Critical Reviews in Biotechnology

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A Review of Plastic Waste Biodegradation

Ying Zheng, Ernest K. Yanful & Amarjeet S. Bassi

To cite this article: Ying Zheng, Ernest K. Yanful & Amarjeet S. Bassi (2005) A Review
of Plastic Waste Biodegradation, Critical Reviews in Biotechnology, 25:4, 243-250, DOI:
10.1080/07388550500346359

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Critical Reviews in Biotechnology, 25:243–250, 2005
Copyright
c Taylor & Francis Inc.
ISSN: 0738-8551 print / 1549-7801 online
DOI: 10.1080/07388550500346359

A Review of Plastic Waste Biodegradation

Ying Zheng and
Ernest K. Yanful ABSTRACT With more and more plastics being employed in human lives
Department of Civil and and increasing pressure being placed on capacities available for plastic waste
Environmental Engineering disposal, the need for biodegradable plastics and biodegradation of plastic
Amarjeet S. Bassi wastes has assumed increasing importance in the last few years. This review
Department of Chemical and looks at the technological advancement made in the development of more eas-
Biochemical Engineering ily biodegradable plastics and the biodegradation of conventional plastics by
The University of Western microorganisms. Additives, such as pro-oxidants and starch, are applied in syn-
Ontario, London, Ontario, thetic materials to modify and make plastics biodegradable. Recent research has
Canada
shown that thermoplastics derived from polyolefins, traditionally considered
resistant to biodegradation in ambient environment, are biodegraded follow-
ing photo-degradation and chemical degradation. Thermoset plastics, such as
aliphatic polyester and polyester polyurethane, are easily attacked by microor-
ganisms directly because of the potential hydrolytic cleavage of ester or urethane
bonds in their structures. Some microorganisms have been isolated to utilize
polyurethane as a sole source of carbon and nitrogen source. Aliphatic-aromatic
copolyesters have active commercial applications because of their good mechan-
ical properties and biodegradability. Reviewing published and ongoing studies
on plastic biodegradation, this paper attempts to make conclusions on poten-
tially viable methods to reduce impacts of plastic waste on the environment.

KEYWORDS thermoplastics, polyolefins, additive, thermoset plastics, polyester,

polyurethane.

1. INTRODUCTION
Plastics are man-made long chain polymeric molecules.30 They are widely
used, economical materials characterized by excellent all-round properties, easy
molding and manufacturing. Traditionally plastics are very stable and not read-
ily degraded in the ambient environment. As a result, environmental pollution
from synthetic plastics has been recognized as a large problem. For instance,
statistics published by the United States Environmental Protection Agency in
2003 indicated that, before recycling, approximately 236 million tons of mu-
nicipal solid waste (MSW) was generated in the United States in that year, of
which 11.3% was composed of plastics.32 Only a small fraction of this plastic
Address correspondence to Amarjeet
S. Bassi, Department of Chemical and waste (mostly soft drink and other bottles) was recovered.32 Thus the remain-
Biochemical Engineering. The ing quantity of plastic waste was required to be disposed. Most of this plastic
University of Western Ontario,
London, Ontario N6A 5B9, Canada.
waste has been accumulating in landfills. Therefore, in order to save capacity
E-mail: abassi@uwo.ca for plastic waste disposal, there is a growing interest both in the development
243
of newer, readily biodegradable plastics and in the TABLE 1 Main plastics and their applications (the list is not
exhaustive).
biodegradation of conventional plastic waste. The
present study reviews current research in these areas. Plastics Applications

