44% mineralization Thermally-oxidized at 100C Carbonyl formation Accelerated Ageing. Thermal degradation caused by contact with metals Decrease in chemiluminensence intensity Increase in oxidation rates Microbial growth Erosion of the lm surface Gorghium et al. [102] Bonhomme et al. [61] 14 days Drop in molecular weight Khabbaz et al. [40] Cumulative CO2 emissions ~1700 mg CO2 (70 mg/g soil) Chiellini et al. [2] 3237 years in soil About 2/3 decrease of thickness 1 month in inoculum Not mentioned Rate or duration of degradation Reported degradation Reference Nakamura et al. [65] Ohtake et al. [29]

Material

Reported result

LDPE/starch

Partially biodegradable

LDPE

Partially biodegradable

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LDPE containing totally degradable plastic additives (TDPA) and pro-oxidants

Biodegradable

LDPE with pro-oxidants LLDPE

Environmentally Degradable

LDPE, LLDPE, HDPE, UHMWPE Pre-heated at 60C in an air oven Sterilized by UV/inoculated to simulated the effect of the 30 min] compost environment. Incubated for 6 months at 27C Incubated in the presence of in soil containing 85% of water selected microorganisms Buried in extremely acidic 28 days environment (coal runoff basin)

Thermally degradable Addition of metals

PE

Biodegradable

PAH

Biodegradable

60% mineralization CO2 production from 010% depending on the hydrocarbon Reported density ~0.96 g/cm3 35% weight loss for HDPE, 5% for LDPE, > 5% for NP Produced biomass ~300 lg/l ~7 g CO2/50 ml 1727% O2 consumption Decrease in tensile strength > 10% CO2 production

Stapleton et al. [98]

LDPE, HDPE, LLDPE

Degradable

Articial accelerated weathering 1600 h using a Xenon lamp (UV- and Xenon arc radiation) of 65000 W and 800 h using UVB lamp 0.60 W/m2 irradiance at 313 nm Controlled biologically active soil 7 months Pre-thermally oxidized in an oven 140 days 4070 and then in compost Soil mixed with 50% (w/w) 15 months at room temperature mature and 40% humidity municipal solid waste compost Photooxidized with ultraviolet radiation at solar weight lengths from Xenon lamp 1,380,000 kJ/m2 for 98.7 h 6 months

Gulmine et al. [99]

LDPE/starch (12%)

Biodegradable

Orhan et al. [103] Weiland et al. [59] Orhan et al. [104]

LDPE LLDPE

Biodegradable

LDPE/starch with pro-oxidants HDPE NP

Biodegradable

PP/ starch (blended with Mater-Bi

Partially Biodegradable

Weight loss

Morancho et al. [100].

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Table 1 continued Conditions Pre-aged thermally Changes in molecular weight. Oxidation accompanied by the production of low molar mass, oxidized fractions, which are due to their wettability and functionality, May become vulnerable to microorganisms Detected surface erosion variations in intrinsic viscosity weight loss per surface area, colonization of fungus chain scission, evolution of hydroxyl and carbonyl groups Subjected to biodegradation by a consortium of four fungi during 9 months Incubation of polyethylene with B. borstelensis (30 days, 50C) Morphological, structural, surface changes and mineralization. Manzur et al. [107] Thermally oxidized in air in an oven at two different temperatures, 55 and 70C, under dry (uncontrolled humidity) and approximately 75% relative humidity (RH, saturated NaCl solution) conditions. 100 h irradiation Buried 46 weeks in compost and culture environment Chiellini et al. [105] Rate or duration of degradation Reported degradation Reference

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Pandey et al. [106]. Physicochemical treatments thermal treatment at 105 and 150C or accelerated aging treatment Polyethylene-degrading microorganism Brevibaccillus borstelensis strain 707 (isolated from soil) Degradation of polyethylene in the presence of mannitol. Maximal biodegradation was obtained in combination with photo-oxidation. Hadad et al. [96]

Material

Reported result

PE containing pro-oxidant

Potential assimilation by microorganisms.

Ethylene-propylene copolymers (E-P copolymer), Isotactic polypropylene (i-PP), LDPE

Bioassimilation that UV-irradiated (photoirradiation can be followed of the lms was carried out by microbial attack in a accelerated weathering chamber (SEPAP 12/24) at 60C).

LDPE

Biodegradable

LDPE

Biodegradable

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The processing: moulding, extrusion etc, accuracy of shaping. The long-term behaviour: ageing (heat, sunlight, weathering, wet environment), creep, relaxation, fatigue. The cost.

Degradation and Biodegradation Related Additives General The most common types of additives used in (bio?)degradable lms are cobalt acetylacetonate, nickel or ferrous dithiocarbamate, magnesium stearate or carboxylate, styrene-butadiene copolymer, starch [70] where the incorporated amount is up to 20%, of which 7% is generally starch, which is often associated with peroxides [20, 26, 29, 53, 67, 70]. In the case of polyethylene, the degradation rate of the material in soil is independent of the nature of these additives [30]. The additives accelerate the breakdown and increase the production of oxide derivatives [53, 70]. The photodegradation can be enhanced by the addition of small levels of UV degradation promoters or photo-initiators. For example, Fe, Ni or Co chlorides or dithiocarbamates, organometallic additives, cerium based additives (Rhone-Poulenc) [108]. More or less high levels of comonomers can also be used such as Ethylene-carbon monoxide copolymer (Dow), Ecolyte masterbatches of PE, PP, PS (Enviromer Enterprise, Dow and DuPont) [101, 102, 109]. In an effort to promote possible biodegradation conditions, for well-known non-biodegradable polymers, high levels of biodegradable additives have been used. In such case, sources of nutrients for micro-organisms were used but the conventional polymer, polyethylene particularly, has not been biodegraded [101]. Only the biodegradable additives are completely biodegraded. In particular, in these cases it has been shown that: The skeleton of the conventional polymer is weak and brittle and can disappear visually (but not necessarily physically) more easily. The surface area is highly increased and promotes chemical and bacterial attacks (at unknown rate of possible (bio?)degradation, if any; refer to the controversial data described earlier). One of the most industrialized ways is the addition of starch-based materials but other biodegradable additives have also been used.

thermal stability of the system for a little variation of the temperature [2, 19]. The most active pro-oxidants are those based on metal combinations capable of yielding two metal ions of similar stability and with oxidation number differing by one unit only e.g. Mn2+/Mn3+ [19]. Thus material degrades by a free radical chain reaction involving oxygen from the atmosphere. The primary products are hydroperoxides which can either thermolyse or photolyse under the catalytic action of a pro-oxidant, leading to chain scission and the production of low molecular mass oxidation products such as carboxylic acids, alcohols, ketones and low molecular mass hydrocarbon waxes [19]. The rate of degradation depends on the type of polymer, type and amount of the additives, temperature and other conditions. As the fate of the remains of degraded polymers containing such additives in the soil is unknown, systematic research is needed in this direction. Specialties such as Addiex, Ciba EnvirocareTM and AGPTM, ECM Masterbatch Pellets by ECM Biolms, EcoSafe Biodegradable Compost, TDPA are examples of some marketed specialties (the information given below, including the suggested applications, is provided by the corresponding industries): Addiex for PE, PP and PS. AddiFlex additives are degradable, biodegradable, and/or photodegradable [110]. They are sold in pellets of masterbatches. The addition level depends on the degradation mode. Biodegradable ones are normally added to PE or PP, and eventually PS at 15% to 30%. Photodegradable ones are added at 3% level. The pellets can be fed directly into the extruders or preblended. EcoSafe Biodegradable Compost, TDPA. These additives lead to two-steps degradation by oxo-degradation in 1218 months in a landll [110]. Ciba Envirocare TM and AGPTM for PE, PP. These additives are based on thermal and/or photo-oxidation. The lms after a season of outdoor exposure are sufciently brittle to be easily mixed with the soil during ploughing [110]. ECM Masterbatch Pellets by ECM Biolms. The pellets are added at 2% to PE [110]. Limitations One major drawback of most polymers is the problem with their disposal. Since they may be resistive to degradation (depending on the polymer, additives, conditions etc), nondegradable polymers tend to accumulate in what is todays most popular disposal system, the landll. This brings questions about what effects polymers have on the environment, whether they biodegrade at all, and if they do, what is the rate of (bio?)degradation, what effect the

Pro-oxidants Pro-oxidants such as manganese soaps can be used to speed up the thermo-oxidation of the polymers. This solution is difcult to control because of the high decrease of the

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products of (bio?)degradation have on the environment, including the effects of the additives used. Regarding the additives, according to the National Industry Chemical Notication and Assessment Scheme or the EU Directive 67/548/EEC [7] a polymer in order to be (bio?)degradable: Must not contain additives that are assigned or may be assigned any of the following risk phrases (or combinations thereof): greater than 0.1% of substances classied as carcinogenic according to the approved criteria for the classication of hazardous substances by the National Industry Chemical Notication and Assessment Scheme; greater than 0.2% of any ingredient that is classied or may be classied as mutagenic or tetragenic according to the approved criteria for the classication of hazardous substances; Must have a minimum natural material or starch content of 30%. Plastic additives must not include more than 40% aromatic polyesters or other degradable plastics by weight. The hazardous material content shall be limited to one of the following internationally determined benchmarks for compostable biopolymers depicted in Table 2. Ecotoxicity: The germination rate and the plant biomass of the sample composts of plant species should be more than 90% of those from the corresponding black compost.

Tests and Standards on Biodegradability Testing Biodegradability According to Standard Testing Methods In the United States an acknowledged authority for establishing denitions, test methods and standards, is the American Society for Testing and Materials (ASTM), through its Institute for Standards Research. The European counterpart is the Comitee Europeen de Normalisation (CEN)the European Committee for Standardization. Individual European Countries have their own organizations. The International Standards Organization (ISO) aims to reconcile differences. The development of testing methods is presented in the table below (Table 3) [111]. Some of the methods used to assess biodegradability include the measurement of carbon dioxide production, as with the Sturm test and soil test. Other methods involve measurements of molecular weight and molecular weight distribution; tensile properties, weight loss; extent of fragmentation; enzyme assays; biochemical oxygen demand (BOD); and ecotoxicity, as with cress read test and earth worm test (ASTM D5338-98, ASTM 6340-98) [6]. Multiple test procedures are necessary in evaluating the biodegradability of a material because some tests are subject to false-positive interpretations, that are concluding incorrectly that degradation or biodegradation has occurred [6, 7]. For example, observed weight loss may result not from polymer degradation, but from the leaching of additives, including plasticizers. However, carbon dioxide production might result from the degradation of lowmolecular weight fraction of the polymer, with no degradation of longer chains. In another case, a large loss of material strength might come from a very small change in its chemical makeup. Strength is often disproportionately affected by the loss of additives and 90% decrease of strength can result from as little as 5% mineralization [14]. Because of its dependence on many environmental factors, the biodegradability of a plastic, or polymer in laboratory evaluations will not be relevant to all disposal environments. Some tests might show it to be potentially or
Table 3 Development of degradable methods Year Test Method Standard ISO 4892 ISO 846, ASTM G 21, ASTM D 5338 ISO 14851, ISO 14852, ISO 14855 ISO 16929, ISO 17556, ISO 20200, ISO 14853

No benchmarks have been established so far concerning biodegradation of polymers in soil.