Low density polyethylene Films and packaging

2. TYPES OF PLASTICS AND USAGE (LDPE), linear low density
polyethylene (LLDPE),
2.1. Types of Plastics and Properties polyvinylchloride (PVC)
for Degradation Polyethylene terephthalate Bottles, tubes, pipes,
(PET), PVC, high density insulation molding
Plastics are synthetic polymers. There are two main polyethylene (HDPE)
processes in the manufacture of synthetic polymers. Polystyrene (PS), Tanks, jugs, containers
The first involves breaking the double bond in the polypropylene (PP), PVC
original olefin by additional polymerization to form LDPE, LLDPE Bags
Polyurethane (PUR) Coating, insulation, paints,
new carbon-carbon bonds, the carbon-chain polymers.
packing
For example, the fabrication of polyolefins, such as
polyethylene and polypropylene, is based on this gen-
eral reaction. The second process is the elimination of polyethylene (LDPE), polypropylene (PP), polystyrene
water (or condensation) between a carboxylic acid and (PS) and other resins. The major classes of thermosetting
an alcohol or amine to form polyester or polyamide. plastics include polyester, one of which is polyethylene
Polyurethane is also made by this general reaction.30 terephthalate (PET), and polyurethane (PUR).6
Plastics are divided into two groups: thermoplastics Table 2 shows percentage distribution of plastic resins
and thermoset plastics.2 Thermoplastics are the prod- in terms of sales and use in 2004 in the United States,
ucts of the first kind of general reaction mentioned Canada and Mexico, published by The American Plas-
above. Thermoplastics can be repeatedly softened and tics Association.5 It is notable that 92% of plastics
hardened by heating and cooling. In thermoplastics, the employed are non-biodegradable thermoplastics. As
atoms and molecules are joined end-to-end into a series a consequence, the environmental impact caused by
of long, sole carbon chains. These long carbon chains thermoplastics, the main packaging materials, is a ma-
are independent of the others.3 This structure in which jor concern. To deal with this environmental prob-
the backbone is solely built of carbon atoms makes ther- lem related to non-biodegradable thermoplastics, re-
moplastics resistant to degradation or hydrolytic cleav- search to modify non-biodegradable thermoplastics to
age of chemical bonds. Consequently, thermoplastics biodegradable materials is of great interest. Although
are considered non-biodegradable plastics. Thermoset thermoset plastics comprise only 8% of the total
plastics are synthesized from the second kind of gen- amount of plastics,5 their susceptibility to biodegrada-
eral reaction stated above. They are solidified after being tion also raises attention. Several investigations have
melted by heating. The process of changing from the liq-
uid state to the solid state is irreversible.2 Distinguished TABLE 2 Percentage distribution of plastic resins: sales and
captive use in North America (2004) (5 adapted from American
from the linear structure of thermoplastics, thermoset Plastics Council Year End Statistics 2004).
plastics have a highly cross-linked structure.2,30 Since
Type of plastic resin Percentage distribution
the main chain of thermoset plastics is made of hetero-
atoms, it is possible that they are potentially susceptible Polypropylene (PP) 18.4%
Polyvinyl chloride (PVC) 15.8%
to be degraded by the hydrolytic cleavage of chemical
Polystyrene (PS) 6.7%
bonds such as ester bonds or amide bonds.23 High density polyethylene 17.4%
(HDPE)
2.2. Application of Plastics Low density polyethylene (LDPE) 8.2%
Linear low density polyethylene 12.1%
Thermoplastics are widely used in packaging and (LLDPE)
fabrication of bottles and films (Table 1). The ma- Other thermoplastics 12.5%
jor types of thermoplastic material include linear, low- Thermoplastics total 92.0%
density polyethylene (LLDPE), high density polyethy- Thermosets and other plastics 8.0%
Total 100%
lene (HDPE), polyvinyl chloride (PVC), low density