Table 2 Internationally determined benchmarks for compostable biopolymers concerning hazardous material Chemical DIN V 54900-1 (German Standard) Limit values (mg/kg) Zn Cu Ni Cd Pb Hg Cr Mo Se As F 100 23 15 0.3 30 0.3 30 EN 13432 (EU Standard) Limit values (mg/kg) 150 50 25 0.5 50 0.5 50 1 0.75 5 100 Green Plastics (Japanese Standard) Limit values (mg/kg) 150 37.5 25 0.5 50 0.5 50 1 0.75 3.5 100

Before Photo degradable test 1995 1995~ 2001~ 2003~ Fungus erosion testing composting testing Biodegradable testing Disintegration or biodegradation

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inherently biodegradable without showing it to be actually biodegradable in a specic disposal environment (ASTM 6400-99, ASTM 5338-98, ASTM 6340-980 [6]. Criteria used in the Evaluation of Biodegradable Polymers A large number of intrinsic properties of a polymer can be measured. Some properties whilst producing absolute indicators that the polymer has undergone scission e.g. molecular weight distribution or intrinsic viscosity changes, require specialist analytical equipment but tell little of the ultimate mineralization or biodegradability of the polymer, Weight loss has limited use particularly where the polymer fragments and the integrity of the specimens are lost during the test. Mechanical property changes are difcult to interpret in relation to structural alterations although they may be sensitive to small changes in molecular weight [52] and they are applicable only before fragmentation of the samples. The test methods used for the evaluation of biodegradability are depicted in Fig. 1. Plastic bags and other products, e.g. agricultural mulching lms, made with polyethylene (PE) are appearing on the market with the claim of being degradable, or bio-, UV- or oxo-degradable, and sometimes even compostable. The underlying technology is based on

special additives (master batch) which, if incorporated into standard PE resins, are purported to accelerate the degradation of the lm products (refer to earlier sections). However this technology and the products are not new, and since their rst appearance on the market in the 80s many doubts have been expressed as to whether these products provide what they promise. Such doubts are still valid. IBAW (the international industry organisation for bioplastics and biodegradable polymers), has published a position, which outlines the questions raised by degradable PE products [7]. Compliance with EN 13432The Underlying Test Scheme for Evaluation The EU Directive on Packaging and Packaging Waste (94/ 62/EC) [92] denes requirements for packaging to be considered recoverable. The harmonized standard EN 13432 [92] amplies these requirements with respect to organic recovery and biodegradable packaging. The EN 13432 lays down laboratory test procedures for biodegradability and compostability and for the determination of potential harmful material constituents in packaging and packaging materials. Whenever a packaging product is placed on the market as degradable, conformance with the requirements of 94/62/EC is to be assessed through the

Fig. 1 Test methods for evaluating biodegradability [36]

Determine disposal route in environment Is environmental compartments part of biosphere? Select test system most appropriate to disposal route

Determine solubility and toxicity of chemical substance Is solubility >10 ppm? Apply any measurement system Are anaerobic conditions required? Modify test system to accommodate anaerobic conditions Incorporate or disposal system and CO2 measuring system

Apply test system suitably modified

Is level of biodegradation acceptable?

Is more data required?

Apply modifications to test system to encourage biodegradation (second tier of testing)

Consider long term simulation (third tier of testing)

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use of EN 13432. No PE additive or PE with special additives has yet been shown to comply with EN 13432 [92]. Certication and Labelling Required Product certication based on EN 13432 [92] and labelling through an accredited conformity assessment body are to be applied to all plastic products that are claimed to be degradable, biodegradable or compostable [92]. A responsible industry has developed an environmental self-commitment on product certication to achieve the highest possible product safety and lowest possible environmental impact. The commitment was ofcially acknowledged by the EU Commission in February 2005 [7]. Presence of Oxo-biodegradable Additives Product Safety and Ecotoxicity: The so called oxo-biodegradable additives pose several concerns regarding safety and ecotoxicity. These additives are based on ionic metals that trigger PE fragmentation. Some metal compounds used in these products are classied and labelled under the EU Directive 67/548/EEC [92] on Dangerous Substances as causing adverse effects on humans and the environment. For instance, cobalt Co(II), has been found in concentrations higher than 4,000 mg/kg in some oxobiodegradable additives [IBAW position dated 6th June 2005 on degradable PE shopping bags7]. At such high concentrations these materials are considered harmful if released into the environment, and are regulated at the workplace of plastic manufacturers and converters, since metal fumes might be released through dust or under heating [7]. During the fragmentation process however, regulated metals may be liberated into the environment with the consequence of adding (eco)toxic persistent and bio accumulative CMR substances (Carcinogenic, Mutagenic, toxic to Reproduction) [7]. The Risk of Persistency and Bio-Accumulation: It is well established that standard PE is not biodegradable [7]. It has been demonstrated in case studies that the so-called oxobiodegradable PE products may fragment into very small particles after exposure to UV light or dry heat [7]. However after fragmentation, PE is still to a large extent resistant to biodegradation and, therefore, due to the slow process, the potential of persistency in the environment and bioaccumulation of liberated regulated metals and PE fragments in organisms is high [7]. Therefore, is has been suggested that the presence of oxo-biodegradable additives in polyethylene, does not justify labelling the material as biodegradable material [70]. Littering: Oxo-biodegradable PE products have been described as a solution to littering problems, as after

trashing they supposedly decompose in the natural environment [7]. De facto such a concept promotes littering and endangers organic recovery schemes which are built up to promote sustainability [7]. Plastic Recycling Schemes: Oxo-biodegradable products endanger not only organic recovery but also recycling processes of plastics. The additives destabilise plastic recyclates of mixed origin, which may lead to a reduced value of recycled plastics. Plastic recovery and recycling schemes may not be prepared to accept products that contain additives that promote degradation [7]. Parameters Affecting the Performance of Standard Tests Studies and investigations aimed at improving the feasibility and the reproducibility of laboratory methods to assess the biodegradation of EDPs are continuously in progress. This is due to the fact that some operative difculties can arise during the performance of the tests, thus affecting the accuracy of the measurements as based on the monitoring of suited parameters of choice. and the increasing number of new and structurally different EDP based materials [54]. A relatively large number of specic problems might be encountered during the performance of tests designed to assess the extent of biodegradation as CO2 release or O2 uptake especially under solid-state conditions and in the presence of organic rich incubation media such as mature compost. On the contrary, the tests carried out in aqueous medium are considered easier to set up and generally more reproducible. Therefore, the response of a standard test could be signicantly affected by some external parameters that often are intrinsically variable (e.g. microbial inoculum) or relatively poorly addressed in the standard specications. In particular, the biodegradation kinetics of a test material under solid state conditions can be inuenced by the materials concentration in the solid medium, as well as by the nature of the microbial populations; whereas the test results might vary signicantly depending upon the test duration and the reference (positive) material designed in the standard test specications [54]. Standards for Testing Biodegradable Plastics The main international organizations that have established standards or testing methods are: American Society for Testing and Materials (ASTM) [6] European Standardisation Committee (CEN) [92] International Standards Organisation (ISO) [112] National Institute for Standards Research (ISR) (USA) [113]

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German Institute for Standardisation (DIN) [114] Organic Reclamation and Composting Association (ORCA) (Belgium) [115]. Association Francaise de Normalization (AFNOR, France) [116].

Three other bio-test methods have become ASTM Standards. They are: Standard test method for assessing the aerobic biodegradation of plastic materials in an activated sludgewaste water treatment system (D5271-92) [6]. Standard test method for determining the aerobic biodegradation of plastic materials under controlled composting conditions (D5338-93) [6]. Standard test method for determining the aerobic biodegradability of degradable plastics by specic microorganisms (D5247-92) [6].

International Standards Organization Criteria Three International Standards Organization (ISO) [112] standards have set the criteria by which European biodegradable plastics are currently assessed (additional EN standards have also been developed or are under development as discussed later on). These are: ISO 14855 (aerobic biodegradation under controlled conditions); ISO 14852 (aerobic biodegradation in aqueous environments); and ISO 15985 (anaerobic biodegradation in a high solids sewerage environment).

ISO 14855 is a controlled aerobic composting test, and ISO 14851 and ISO 14852 are biodegradability tests specically designed for polymeric materials. An important part of assessing biodegradable plastics is testing for disintegration in the form in which it will be ultimately used. Either a controlled pilot-scale test or a test in a full-scale aerobic composting treatment facility can be used. Due to the nature and conditions of such disintegration tests, the tests cannot differentiate between biodegradation and abiotic disintegration, but instead demonstrates that sufcient disintegration of the test materials has been achieved within the specied testing time.

ASTM Standards The ASTM standards have test methods that measure the intrinsic biodegradability of plastic materials designed for biodegradability, and are full-edged. These test methods measure the percent conversion of the carbon from the designed biodegradable plastic to CO2 in aerobic environment and CH4 (plus some CO2) in a anaerobic environment. The test material is the sole carbon source for the microorganism in the experiment. The two bio-test methods that apply in the presence of municipal sewer sludge, and so they do not simulate soil conditions, are: Standard Test Method for Determining the Aerobic Biodegradation of Plastic Materials in the Presence of Municipal Sewer Sludge (D5209-91) [6]. Standard Test Method for Determining the Anaerobic Biodegradation of Plastic Materials in the Presence of Municipal Sewer Sludge (D5210-91) [6].