Y. Zheng et al. 244

been carried out on the biodegradation of thermo-set epoxidized rubber were required as compatibilizers. The
plastics such as polyurethane and are discussed later. results showed that the blends were subject to different
kinds of degradation. However, the degree of degrada-
tion was a function of the type of polymer and the
2.3. Biodegradable blend composition. The biodegradation of the poly-
Plastics—Limitations and Obstacles olefin chain was clearly observed. Therefore, with the
for Use development of starch-plastic as well as the discovery of
other additives added to synthetic plastics, biodegrad-
Table 3 shows some of the different types of
able polyolefins provide an attractive option for reduc-
biodegradable plastics being considered. New applica-
ing plastic waste in the environment.4 The following
tions based on synthetic polyester–based biodegradable
section reviews biodegradable polyolefins and specifi-
resins have been commercialized, especially in the pack-
cally examines the degradation of polyethylene (PP).
aging industry, paper coating and garbage bags. These
polyesters are made using modified polyethylene poly-
merization processes and as blends. A second–class of 3.1. Biodegradable Polyolefins
biodegradable polyesters include polylactic acid and
Traditionally, polyolefins are considered to be non-
thermoplastic starch-based polymers. These polyesters
biodegradable for three reasons. First, the hydropho-
environmentally degrade to water and carbon dioxide
bic character of polyolefins makes this material resis-
when exposed to microorganisms and water in com-
tant to hydrolysis. Secondly, the use of anti-oxidants
posting piles. A third type of biodegradable plastics in-
and stabilizers during manufacture keeps polyolefins
cludes aliphatic co-polyesters such as polyhydroxyalka-
from oxidation and biodegradation.17 Thirdly, poly-
noates or PHAs produced by bacteria. Potato, corn and
olefins have high molecular weights36 of 4000 to 28,000.
wheat starch are renewable raw materials for starch–
Therefore, to make polyolefins biodegradable, these fac-
based plastics. While a number of alternatives have
tors have to be considered. The study of Bonhomme
emerged, one of the main limitations for synthetic
et al.7 indicated that the molecular weight of biodegrad-
biodegradable polymers such as polyesters and starch–
able polyolefins must be less than 500. Accordingly,
based blends is higher cost compared to synthetic poly-
the principle of making biodegradable polyolefins in-
mers such as LDPE, PP, PS, and PET. Another serious
volves adding special additives to the synthetic poly-
obstacle is a lack of suitable infrastructure for sorting,
olefins so that the modified structures are suscepti-
recycling and composting solid wastes.
ble to photo-degradation and chemical degradation.
As a result, the long carbon chains are broken to
shorter segments and their molecular weights are re-
3. DEGRADATION OF
duced below 500. Microorganisms can then assimilate
THERMOPLASTIC POLYOLEFINS the polyolefins monomeric and oligomeric breakdown
Generally speaking, synthetic polyolefins are inert products previously derived from photo and chemical
materials whose backbones consist of only long car- degradations.7,36,39
bon chains.36 This characteristic structure makes poly- As commercial products, synthetic polyolefins resist
olefins non-susceptible to degradation by microorgan- oxidation and biodegradation because of the presence
isms. However, a comprehensive study of polyolefin of anti-oxidants and stabilizers. The use of pro-oxidant
biodegradation has shown that some microorganisms additives makes polyolefins oxo-bio-degradable. First,
could utilize polyolefins with low molecular weight.36 pro-oxidant activities can change the polyolefins’
This biodegradation always follows photo-degradation surface from hydrophobic character to hydrophilic.
and chemical degradation. Although traditional poly- Secondly, pro-oxidants can catalyze the breakdown the
olefins are non-biodegradable, their biodegradability long chain of polyolefins and produce lower molecular
is enhanced when blending with starch or other weight products either during photolysis or thermoly-
polyesters. Zuchowska et al.38 investigated the degra- sis. Jakubowicz17 studied the thermo-oxidative degra-
dation of blends of low density polyethylene (PE) or dation of polyethylene films during composting condi-
isotactic polypropylene (PP) with glycerol plasticized tions and in the presence of pro-oxidant additives. He
starch (GS). Glycerol mono-ethers, fatty alcohols or found that metal combinations were the most active

245 A Review of Plastic Waste Biodegradation

TABLE 3 Biodegradable plastics (21 adapted from Leaversuch).
Type of Names of
biodegradable plastic Applications some manufacturers Limitations for use

Synthetic polyester blends Flexible films and tubing. Dupont 1. Higher cost
(Amorphous) Properties similar to LDPE 2. Lack of infrastructure for
disposal such as composting
and recycling
Semi-crystalline polyesters Rigid Containers, packing Dupont 3. May require blending with
Aromatic-Aliphatic General purpose and Eastman, other polyesters or polymers
Copolyesters films, lawn and garden BASF to obtain desired properties
bags, netting, food wraps 4. Bacterial derived
Polylactic acid Coatings Cargill-Dow biopolymers such as
Starch based blends Films, packing, packaging Novamont PHAs will require
Polyhydroxyalkanoates Film, sheets, elastomers Proctor and more experimental
(PHAs) Gamble testing and evaluation
Polycaprolactone Films, sheets, packaging, Union Carbide,
coatings Dow Performance
Chemicals