The rst two simulate environments that are representative of waste management infrastructures such as composting and waste-water treatment system. The test methods permit the quantication of biodegradability in specic waste management infrastructures. While these test methods give a quantitative measure of biodegradability in such environments, parallel tests in real world systems need to be run to conrm and establish biodegradability. ASTM is currently developing standard practices for exposing degradable plastics to such real systems environments and reporting the resulting data [6]. The specic microorganisms test method does not represent any real world waste management infrastructure but provides a standard test method to quantify biodegradability using well-dened microbial cultures commonly present in the environment [6]. Aquatic Biodegradability: Mitigating the hazards to marine life by designing bio and photodegradable plastics that would degrade in a marine environment is one of the targets for industry. Thus, to evaluate the biodegradability potential in an aquatic environment, a Standard Practices for Exposing Plastics to a Simulated Marine and Fresh-Water Environments were developed and are now at the Society balloting stage [6]. A Standard Test Method to quantify the amount of degradation in such environments is currently being developed and will build on the two aquatic test practices discussed: A Standard Practice for Weathering of Plastics under Marine Floating Exposure [D5437-93] [6]. Composting Environment: Composting is fast becoming an important waste management strategy. Biodegradable plastics that will be compostable in an appropriate composting infrastructure are being designed. As discussed earlier, a Standard Test Method for Determining the Aerobic Biodegradation of Plastic Materials under Controlled Composting Conditions has been developed. Two Standard Practices for exposing plastics to a simulated compost environment with and without an externally heated reactor have also been developed [6]. Others: A number of other specic test methods are under various stages of development for example, a high solids anaerobic digester system, and accelerated (biologically active) landll conditions.

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EN Standards (European Committee for Normalisation) The European Committee for Normalisation (CEN) [92] established the norm standard (CEN prEN 13432) in 1999. The norm provides the European Commissions European Directive on Packaging and Packaging Waste with appropriate technical regulations and standards. This norm is a reference point for all European producers, authorities, facility managers and consumers. The standard species requirements and procedures to determine the compostability of plastic packaging materials based on four main areas, biodegradability; disintegration during biological treatment; effect on the biological treatment process; and effect on the quality of the resulting compost. Importantly, the packaging material that is intended for entering the bio-waste stream must be recognizable as biodegradable or compostable, by the end user. The strictest European standard for biodegradability is CEN 13432. This standard can apply to other packaging materials in addition to polymers, and incorporates the following tests and standards, ISO 14855; ISO 14855 (respirometric); ISO 14852; ASTM D5338-92; ASTM D5511-94; ASTM D5152-92; ASTM E1440-91; Modied OECD 207; and CEN TC 261/SC4/WG2. OK Compost Certication and Logo: The OK Compost logo can be used on the labelling of biodegradable plastics and other materials to signify that the material is 100% compostable and biodegradable. The logo is owned and managed by AVI (AIB Vincotte Inter, Brussels, Bel gium), [117], and is based on the CEN 13432 standard [92]. Compost Toxicity Tests For a comprehensive assessment of toxicity associated with compost applications, plastics can be tested on both plant and animal species. Toxicity screening of some commercial degradable plastics using cell culture testing has been reported in literature [98]. A number of polyester types were tested including a plasticized cellulose acetate, an aliphatic polyester (Bionolle), polyhydroxybutyrate-cohydroxyvalerate (BiopolTM), and polycaprolactone (TONETM polymer). Cell culture medium with serum was used as the extraction medium. The relative MTT activity of cells cultured in fresh extracts indicate that TONETM polymer (all shapes) and Bionolle (test bars and lms) are comparable to materials currently used in food with no toxic effects on cells. Plant Phytotoxicity Testing While a product may not negatively impact plant growth in the short term, over time it could become phytotoxic due to

the build-up of inorganic materials, which could potentially lead to a reduction in soil productivity. For this reason some manufacturers use plant phytotoxicity testing on the nished compost that contains degraded polymers. Phytotoxicity testing can be conducted on two classes of owering plants. These are monocots (plants with one seed leaf) and dicots (plants with two seed leafs). Representatives from both of these classes are typically used in toxicity testingsummer barley to represent monocots and cress to represent dicots. Tests involve measuring the yield of both of these plants obtained from the test compost and from control compost [98]. Animal Toxicity Test Animal testing is generally carried out using earthworms (as representative soil dwelling organisms) and Daphnia (as representative aquatic organisms). Earthworms are very sensitive to toxicants. Since earthworms feed on soil, they are suitable for testing the toxicity of compost. In the acute toxicity test, earthworms are exposed to high concentrations of the test material for short periods of time. The toxicity test is a European test (OECD guideline #207) [7, 92] in which earthworms are exposed to soil and compost in varying amounts. Following 14 days of exposure, the number of surviving earthworms is counted and weighed and the percent survival rate is calculated. Compost worms (Eisenia fetida) are used for testing the toxicity of biodegradable plastic residues. These worms are very sensitive to metals such as tin, zinc, heavy metals and high acidity. For this test worms are cleaned and accurately weighed at intervals over 28 days. The compost worm toxicity test is considered to be an accurate method. The Daphnia toxicity test can establish whether degradation products present in liquids pose any problem to surface water bodies. In the test, Daphnia are placed in test solutions for 24 h. After exposure the number of surviving organisms is counted and the percent mortality is calculated. Difference between Standards for Biodegradation and Compostability ASTM standard establishes criteria (specications) for plastics and products made from plastics to be labelled degradable, compostable and biodegradable. It establishes whether plastics and products made from plastics will compost satisfactorily, including biodegrading at a rate compared to known compostable materials. These standards are comparable to those that have been developed (since 2002) by the European Committee for Standarization (CEN) and in harmony with the Deutsches Institut f}r u Normung (DIN) standards. The main point of differentiation

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between the various international standards is the percentage of biodegradation (under physical conditions in the landll) required for compliance but also the conditions and the time. This is an important issue that is under discussion at ISO level [46]. Some of the standards that apply for degradation, biodegradation and composting of polymers are summarized in Table 4 [119].