pro-oxidants. To be active as catalysts, it is necessary of starch is too high, the mechanical properties of the
that two metal ions of similar stability be involved in material may be adversely affected. On the contrary, if
the metal combinations, and also when the two metal the amount of starch is too low, the material may not
ions are oxidized by oxidants, the oxidation number of biodegrade.9,38 For instance, an experiment was con-
the metal ion must be only one unit different from the ducted by Zuchowska et al.38 to examine properties
one before oxidation. For example, Mn (manganese) of starch blends containing 40% polyolefin and 60%
is a suitable metal participating in metal combination plasticized starch (40 PE-SG) or 50% polyolefin and
for pro-oxidant activity. As an oxidation-reduction cat- 50% plasticized starch (50 PP-SG). The results showed
alyst, two Mn2+ ions with similar stability can form that after aging in soil for four months, both samples
and would be oxidized to Mn3+ and then later reduced had a very large weight loss (ca. 55 or 43%), indicat-
to Mn2+ . Thus, when polyolefins are exposed to the ing the degradation of materials. The 40 PE-SG, with
environment, a free radical chain in the material can higher starch content, lost more weight, implying more
react with oxygen from the atmosphere and produce material was degraded. Relative changes in mechani-
hydro-peroxides that can, in turn, be hydrolyzed and cal properties showed that the tensile strength of both
photolyzed. Also the pro-oxidant catalyzes the reaction blends did not change significantly, whereas elongation
of chain scission in the polymer, producing low molec- at break changed considerably, especially in the blend
ular mass oxidation products, such as carboxylic acids, containing higher amounts of starch. The addition of
alcohols and ketones. Furthermore, peroxidation modi- starch to polyolefins modifies their structure. Therefore,
fies the material surface character from hydrophobic to in starch blends, there is a continuous starch phase that
hydrophilic. Consequently, microorganisms can access is favorable to microorganisms and is easily attacked
the material surface, bio-assimilate the low molecular by microorganisms under the catalytic action of α- and
mass, hydrophilic oxidant products and facilitate the β- amylase enzymes. Under the effect of this reaction,
biodegradation process. the continuous starch phase is removed, resulting in
Starch can also be blended into the polymers for porous polyolefin starch blends. If pro-oxidants are also
producing biodegradable polyolefins.27,28,38 However, present, an accelerated degradation of polyolefins ma-
as mentioned earlier, without the addition of a suitable trix will occur.38
pro-oxidant system, biodegradation will simply cause
the removal of starch and leave behind shorter chains
of unmodified polyolefin.
3.2. Biodegradation of Polyethylene
The amount of starch required to be added to syn- Since polyethylene (PE) is widely used as pack-
thetic polyolefins needs to be optimized. If the amount aging material (Table 2), considerable research not

Y. Zheng et al. 246

only on biodegradable polyethylene but also on inserted functional groups that were susceptible to mi-
biodegradation of polyethylene has been recently croorganisms. The experimental result showed that with
conducted.7,8,11,12,17,34 The results of these studies the fungus activity, polyethylene with a starting molec-
indicated that polyethylene was biodegraded follow- ular weight in the range of 4000 to 28,000 was de-
ing photo-degradation and/or chemical degradation. graded to units with a lower molecular weight of 500
Biodegradation of polyethylene is known to occur after three months of liquid cultivation, which indi-
by two mechanisms: hydro-biodegradation and oxo- cated the biodegradation of this polyethylene. Over-
biodegradation.7 These two mechanisms agree with all, polyethylene degradation is a combined photo- and
the modifications due to the two additives, starch bio-degradation process. First, either by abiotic oxida-
and pro-oxidant, used in the synthesis of biodegrad- tion (UV light exposure) or heat treatment, essential
able polyethylene. Starch blend polyethylene has a abiotic precursors are obtained. Secondly, selected ther-
continuous starch phase that makes the material hy- mophilic microorganisms degrade the low molar mass
drophilic and, therefore, catalyzed by amylase en- oxidation products to complete the biodegradation.7
zymes. Microorganisms can easily access, attack and
remove this part. Thus the hydrophilic polyethylene
4. DEGRADATION OF THERMOSET
with the matrix continues to be hydro-biodegraded. For
the biodegradable polyethylene synthesized by adding PLASTICS, POLYESTER AND
pro-oxidant additive, biodegradation occurs following POLYURETHANE
photo-degradation and chemical degradation. As men- Thermoset plastics, such as polyester and
tioned in section 3.1, the pro-oxidant is a metal com- polyurethane, have recently become materials of
bination. After transition metal catalyzed thermal per- considerable interest because of their potential
oxidation, biodegradation of the low molecular weight biodegradability. It was found that due to their hy-
oxidation products occurs sequentially.7,11,36 Ei-Shafei drolysable ester bonds, polyester and polyurethane are
et al.11 investigated the ability of fungi and Streptomyces biodegradable.3,14,23,24,33
strains to attack degradable polyethylene consisting
of disposed polyethylene bags containing 6% starch.
Microorganisms employed in the investigation were
4.1. Degradation of Polyesters
eight different isolated Streptomyces strains and two fungi There are two kinds of polyesters: aliphatic and aro-
Mucor rouxii NRRL 1835 and Aspergillus flavus. After matic. Their biodegradability is completely different.
ten days of heat treatment, polyethylene films were Muller et al.23 concluded that pure aromatic polyesters
incubated and shaken at 125 rpm at 30◦ C in 0.6% are quite insensitive to any hydrolytic degradation. It
yeast extract medium (pH 7.5) for Streptomyces spp. was observed that direct microbial or enzymatic at-
and in 3% yeast extract medium (pH 5.5) for fungi. tack of pure aromatic polyester was not significant.22,31
Active enzymes were detected and biodegradation of However, other research has recently claimed that aro-
polyethylene was confirmed by testing changes in me- matic polyester could be disintegrated by microbial
chanical properties, such as tensile strength and percent strains of Trichosporum and Arthrobacter in a time scale of
elongation. Yamada-Onodera et al.36 isolated a strain weeks. Some growth of Aspergillus niger was found on
of the fungus Penicillium simplicissimum YK to biode- the surface of aromatic polyesters.15 Because no con-
grade polyethylene. They also discussed pretreatment of trol samples were tested and the degradation test meth-
polyethylene before fungus cultivation to make degra- ods used were very basic, the results were considered
dation more complete. In contrast to the research done not completely convincing. On the contrary, aliphatic
by Ei-Shafei et al.11 that used polyethylene-containing polyester is considered to be susceptible to microbial
starch as a carbon source to help microorganisms grow, attack. Aliphatic polyester degradation is seen as a two-
Yamada-Onodera et al.36 investigated biodegradation of step process: the first is depolymerization, or surface
polyethylene without additives. UV light or oxidizing erosion. The second is enzymatic hydrolysis, which pro-
agents, such as a UV sensitizer, were used at the be- duces water-soluble intermediates that can be assimi-
ginning of the process to activate an inert material, lated by microbial cells.23
polyethylene. Polyethylene was also treated with ni- In order to solve the problem of aromatic polyes-
tric acid at 80◦ C for 6 days before cultivation with ter non-degradability, aliphatic-aromatic co-polyesters