Appendix Denitions of Degradation Processes Ageing: the process of growing old or developing the appearance and characteristics of old age; the change of properties that occurs in a material as a result of degradation

Table 4 List of standards on degradation, biodegradation and compostability No. of standard 98/710671 DC Date of publication 31/07/1998 Title Conditions Nature/Objective of the test Composting, biodegradation Evaluation parameter Application

Test scheme and evaluation criteria for the nal acceptance of packaging. New European Standard Packaging. Requirements for packaging recoverable through composting and biodegradation Test method for determining Aerobic the anaerobic biodegradation of plastic materials in the presence of municipal sewage sludge Test method for determining Aerobic the aerobic biodegradability of degradable plastic by specic microorganisms. Test method for determining Aerobic the aerobic biodegradation of plastic materials an activated sludge wastewater treatment system Test method for determining aerobic biodegradation of plastic materials under controlled composting conditions Practice for exposing plastics to a simulated compost environment. Test method for determining Anaerobic anaerobic biodegradation of plastic materials under highsolids anaerobic-digestion conditions Practice for exposing plastics to a simulated compost environment using an externally heather reactor Test method for determining Anaerobic anaerobic biodegradation of plastic materials under accelerated landll conditions Aerobic

Packaging

ASTM D 5210

01/12/1998

Biodegradation

CO2/CH4

Plastic

ASTM D 5247

01/07/1992

Biodegradability

Mw, MP (molecular weight, mechanical properties) O2

Plastic

ASTM D 5271

01/09/1993

Biodegradation

Plastic

ASTM D 5338

01/08/1999

Composting

CO2

Plastic

ASTM D 5509

01/08/1996

Composting

Plastic

ASTM D 5511

01/04/1994

Biodegradation

Plastic

ASTM D 5512

01/08/1996

Composting

Plastic

ASTM D 5526

01/11/1994

Biodegradation

Plastic

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146 Table 4 continued No. of standard ASTM D 5988 Date of publication 01/09/1996 Title Conditions Nature/Objective of the test Biodegradation in the soil

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Evaluation parameter

Application

Test method for determining aerobic biodegradation in soil of plastic materials or residual plastic materials after composting Test method for determining weight loss from plastic materials exposed to simulated municipal solid waste (MSW) aerobic compost environment

Aerobic

Plastic

ASTM D 6003

01/02/1997

Composting

Plastic

ASTM D5209

01/09/1992

Standard Test Method for Aerobic Determining the Aerobic Biodegradation of Plastic Materials in the Presence of Municipal Sewage Sludge Standard Test Method for Anaerobic Determining the Anaerobic Biodegradation of Plastic Materials in the Presence of Municipal Sewage Sludge Test method for determining Anaerobic the anaerobic biodegradation potential of organic chemicals Standard test method for determining biodegradability of materials exposed to municipal solid waste composting conditions by compost respirometry Test method for determining the stability of compost by measuring oxygen consumption Test method for biodegradation by a shake-ask die-away method

Biodegradation

Plastic

ASTM D5210

1992

Biodegradation

Plastic

ASTM E 1196

01/12/1992

Chemical and organic products Composting

ASTM D 5929

01/05/1996

ASTM D 5975

01/10/1996

Composting

O2

ASTM E 1279

1989

CEN ENV 12920 11/1997 CSA Z 218-0 (Canada) 1993

Characterization of wasteMethodology for the determination of the leaching behaviour of waste under specied conditions Test method for determining the anaerobic biodegradability of plastic materials Anaerobic Biodegradability Plastic

EN 13193 EN 13427 EN 13432

01/05/2000 01/09/2000 01/09/2000

Packaging and the environmentTerminology Packaging Requirements for the use of European Standards in the eld of packaging and packaging waste Packaging. Requirements for packaging Composting recoverable through composting and biodegradation. Test scheme and evaluation criteria for the nal acceptance of packaging Plastics. Evaluation of the action of microorganisms Qualite de leau. Selection des Biodegradability essais de biodegradabilite

Packaging Packaging Packaging

EN ISO 846 FD ISO/TR 15462

01/06/1997 1997

Plastic

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147

Water qualityEvaluation in an aqueous medium of the ultimate aerobic biodegradability of organic compoundsMethod by analysis of biochemical oxygen demand (closed bottle test)

Aerobic aquatic media

Organic composition

ISO 10708:1997

01/01/1997

Water qualityEvaluation in Aerobic an aqueous medium of the aquatic ultimate aerobic media biodegradability of organic compoundsDetermination of biochemical oxygen demand in a two-phase closed bottle test Water qualityDetermination Aquatic of the elimination and media biodegradability of organic compounds in an aqueous mediumActivated sludge simulation test Water qualityEvaluation of the ultimate anaerobic biodegradability of organic compounds in digested sludgeMethod by measurement of the biogas production Anaerobic

Total biodegradability

DBO

Organic composition

ISO 11733

2004

Biodegradability

Organic composition

ISO 11734

14/12/1995

Total biodegradability

Free biogas

Organic composition

ISO 14593:1999

15/03/1999

Water qualityEvaluation of Aerobic aquatic ultimate aerobic media biodegradability of organic compounds in aqueous mediumMethod by analysis of inorganic carbon in sealed vessels (CO2 headspace test) Biodegradable Mulching Film: soil or Test Methods And Criteria aqueous media