247 A Review of Plastic Waste Biodegradation

were made. The idea was that by introducing aliphatic trogen source by Comamonas acidovorans.1,24 To purify
components into aromatic polyester, its hydrolytic sus- and characterize polyurethanase enzymes, the growth
ceptibility should be increased.19 Raw materials consist- of Pseudomonas chlororaphis, Comamonas acidovorans, and
ing of copolyesters of 1,4-butanediol, terephthalic acid Pseudomonas fluorescens on polyurethane has been pre-
and adipic acid (BTA-copolyesters) are preferentially viously studied Two kinds of PUase enzyme were iso-
used for commercial biodegradable copolyesters. The lated and characterized by Howard et al.14 Allen et al.3
greater the fraction of terephthalic acid, the lower the and Vega et al.33 These were shown to be a cell-associated
rate of biodegradation of the copolyesters. In biodegra- membrane bound PU-esterase and an extra-cellular PU-
dation assaying of copolyesters, Thermomonospora fusca esterase. An investigation of the action of these two en-
DSM43793 was used. Copolyester has been observed zymes during the polyurethane biodegrading is quite
to be degraded in mineral media within days,20 and helpful for an increased understanding of the mecha-
films, approximately 90-µ m thick, were totally disinte- nism of polyurethane biodegradation. These two en-
grated within 7 days on agar plates at 55◦ C. A detailed zymes play different roles in polyurethane biodegra-
analysis of the intermediate and final products from dation. The membrane bound PU-esterase provides
the degradation of the commercial, aliphatic-aromatic cell-mediated access to the hydrophobic polyurethane
copolyester, Ecoflex, was undertaken by Witt et al.35 surface. Then the extracellular PU-esterase sticks on
using GC-MS measurements. Similar to the process of the surface of the polyurethane. Under these enzy-
aliphatic polyester degradation from depolymerization, matic actions, bacteria could adhere to the surface of
aromatic and aliphatic oligomers are intermediates that polyurethane and hydrolyze PU substrate to metabo-
are, at least, slightly water-soluble and can be metab- lites. Results obtained by Nakajima-Kambe et al.24
olized by microorganisms. However, final degradation and Howard et al.14 indicate that the polyurethane
of longer aromatic oligomers has not been achieved sig- biodegradation was due to the hydrolysis of ester
nificantly. This aspect needs further study. bonds.
In an experimental study conducted by the authors
of this review to obtain a simple culture medium for en-
4.2. Degradation of Polyurethane gineering application, the effects of YES (Yeast extract
Polyurethane (PUR) is commonly utilized as a con- salts) medium components on polyurethane (Impranil
stituent material in many products including furni- DLN) biodegradation by Pseudomonas chlororaphis were
ture, coating, construction materials, fibers, and paints. investigated.37 The results showed that Pseudomonas
Structurally, PUR is the condensation product of chlororaphis could grow and degrade Impranil DLN as a
polyisocyanate and polyol having intramolecular ure- sole carbon and nitrogen source in the modified YES
thane bonds (carbonate ester bond, -NHCOO-).29 medium with no additional carbon and nitrogen source,
The urethane bond in PUR has been reported to be yeast extract, NH4 Cl and gelatin. However, the bacte-
susceptible to microbial attack.25 The hydrolysis of ria grew much better and degraded more Impranil DLN
ester bonds in PUR is postulated to be the mecha- in the YES medium with the addition of gelatin than
nism of PUR biodegradation. The breakdown products in the one without gelatin, indicating some induction
of the biodegradation are derived from polyester seg- effects may have occurred as a result of the presence
ment in PUR when ester bonds are hydrolyzed and of the gelatin. After 10 days of incubation, the amount
cleaved.25 of polyurethane degraded was about 50%, and bacterial
Three types of PUR degradation have been identified concentration reached the maximum of 1010 cfu/mL.
in literature: fungal biodegradation, bacterial biodegra- Additionally, FTIR spectroscopy was used to confirm
dation and degradation by polyurethanase enzymes.13 that the mechanism of polyurethane biodegradation
For example, four species of fungi, Curvularia sene- was the hydrolysis of the ester bond in polyurethane.
galensis, Fusarium solani, Aureobasidium pullulans and The decrease of the ratio of ester bond over ether
Cladosporium sp, were obtained from soil and found to bond was also approximately 50%, which agreed with
degrade ester-based polyurethane.10 Kay et al.18 isolated the measured amount of polyurethane degraded. These
and investigated 16 different bacteria in their ability findings have potential benefits in future studies on
to degrade PUR. In another comprehensive study in PUR biodegradation in landfills or in other plastic waste
Japan, PUR was biodegraded as a sole carbon and ni- treatment processes.

Y. Zheng et al. 248

 4.3. Degradation of ACKNOWLEDGEMENTS
Polyhydroxyalkanoates Funding for the research was provided by Individ-
Bacteria produce polyhydroalkanoates as energy stor- ual Discovery Grants from the Natural Sciences and
age materials. A good example of this is polyhy- Engineering Research Council of Canada awarded to
droxybutyrate (PHB), which is made by numerous Dr. Ernest Yanful and to Dr. Amarjeet Bassi.
microorganisms.26 PHAs are easily metabolized. The
enzymes responsible for the biodegradation, PHA de-
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