Total biodegradability

Analyses of inorganic carbon

Organic composition

AFNOR NF U 52-001

material characteristics, ecotoxicity, biodegradation

hazardous mulching substances lms heavy metals, organic substances, earthworms, algae, CO2

(whether degradation is due to one factor or is due to the combined action of several factors) [118]. Biodegradation: degradation that is caused by biological activity, especially by enzymatic action, (ISO/CD 16929). Biodegradation phase: the time in days from the end of the lag phase of a test until about 90% of the maximum level of biodegradation has been reached (ISO/DIS 17556). Degradation: an irreversible process leading to a signicant change of the structure of a material, typically characterized by a loss of properties (e.g. integrity,

molecular weight, structure or mechanical strength) and/or fragmentation. Degradation is affected by environmental conditions and proceeds over a period of time comprising one or more steps (ASTM D-6400.99) [6]. Disintegration: The falling apart into very small fragments caused by degradation mechanisms (ASTM D6400.99) [6]. Lag phase: the time required in days for adaptation and selection of the degrading micro-organisms to be achieved and the biodegradation degree of a chemical compound or

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organic matter has reached 105 of the theoretical maximum biodegradation derived form the theoretical amount of evolved carbon dioxide and theoretical oxygen demand (ISO/DIS 17556). Maximum level of biodegradation: the maximum biodegradation in percent a chemical compound or organic matter achieves in a test, above which no further biodegradation takes place (ISO/DIS 17556). Natural ageing: a standardized articial process for imparting the characteristics and properties of age [118]. Plateau phase: The times form the end of the biodegradation phase (maximum level of biodegradation) until the end of the test (ISO/DIS 17556). Primary Biodegradation is the alteration in the chemical structure of a substance, brought about by biological action, resulting in the loss of a specic property of that substance (EPA OPPTS 835.3110). Primary Biodegradation: Minimal transformation that alters the physical characteristics of a compound while leaving the molecule largely intact. Partial biodegradation is not necessarily a desirable property, since the intermediary metabolites formed can be more toxic than the original substrate. Therefore, mineralization is the preferred aim (EPA OPPTS 835.3110). Theoretical amount of evolved carbon dioxide: the maximum theoretical amount of carbon dioxide evolve after completely oxidizing a chemical compound calculated from the molecular formula; expressed as mg carbon dioxide evolved per mg or g test compound (ISO/DIS 17556). Theoretical oxygen demand: the maximum theoretical amount of oxygen required to oxidize a chemical compound completely calculated from the molecular formula; expressed as mg oxygen required per mg or g test compound (ISO/DIS 17556). Ultimate biodegradation (aerobic) is the level of degradation achieved when the test compound is totally utilized by microorganisms resulting in the production of carbon dioxide, water, mineral salts, and new microbial cellular constituents (biomass) (EPA OPPTS 835.3110). Ultimate Biodegradation (Complete biodegradation): Molecular cleavage must be sufciently extensive to remove biological, toxicological, chemical and physical properties associated with the use of the original product, eventually forming carbon dioxide and water (EPA OPPTS 835.3110). Ultimate biodegradation: degradation achieved when a material is totally utilized by microorganisms resulting in the production of carbon dioxide (and possibly methane in the case of anaerobic biodegradation), water, inorganic compounds, and new microbial cellular constituents (biomass or secretions or both) (ASTM D-6046.02) [6].

Weathering: the natural process under real conditions imparting the characteristics and properties of age [118]. Denitions of Materials Undergoing Various Degradation Processes Biodegradable material: a material that has the proven capability to decompose in the most common environment where the material is disposed of within 3 years through natural biological processes into non-toxic carbonaceous soil, water, carbon dioxide or methane [120]. Biodegradation is measured according to the ASTM dened standards [6]. Biodegradable material: a material for which the biodegradation process is sufcient to mineralise organic matter into carbon dioxide or methane respectively, water and biomass (ISO/CD 16929). Biodegradable plastic: a degradable plastic in which the degradation results from the action of naturally occurring microorganisms such as bacteria, fungi, and algae (ASTM D-6400.99), (ASTM D-2096.01) [6]. Biopolymer: a material that is partially comprised of natural starch additives with the characteristics of a plastic product (ASTM D-6400.99) [6]. Compostable material: a material that is biodegradable under composting conditions (ISO/CD 16929). Compostable plastic: a plastic that undergoes degradation by biological processes during composting to yield CO2, water, inorganic compounds, and biomass at a rate consistent with other known compostable materials and leave no visible, distinguishable or toxic residue (ASTM D-6400.99), (ASTM D-2096.04) [6]. Compostable plastic: plastic capable of undergoing biological decomposition in a compost site as part of an available program, such that the material is not visually distinguishable and breaks down into carbon dioxide, water, inorganic compounds, and biomass, at a rate consistent with known compostable materials (ASTM D-6002) [6]. Degradable plastic: a plastic designed to undergo a signicant change in its chemical structure under specic environmental conditions, resulting in a loss of some properties that may vary as measured by standard test methods appropriate to it (ASTM D-6400.99) [6]. Degradable plastic: a plastic designed to undergo a signicant change in it is chemical structure under specic environmental conditions resulting in a loss of some properties that may vary as measured by standard test methods appropriate to the plastic and the application in a period of time that determines its classication (ASTM D2096.01) [6]. Degradable: A material is called degradable with respect to specic environmental conditions if it undergoes degradation to a specic extent within a given time

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149 14. Grifn GJL (1994) Chemistry and technology of biodegradable polymers. Blackie Academic Professional, Chapman & Hall 15. Scott G (1975) Polym Age 6:54 16. Scott G, Wiles DM (2001) Biomacromolecules 2(3):615 17. Scott G (2000) Polym Degrad Stabil 68:1 18. Stevens ES (2002) Biocycle 43(12):42 19. Jakubowicz I (2003) Polym Degrad Stabil 80:39 20. Karlsson S, Hakkarainen M, Albertsson A-C (1997) Macromolecules 30:7721 21. Wackett L, Hershberger DC (2001) Biocatalysis and biodegradation. Microbial transformation of organic compounds. ASM Press, Washington DC 22. Barak L, Coquest Y, Halbach TR, Molina JAE (1991) J Environ Qual 20:173 23. Schmitt J, Flemming H-C (1998) Int Biodeter Biodegr 41:1 24. Albertsson A-C, Karlsson S (1988) J Appl Polymer Sci 35:1289 25. Albertsson A-C, Karlsson S (1990) Prog Polym Sci 15:177 26. Albertsson A-C, Barenstedt C, Karlsson S, Lindberg T (1995) Polymer 36:3075 27. Billingham NC, Bonora M, De Corte D (2004) Environmentally degradable plastics based on oxodegradation of conventional polyolens. Plastics Solutions Canada Inc. 28. Liu M, Horrocks AR (2002) Polym Degrad Stabil 75:485 29. Ohtake Y, Kobayashi T, Asabe H, Murakami N (1998) Polym Degrad Stabil 60:79 30. Ohtake Y, Kobayashi T, Asabe H, Murakami N, Ono K (1998) J Appl Polym Sci 70:1643 31. Orhan Y, Hrenovic J, Buyukgungor H (2004) Acta Chim Slov 51:578 32. Stevens ES (2002) Green plastics: an introduction to the new science of biodegradable plastics. Princeton University Press 33. Broska R, Rychly J (2001) Polym Degrad Stabil 72:271 34. Karlsson S, Albertsson AC (1998) Polym Eng Sci 38(8):1251 35. Goldstein N, Block D (2000) Biocycle J Compost Organ Recycl 41(8):40 36. Martin A (1994) Biodegradation and bioremediation. Academic Press Inc 37. Narayan R (1994) Proceedings: Third International Scientic Workshop on Biodegradable Plastics and Polymers; Osaka, Japan, Nov 911, 1993, Impact of Governmental Policies, Regulations, and Standards Activities on an Emerging Biodegradable Plastics Industry. In: Doi Y, Fukuda K (eds) Biodegradable plastics and polymers. Elsevier, New York, pp 261 38. Demicheli M (1996) Biodegradable plastics from renewable sources. IPTS Report, 10 39. Guides for the use of environmental marketing claims, U.S. Federal Trade Commission, Washington D.C., July, 1992 40. Khabbaz F, Albertsson A-C, Karlsson S (1999) Polym Degrad Stabil 63:127 41. Kitch D (2001) Biocycle J Compost Organ Recycl 42(2):74 42. Agamuthu P, Putri Nadzrul Faizura (2005) Waste Manage Res 23:95 43. Albertsson A-C (1980) Eur Polym J 16:623 44. Narayan R (1992) ACS Symp Ser 476 45. Rabek J (1996) Photodegradation of polymers physical characteristics and application. Springer, Germany 46. Pospsil J, Pilar J, Billingham NC, Marek A, Horak Z, Nespurek S (2006) Polym Degrad Stabil 91:417 47. Biodegradable Plastics (2002) Developments and Environmental Impacts, Nolan-ITU Pty Ltd, Prepared in association with ExcelPlas Australia, October, 2002 48. Biron M (2005) Collateral effects of additives, Part 2 Unexpected and surprising effects of specic additives, SpecialChem 49. Biron M (2005) The additives for thermoplastics: a review III Specic property enhancement, SpecialChem

measured by specic standard test methods (ASTM D-6400.99) [6]. Hydrolytically degradable plastic: a degradable plastic in which the degradation results from hydrolysis (ASTM D-2096.03) [6]. Inherently biodegradable: is a classication of chemicals for which there is unequivocal evidence of biodegradation (primary or ultimate) in a standard test of biodegradability. Requires worst possible case estimates of likely environmental concentrations and therefore further simulation tests may be required (EPA OPPTS 835.3110). Non-biodegradable: Negligible (as compared to inherently biodegradable) biotic removal of material under standard test conditions (EPA OPPTS 835.3110) Oxidatively degradable plastic: a degradable plastic in which degradation results from oxidation (ASTM D2096.03) [6]. Readily biodegradable is an arbitrary classication of chemicals which have passed certain specied screening tests for ultimate biodegradability; these tests are so stringent that it is assumed that such compounds will rapidly and completely biodegrade in aquatic environments under aerobic conditions (EPA OPPTS 835.3110). Readily biodegradable: Rapid and complete mineralization (EPA OPPTS 835.3110) Photodegradable plastic: a degradable plastic in which degradation results from the action of natural daylight UV radiation (solar weight lengths). (ASTM D-2096.02) [6]. Partially biodegradable: Blends of non-biodegradable polymers with biodegradable (usually starch) material. Biodegradation of these materials is limited to the accessible by the micro-organisms part of the biodegradable compound [6].

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